CN109205651A - A kind of preparation method of ultra-fine porous hollow calcium carbonate - Google Patents
A kind of preparation method of ultra-fine porous hollow calcium carbonate Download PDFInfo
- Publication number
- CN109205651A CN109205651A CN201811307368.7A CN201811307368A CN109205651A CN 109205651 A CN109205651 A CN 109205651A CN 201811307368 A CN201811307368 A CN 201811307368A CN 109205651 A CN109205651 A CN 109205651A
- Authority
- CN
- China
- Prior art keywords
- carbonate
- calcium
- product
- ultra
- porous hollow
- 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.)
- Pending
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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of preparation methods of ultra-fine porous hollow calcium carbonate, it is to obtain removal of impurities filtrate, as raw material, cleaner to be added to handle raw material containing calcium wasting liquid, then it is reacted with the chemical precipitation method filtrate that will clean with carbonate solution, obtains ultra-fine porous hollow calcium carbonate.The ultra-fine porous hollow calcium carbonate partial size of the method for the present invention preparation is small, and large specific surface area, spherical rounding, performance is good, and the raw material of use is to contain calcium wasting liquid, at low cost.
Description
Technical field
The present invention relates to a kind of preparation method of calcium carbonate, especially a kind of preparation side of ultra-fine porous hollow calcium carbonate
Method.
Background technique
Porous calcium carbonate does not have toxicity due to specific surface with higher and porosity, at present in pharmaceutical carrier, loading
Large biological molecule, polymerizing template, biomimetic mineralization, chromatography, medicament slow release, super hydrophobic surface building etc. have to answer extensively
With receiving more and more attention.
Yang Hui etc. will be using n-hexane as dispersed phase, and water is continuous phase, and Tween-80 is emulsifier, and calcium chloride and sodium carbonate are
Raw material, the method combined using emulsion method with precipitation reaction are prepared for ultra-fine porous calcium carbonate microballoon (Yang Hui, Li Huan mono-
Preparation method [P] Chinese Patent Application No. of the ultra-fine porous calcium carbonate microballoon of kind: 201310146254.X).Strongly fragrant equality is with chlorination
Calcium and ammonium hydrogen carbonate are raw material, and sulfuric acid is crystal controlling agent, and using liquid carbonization, it is porous super less than 1 μm to be prepared for partial size
Thin calcium carbonate (Yu Ping, Yu Wenliang, room ancient cooking vessel industry Ultra-fine Calcium Carbonate with Porosity preparation research [J] chemistry world, 2006,
(12): 720-722,711,716.).For Zhang Tenglong etc. using sodium carbonate and calcium nitrate as raw material, kayexalate is living for surface
Property agent, is prepared for even porous calcium carbonate microparticle (Zhang Tenglong, Pang Yichuan, Feng that partial size is about 1.2 μm in room temperature aqueous solution
The simple preparation of outstanding porous calcium carbonate particle and its pattern control [J] colleges and universities chemical engineering journal, 2015,29 (2): 377-
381.)。
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of ultra-fine porous hollow calcium carbonate.The method of the present invention technique letter
Single, strong operability, production cost is low, is suitble to large-scale industrial production, and the ultra-fine porous hollow calcium carbonate partial size of preparation is small, than
Surface area is big, spherical rounding；The raw material of use is containing calcium wasting liquid, and raw material is cheap and easy to get, it can be achieved that the recycling containing calcium wasting liquid.
