CN105543959A - Method for synthesizing calcium carbonate nanowhiskers based on potassium biphthalate and potassium sulfate - Google Patents
Method for synthesizing calcium carbonate nanowhiskers based on potassium biphthalate and potassium sulfate Download PDFInfo
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- CN105543959A CN105543959A CN201511022953.9A CN201511022953A CN105543959A CN 105543959 A CN105543959 A CN 105543959A CN 201511022953 A CN201511022953 A CN 201511022953A CN 105543959 A CN105543959 A CN 105543959A
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- calcium carbonate
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- potassium sulfate
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention relates to a method for preparing calcium carbonate nanowhiskers by utilizing binary complex crystal-form control agent of potassium biphthalate and potassium sulfate. According to the preparation method, the calcium carbonate nano-whiskers are prepared by adopting calcium hydroxide slurry as a raw material and a mixture of potassium biphthalate and potassium sulfate as the binary complex crystal-form control agent through a carbon dioxide carbonization method. The method is characterized in that the binary complex crystal-form control agent of potassium biphthalate and potassium sulfate is utilized to effectively control synthesis of the calcium carbonate nano-whiskers; and filtrate containing potassium biphthalate and potassium sulfate is reclaimed and recycled. The calcium carbonate nano-whiskers have the characteristics of high purity, high length-diameter ratio, high quality and the like. Furthermore, the preparation process has the advantages of simple method, short synthesis cycle and the like, is easy to operate, and is suitable for large-scale production of calcium carbonate nano-whiskers.
Description
Technical field
The invention belongs to aragonite calcium carbonate nano whisker field, be specifically related to a kind of method utilizing binary compound chemical additives to prepare calcium carbonate nano whisker.
Technical background
Calcium carbonate crystal whisker is a kind of white non-toxic, odorlessness, pressed powder in puffy.According to the different performance of calcium carbonate crystal whisker, calcium carbonate crystal whisker has a wide range of applications in fields such as plastics, coating, rubber, building, automobile, electron devices.
So far, the synthetic method of calcium carbonate crystal whisker mainly contains: (1) carbonation method; (2) soluble calcium salt and manufacture of carbonates method; (3) Ca (HCO
3)
2thermal degradation method method; (4) ureal antigen; (5) sol-gel method; (6) high-gravity reactive precipitation; (7) electrochemical process etc.
Such as, Chinese patent CN1800451A discloses a kind of preparation method of calcium carbonate crystal whisker, provide a kind of high molecular weight water soluble polymer and rare earth ion of utilizing to the control synthesis of calcium carbonate crystal whisker and surface modification, adopt hydrothermal method, by urea pyrohydrolysis calcium carbonate crystal whisker.But the method complex operation, long reaction time, reactor pressure is large, and interpolation rare earth ion causes the deficiencies such as expensive raw material price, and the method for the whisker of obtained calcium carbonate should not be promoted.
As for CO
2the carbonation method participated in, its equipment is simple, easy operation control and easily realize the advantages such as industrialization, has the value that large-scale industrial is produced.In existing carbonating research report, in order to the mass-producing realizing calcium carbonate crystal whisker controls synthesis, need some processing condition are regulated and controled, comprise temperature of reaction, stirring velocity, CO
2pass into speed etc., particularly usually introduce some calcium carbonate crystal seed or chemical additives etc.Common calcium carbonate crystal whisker chemical additives comprises MgCl
2(CN1552959A, CN1641077A, CN101935865A, CN101684570A), phosphoric acid and soluble phosphate (CN1442363A) etc.Although introduce the large-scale production that this type of chemical additives can realize calcium carbonate crystal whisker, the calcium carbonate crystal whisker in bibliographical information is micron-scale, fails to reach Nano grade.Therefore, how to realize the large-scale production of the calcium carbonate crystal whisker of nano-scale, remain one of emphasis being worth research in calcium carbonate field.
Summary of the invention
The present invention is intended to utilize the method for the binary compound chemical additives of Potassium Hydrogen Phthalate and potassium sulfate to prepare the calcium carbonate nano whisker of high-quality.Technical problem to be solved is to provide a kind of preparation method increasing whisker output, easy and simple to handle, the measured calcium carbonate nano whisker of matter.