Technical solution of the present invention: a kind of preparation method of ultra-fine porous hollow calcium carbonate, it is to be former containing calcium wasting liquid
Material, adds cleaner to carry out removal of impurities processing to raw material, obtains removal of impurities filtrate, then will removal of impurities filtrate and carbonate with chemical precipitation method
Solution is reacted, and ultra-fine porous hollow calcium carbonate is obtained；The following steps are included:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid for 1~
The ratio of 10:1 is added to after containing 10~60min of cleaner solution & stir that concentration is 2~40wt% is added in calcium wasting liquid
The ammonia spirit that the sodium hydroxide solution or concentration that concentration is 1~20wt% are 5~28wt%, the pH value containing calcium wasting liquid is transferred to
8~11, continue 10~60min of stirring, filters, must clean filtrate, i.e. A product；
It b, is that the measurement carbonate of 1:1~2 is water-soluble by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product
Liquid；Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 40~80r/min, while being added into stirred tank two/
One A product and the carbonate aqueous solution of half stir 10~30min, obtain B product；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 800~5000:1, continues stirring 20
~60min, then remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously, continue to stir 30-150min,
Obtain C product；The concentration of the carbonate aqueous solution is 0.1~1.5molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In the preparation method of ultra-fine porous hollow calcium carbonate above-mentioned, described contains calcium wasting liquid；It is with hydrochloric acid method or nitric acid
Method decomposing rock phosphate with hydrogen simultaneously produces phosphoric acid, calcium dihydrogen phosphate, calcium phosphate, calcium ammonium nitrate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphoric acid hydrogen
The calcium content generated after calcium is 0.2~2.0molL- 1Waste liquid.
In the preparation method of ultra-fine porous hollow calcium carbonate above-mentioned, the cleaner；Be hydrogen peroxide, vulcanized sodium,
One or more of potassium sulfide or ammonium sulfide.
In the preparation method of ultra-fine porous hollow calcium carbonate above-mentioned, the carbonate；Be sodium bicarbonate, sodium carbonate,
One or more of ammonium hydrogen carbonate, ammonium carbonate, saleratus or potassium carbonate.
In the preparation method of ultra-fine porous hollow calcium carbonate above-mentioned, the setting agent；It is polyvinylpyrrolidone, ten
One or more of six alkyl trimethyl ammonium bromides, dithizone, aminotriacetic acid or 8-hydroxyquinoline.
The utility model has the advantages that compared with the prior art, the present invention is with hydrochloric acid method or nitrate method decomposing rock phosphate with hydrogen and produces phosphoric acid, phosphorus
After acid dihydride calcium, calcium ammonium nitrate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or calcium monohydrogen phosphate is raw material containing calcium wasting liquid, adds cleaner pair
Raw material carries out removal of impurities processing, and setting agent is then added, and is reacted using the chemical precipitation method filtrate that will clean with carbonate solution,
Obtain ultra-fine porous hollow calcium carbonate.Simple process, strong operability, production cost is low, is suitble to large-scale industrial production, uses
The raw material calcium wasting liquid that contains cheap and easy to get makees raw material, can make the recycling containing calcium wasting liquid.The ultra-fine porous air of the method for the present invention preparation
Heart calcium carbonate shape rounding, partial size be 300~500nm, 100~200nm of wall thickness, specific surface area be 80~120m2·g-1。
Specific embodiment
Embodiment 1.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, comprising the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 5:1
Ratio to containing in calcium wasting liquid be added concentration be 25wt% cleaner solution & stir 35min after, adding concentration is
PH value containing calcium wasting liquid is transferred to 8~11 by the sodium hydroxide solution of 15wt%, continues to stir 35min, and filtering, must clean filtrate,
That is A product；
It b, is that 1:1.5 measurement carbonate is water-soluble by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product
Liquid；Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 60r/min, while half being added into stirred tank
The carbonate aqueous solution of A product and half stirs 20min, obtains B product；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 3000:1, continues to stir 40min,
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously again, continues to stir 90min, obtains C product；The carbon
The concentration of acid salt aqueous solution is 0.12molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method or nitrate method decomposing rock phosphate with hydrogen and to produce the calcium content generated after phosphoric acid containing calcium wasting liquid
For 1.5molL- 1Waste liquid；
The present embodiment is using hydrogen peroxide as cleaner, and sodium carbonate is carbonate, polyvinylpyrrolidone is setting agent.
Embodiment 2.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, comprising the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 1:1
Ratio to containing in calcium wasting liquid be added concentration be 40wt% cleaner solution & stir 60min after, adding concentration is
PH value containing calcium wasting liquid is transferred to 8~11 by the ammonia spirit of 20wt%, continues to stir 60min, filtering, must clean filtrate, i.e. A
Product；
It b, is that 1:1 measures carbonate aqueous solution by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product；
Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 80r/min, while the A product of half are added into stirred tank
With the carbonate aqueous solution of half, 30min is stirred, B product are obtained；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 5000:1, continues to stir 60min,
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously again, continues to stir 150min, obtains C product；The carbon
The concentration of acid salt aqueous solution is 1.5molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method decomposing rock phosphate with hydrogen and to produce the calcium content generated after calcium monohydrogen phosphate and be containing calcium wasting liquid
2.0mol·L- 1Waste liquid.