Technical solution problem of the present invention adopts following technical scheme: preparation Potassium Hydrogen Phthalate and potassium sulfate binary compound chemical additives (strength of solution scope is 0.5% ~ 20%), be then uniformly mixed with calcium hydroxide slurry.CO is passed at 20 ~ 90 DEG C
2gas carries out carbonation reaction.When this pH value of solution reaches near 7, stop carbonation reaction.Water flowing is washed, filter, dry operations such as (50 ~ 120 DEG C), can obtain calcium carbonate nano crystal whisker products.
Compared with the prior art, novelty of the present invention is embodied in:
1, the present invention is with the mixture of Potassium Hydrogen Phthalate and potassium sulfate for binary compound chemical additives, successfully utilizes CO
2carbonic acid acidization has synthesized calcium carbonate nano whisker.
2, the calcium carbonate crystal whisker that the present invention obtains has stuctures and properties and stablizes, and has the features such as purity is high, crystal formation good, length-to-diameter ratio is high, quality better.
3, reaction time of the present invention is short, and easy handling is less demanding to reaction conditions, and the large-scale industrial that can realize calcium carbonate nano whisker is produced.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of calcium carbonate nano whisker prepared by Potassium Hydrogen Phthalate and potassium sulfate binary compound chemical additives (concentration is 5%).
Fig. 2 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by Potassium Hydrogen Phthalate and potassium sulfate binary compound chemical additives (concentration is 10%).
Fig. 3 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by Potassium Hydrogen Phthalate and potassium sulfate binary compound chemical additives (concentration is 13%).
Embodiment 1
Measure the Ca (OH) of 2.6L exquisiteness
2slurries (mass percent concentration is 10%), put into the stainless steel cauldron that volume is 5L.Then, the solution (based on the quality of the calcium carbonate that calcium hydroxide complete reaction generates, usage quantity is 5%) containing Potassium Hydrogen Phthalate and potassium sulfate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 600mLmin to gas
-1), raise carbonation temperature to 80 DEG C.Treat that the pH of feed liquid is down to about 7, stopped reaction.Next, by steps such as filtration, washings, the calcium carbonate filter cake obtained is dried at 110 DEG C, can prepare calcium carbonate nano crystal whisker products.Finally, scanning electron microscope (SEM) is adopted to carry out the test of the constitutional features such as pattern, size of calcium carbonate product, as shown in Figure 1.This product has obvious one dimension Nano structure feature, and its diameter is 20 ~ 30nm, and length is 400 ~ 500nm, thus has larger length-to-diameter ratio 15 ~ 20.
Embodiment 2
Measure the Ca (OH) of 3.9L exquisiteness
2slurries (mass percent concentration is 8%), put into the stainless steel cauldron that volume is 5L.Then, the solution (based on the quality of the calcium carbonate that calcium hydroxide complete reaction generates, usage quantity is 10%) containing Potassium Hydrogen Phthalate and potassium sulfate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 800mLmin to gas
-1), raise carbonation temperature to 90 DEG C.Treat that the pH of feed liquid is down to about 7, stopped reaction.Next, by steps such as filtration, washings, the calcium carbonate filter cake obtained is dried at 110 DEG C, can prepare calcium carbonate nano crystal whisker products.Finally, transmission electron microscope (TEM) is adopted to carry out the test of the constitutional features such as pattern, size of calcium carbonate product, as shown in Figure 2.This product has obvious one dimension Nano structure feature, and its diameter is 20 ~ 30nm, and length is 250 ~ 300nm, thus has larger length-to-diameter ratio 10 ~ 20.
Embodiment 3
Measure the Ca (OH) of 4.1L exquisiteness
2slurries (mass percent concentration is 12%), put into the stainless steel cauldron that volume is 5L.Then, the solution (based on the quality of the calcium carbonate that calcium hydroxide complete reaction generates, usage quantity is 13%) containing Potassium Hydrogen Phthalate and potassium sulfate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 1200mLmin to gas
-1), raise carbonation temperature to 85 DEG C.Treat that the pH of feed liquid is down to about 7, stopped reaction.Next, by steps such as filtration, washings, the calcium carbonate filter cake obtained is dried at 110 DEG C, can prepare calcium carbonate nano crystal whisker products.Finally, transmission electron microscope (TEM) is adopted to carry out the test of the constitutional features such as pattern, size of calcium carbonate product, as shown in Figure 3.This product has obvious one dimension Nano structure feature, and its diameter is 20 ~ 40nm, and length is 250 ~ 500nm, thus has larger length-to-diameter ratio 10 ~ 25.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the preparation method of a calcium carbonate nano whisker, under being included in the existence of binary compound chemical additives, choose calcium hydroxide slurry and carbon dioxide reaction, wherein binary compound chemical additives is the mixture of Potassium Hydrogen Phthalate and potassium sulfate, it is characterized in that: take calcium hydroxide slurry as raw material, after mixing by suitable proportion with the binary compound chemical additives mixture of potassium sulfate (Potassium Hydrogen Phthalate with), pass into carbonic acid gas (CO at a certain temperature
2) gas carries out carbonation reaction, filter after reaction terminates, the filtrate containing Potassium Hydrogen Phthalate and potassium sulfate reclaims Reusability, filter cake through washing, oven dry obtains calcium carbonate nano whisker.