For the present embodiment using vulcanized sodium as cleaner, sodium carbonate is carbonate, cetyl trimethylammonium bromide and dithizone
For cleaner.
Embodiment 3.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, comprising the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 10:
For 1 ratio to after containing the cleaner solution & stir 60min that concentration is 2wt% is added in calcium wasting liquid, adding concentration is 5wt%
Ammonia spirit, the pH value containing calcium wasting liquid is transferred to 8~11, continue stir 10min, filtering, must clean filtrate, i.e. A product；
It b, is that 1:2 measures carbonate aqueous solution by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product；
Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 40r/min, while the A product of half are added into stirred tank
With the carbonate aqueous solution of half, 10min is stirred, B product are obtained；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 800:1, continues to stir 20min, then
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously, continues to stir 30min, obtains C product；The carbonic acid
The concentration of saline solution is 0.1molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method decomposing rock phosphate with hydrogen and to produce the calcium content generated after ammonium hydrogen phosphate and be containing calcium wasting liquid
0.2mol·L- 1Waste liquid.
Potassium sulfide is cleaner in the present embodiment, and ammonium hydrogen carbonate is carbonate；Dithizone is setting agent.
Embodiment 4.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, comprising the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 1:1
Ratio to containing in calcium wasting liquid be added concentration be 30wt% cleaner solution & stir 10min after, add concentration be 8wt%
Sodium hydroxide solution, the pH value containing calcium wasting liquid is transferred to 8~11, continue stir 10min, filtering, must clean filtrate, i.e. A product；
It b, is that 1:2 measures carbonate aqueous solution by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product；
Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 40r/min, while the A product of half are added into stirred tank
With the carbonate aqueous solution of half, 10min is stirred, B product are obtained；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 800:1, continues to stir 20min, then
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously, continues to stir 30min, obtains C product；The carbonic acid
The concentration of saline solution is 0.1molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method decomposing rock phosphate with hydrogen and to produce the calcium content generated after calcium dihydrogen phosphate and be containing calcium wasting liquid
1.6mol·L- 1Waste liquid
Ammonium sulfide and vulcanized sodium are cleaner in the present embodiment, and ammonium carbonate and sodium carbonate are carbonate；Aminotriacetic acid is
Setting agent.
Embodiment 5.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, comprising the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 8:1
Ratio to containing in calcium wasting liquid be added concentration be 35wt% cleaner solution & stir 58min after, adding concentration is
PH value containing calcium wasting liquid is transferred to 8~11 by the sodium hydroxide solution of 18wt%, continues to stir 28min, and filtering, must clean filtrate,
That is A product；
It b, is that 1:1.8 measurement carbonate is water-soluble by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product
Liquid；Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 70r/min, while half being added into stirred tank
The carbonate aqueous solution of A product and half stirs 25min, obtains B product；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 4000:1, continues to stir 50min,
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously again, continues to stir 140min, obtains C product；The carbon
The concentration of acid salt aqueous solution is 0.4molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method decomposing rock phosphate with hydrogen and to produce the calcium content generated after calcium ammonium nitrate and be containing calcium wasting liquid
2.0mol·L- 1Waste liquid.
Hydrogen peroxide and vulcanized sodium are cleaner in the present embodiment, and ammonium hydrogen carbonate and ammonium carbonate are carbonate, dithizone and
Aminotriacetic acid is setting agent.
Embodiment 6.
A kind of preparation method of ultra-fine porous hollow calcium carbonate, includes the following steps:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 4:1
Ratio to containing in calcium wasting liquid be added concentration be 20wt% cleaner solution & stir 20min after, add concentration be 8wt%
Ammonia spirit, the pH value containing calcium wasting liquid is transferred to 8~11, continue stir 20min, filtering, must clean filtrate, i.e. A product；
It b, is that 1:1.3 measurement carbonate is water-soluble by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product
Liquid；Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 50r/min, while half being added into stirred tank
The carbonate aqueous solution of A product and half stirs 15in, obtains B product；
C, in A product: the mass ratio of setting agent is that setting agent is added into B product in the ratio of 900:1, continues to stir 40min, then
Remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously, continues to stir 50min, obtains C product；The carbonic acid
The concentration of saline solution is 0.1molL- 1；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
In step a is with hydrochloric acid method decomposing rock phosphate with hydrogen and to produce the calcium content generated after calcium phosphate and be containing calcium wasting liquid
1.0mol·L- 1Waste liquid.