2. the preparation method of calcium carbonate nano whisker according to claim 1, comprises carbonation reaction; The unit processes such as filtration and drying, is characterized in that:
(1) binary compound chemical additives and calcium hydroxide slurry are uniformly mixed; Pass into CO at a certain temperature
2gas carries out carbonation reaction; Use the pH change of pH meter monitoring reaction system.
(2), after reaction terminates, calcium carbonate product is filtered, washes with water, calcium carbonate nano crystal whisker products can be obtained finally by airflow drying.
(3) filtrate containing Potassium Hydrogen Phthalate and potassium sulfate reclaims Reusability.
3. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, it is characterized in that the usage quantity of this mixing chemical additives is for 0.5% ~ 20% (quality based on the calcium carbonate that calcium hydroxide complete reaction generates).Wherein, the use range of Potassium Hydrogen Phthalate is 0.5% ~ 20%, and the use range of potassium sulfate is 0.5% ~ 20%.
4. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, it is characterized in that in carbonation reaction process, stirring velocity is 100 ~ 2200 revs/min.
5. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, it is characterized in that the temperature of reaction of carbonating is 20 ~ 90 DEG C.
6. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, it is characterized in that the CO used in carbonating
2gas can be pure CO
2gas, may also be CO
2with the mixed gas of air.According to pure CO
2calculate, its velocity range that passes in carbonation reaction is 50 ~ 1200mLmin
-1.
7. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, pH scope at the end of it is characterized in that carbonation reaction is 6.5 ~ 8.5, and preferred pH is near 7.0.
8. the mixture of Potassium Hydrogen Phthalate and potassium sulfate that utilizes according to claim 1 and 2 prepares the method for calcium carbonate nano whisker for binary compound chemical additives, it is characterized in that the airflow drying temperature range of calcium carbonate product is 50 ~ 120 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000272920A (en) * | 1999-03-25 | 2000-10-03 | New Raimu Kenkyusha:Kk | Needle or fibrous shape calcite calcium carbonate and its production |
| CN101613120A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | Sphere, radial magnesium carbonate and preparation method thereof |
| CN101736403A (en) * | 2009-12-14 | 2010-06-16 | 昆明理工大学 | Method for preparing calcium sulfate crystal whiskers by using impurity-containing gypsum as raw material |
| CN104975348A (en) * | 2015-07-20 | 2015-10-14 | 常州碳酸钙有限公司 | Method for producing nano calcium carboante whiskers based on sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent |
| CN104975339A (en) * | 2015-07-20 | 2015-10-14 | 常州碳酸钙有限公司 | Method for preparing nano calcium carbonate whiskers by use of binary complex crystal form control agent of sodium salicylate and ammonium nitrate |
-
2015
- 2015-12-30 CN CN201511022953.9A patent/CN105543959A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000272920A (en) * | 1999-03-25 | 2000-10-03 | New Raimu Kenkyusha:Kk | Needle or fibrous shape calcite calcium carbonate and its production |
| CN101613120A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | Sphere, radial magnesium carbonate and preparation method thereof |
| CN101736403A (en) * | 2009-12-14 | 2010-06-16 | 昆明理工大学 | Method for preparing calcium sulfate crystal whiskers by using impurity-containing gypsum as raw material |
| CN104975348A (en) * | 2015-07-20 | 2015-10-14 | 常州碳酸钙有限公司 | Method for producing nano calcium carboante whiskers based on sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent |
| CN104975339A (en) * | 2015-07-20 | 2015-10-14 | 常州碳酸钙有限公司 | Method for preparing nano calcium carbonate whiskers by use of binary complex crystal form control agent of sodium salicylate and ammonium nitrate |
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