Hydrogen peroxide and ammonium sulfide are cleaner in the present embodiment, and potassium carbonate and sodium carbonate are carbonate, polyvinyl pyrrole
Alkanone is setting agent.
Claims (5)
1. a kind of preparation method of ultra-fine porous hollow calcium carbonate, it is characterised in that: it is, as raw material, to add removal of impurities containing calcium wasting liquid
Agent carries out removal of impurities processing to raw material, obtains removal of impurities filtrate, is then carried out removal of impurities filtrate with carbonate solution with chemical precipitation method
Reaction, obtains ultra-fine porous hollow calcium carbonate；The following steps are included:
A, be within the scope of 20~40 DEG C, by cleaner in reaction temperature: the total moles ratio of calcic heavy metal in waste liquid is 1~10:1
Ratio to containing in calcium wasting liquid be added concentration be 2~40wt% 10~60min of cleaner solution & stir after, add concentration
The ammonia spirit that sodium hydroxide solution or concentration for 1~20wt% are 5~28wt%, the pH value containing calcium wasting liquid is transferred to 8~
11, continue 10~60min of stirring, filters, must clean filtrate, i.e. A product；
It b, is that 1:1~2 measures carbonate aqueous solution by the ratio between molal quantity of carbonate in the molal quantity and carbonate of calcium in A product；
Under the conditions of reaction temperature is 20~40 DEG C and mixing speed is 40~80r/min, while half being added into stirred tank
A product and half carbonate aqueous solution, stir 10~30min, obtain B product；The concentration of the carbonate aqueous solution is 0.1
~1.5molL- 1；
C, in A product: the mass ratio of setting agent be 800~5000:1 ratio setting agent is added into B product, continue stirring 20~
60min, then remaining A product and remaining carbonate aqueous solution are added into stirred tank simultaneously, continue to stir 30-150min, obtains C
Product；
D, C product filter, and wash, dry, obtain ultra-fine porous hollow calcium carbonate.
2. the preparation method of ultra-fine porous hollow calcium carbonate as described in claim 1, it is characterised in that: described contains calcium wasting liquid
It is with hydrochloric acid method or nitrate method decomposing rock phosphate with hydrogen and to produce phosphoric acid, calcium dihydrogen phosphate, calcium phosphate, calcium ammonium nitrate, ammonium hydrogen phosphate, phosphorus
The calcium content generated after acid dihydride ammonium or calcium monohydrogen phosphate is 0.2~2.0molL- 1Waste liquid.
3. the preparation method of ultra-fine porous hollow calcium carbonate as described in claim 1, it is characterised in that: the cleaner is
One or more of hydrogen peroxide, vulcanized sodium, potassium sulfide or ammonium sulfide.
4. the preparation method of ultra-fine porous hollow calcium carbonate as described in claim 1, it is characterised in that: the carbonate is
One or more of sodium bicarbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, saleratus or potassium carbonate.
5. the preparation method of ultra-fine porous hollow calcium carbonate as described in claim 1, it is characterised in that: the setting agent is
One of polyvinylpyrrolidone, cetyl trimethylammonium bromide, dithizone, aminotriacetic acid or 8-hydroxyquinoline with
On.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811307368.7A CN109205651A (en) | 2018-11-05 | 2018-11-05 | A kind of preparation method of ultra-fine porous hollow calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811307368.7A CN109205651A (en) | 2018-11-05 | 2018-11-05 | A kind of preparation method of ultra-fine porous hollow calcium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109205651A true CN109205651A (en) | 2019-01-15 |
Family
ID=64995081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811307368.7A Pending CN109205651A (en) | 2018-11-05 | 2018-11-05 | A kind of preparation method of ultra-fine porous hollow calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109205651A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346254A (en) * | 2020-03-16 | 2020-06-30 | 广东翔龙科技股份有限公司 | Novel pore-assisting agent used in urine retention and preparation process thereof |
| TWI736397B (en) * | 2020-08-20 | 2021-08-11 | 財團法人工業技術研究院 | Hollow calcium carbonate microspheres and method for preparing the same |
| KR102444775B1 (en) * | 2021-07-20 | 2022-09-19 | (주)케이와이텍 | Manufacturing method of precipitated calcium carbonate using waste concrete powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104495901A (en) * | 2014-12-10 | 2015-04-08 | 贵州省冶金化工研究所 | Method for preparing needle-like calcium carbonate |
| CN105502461A (en) * | 2014-09-09 | 2016-04-20 | 天津工业大学 | Hollow calcium carbonate microsphere preparation method |
-
2018
- 2018-11-05 CN CN201811307368.7A patent/CN109205651A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502461A (en) * | 2014-09-09 | 2016-04-20 | 天津工业大学 | Hollow calcium carbonate microsphere preparation method |
| CN104495901A (en) * | 2014-12-10 | 2015-04-08 | 贵州省冶金化工研究所 | Method for preparing needle-like calcium carbonate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346254A (en) * | 2020-03-16 | 2020-06-30 | 广东翔龙科技股份有限公司 | Novel pore-assisting agent used in urine retention and preparation process thereof |
| TWI736397B (en) * | 2020-08-20 | 2021-08-11 | 財團法人工業技術研究院 | Hollow calcium carbonate microspheres and method for preparing the same |
| KR102444775B1 (en) * | 2021-07-20 | 2022-09-19 | (주)케이와이텍 | Manufacturing method of precipitated calcium carbonate using waste concrete powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105498707B (en) | A kind of preparation method and application of modified graphene oxide/Chitosan Composites | |
| CN109205651A (en) | A kind of preparation method of ultra-fine porous hollow calcium carbonate | |
| CN104772113B (en) | A kind of graphene/montmorillonite nano-composite material and preparation method and application | |
| CN105645545B (en) | A kind of preparation method and applications of ferric-polysilicate salt coagulant | |
| CN105668856B (en) | A kind of processing method of heavy metal-containing waste water | |
| CN105622960B (en) | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application | |
| CN107519846A (en) | A kind of graphene/silicon dioxide Pt/Polypyrrole composite material and preparation method and application | |
| CN108101307A (en) | A kind of textile printing and dyeing wastewater processing method | |
| CN105883886B (en) | A kind of method that high-purity αsemiwatergypsum powder is prepared using salt chemical engineering accessory substance | |
| CN107983295B (en) | Core-shell structure iron-copper bi-metal material and its preparation method and application | |
| CN105056899B (en) | A kind of adsorbent that can be used for processing waste water containing dye and its preparation and application | |
| CN110205502A (en) | A kind of method that use adsorbent containing aluminium removes fluorine in lepidolite ore neutrality leachate | |
| CN106423272A (en) | Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof | |
| CN110129561A (en) | A method of using fluorine in modified bentonite adsorbent removal lepidolite ore neutrality leachate | |
| CN109046403A (en) | A kind of regeneration method of useless mercuric chloride catalyst | |
| CN104743606B (en) | Metatitanic acid purification process | |
| CN102965455A (en) | Method for preparing basic chromium sulfate tanning liquor by using tanning chromium sludge | |
| CN209010284U (en) | A kind of fluorine-containing waste acid recycling system | |
| CN106732413A (en) | A kind of preparation method and applications that starch conversion is obtained de-fluoridation adsorbent | |
| CN109731548A (en) | A kind of active carbon/zirconium-manganese oxide composite material and the preparation method and application thereof | |
| CN107185502B (en) | Utilize Tea Saponin-redox graphene composite material processing heavy metal wastewater thereby method | |
| CN105645546B (en) | A kind of efficient emulsifiable oil waste water coagulant special and preparation method thereof | |
| CN108101260A (en) | A kind of processing method of cobalt acid lithium production waste water | |
| CN106745984A (en) | A kind of processing method to phosphonium flame retardant waste water | |
| CN108178239A (en) | A kind of preparation method of stability and high efficiency heavy metal treatment agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190115 |