CN104975339A - Method for preparing nano calcium carbonate whiskers by use of binary complex crystal form control agent of sodium salicylate and ammonium nitrate - Google Patents
Method for preparing nano calcium carbonate whiskers by use of binary complex crystal form control agent of sodium salicylate and ammonium nitrate Download PDFInfo
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- CN104975339A CN104975339A CN201510425703.3A CN201510425703A CN104975339A CN 104975339 A CN104975339 A CN 104975339A CN 201510425703 A CN201510425703 A CN 201510425703A CN 104975339 A CN104975339 A CN 104975339A
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- calcium carbonate
- ammonium nitrate
- sodium salicylate
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Abstract
The invention relates to a method for preparing nano calcium carbonate whiskers by use of a binary complex crystal form a control agent of sodium salicylate and ammonium nitrate. According to the preparation method, a calcium hydroxide slurry is adopted as a raw material so as to prepare the nano calcium carbonate whiskers by use of a carbon dioxide carbonic acid acidification method, and a mixture of sodium salicylate and ammonium nitrate is adopted as a binary complex crystal form control agent. The method is characterized in that the binary complex crystal form control agent of sodium salicylate and ammonium nitrate is utilized to control synthesis of the nano calcium carbonate whiskers, and a filtered solution containing sodium salicylate and ammonium nitrate can be recycled and repeatedly used. The method has the advantages of simple production process, easiness for operation, short synthesis period and the like, and is suitable for large-scale production of the nano calcium carbonate whiskers.
Description
Technical field
The present invention relates to aragonitic nano-calcium carbonate whisker technique field, especially a kind of method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate.
Background technology
Calcium carbonate crystal whisker is the new type whisker material developed in recent years, has excellent high temperature resistant, insulation, the function such as fire-retardant, and the feature such as good physical strength, high elastic coefficient, high rigidity.Therefore, can be used as toughened and reinforced dose of advanced composite material, obtain widespread use in fields such as engineering plastics, polypropylene, nylon, degradative plastics, coating and biological active materials.
At present, the method preparing calcium carbonate crystal whisker both at home and abroad has carbonation method, replacement(metathesis)reaction method, ureal antigen, Calcium hydrogen carbonate thermal degradation method, high-gravity reactive precipitation etc.Prepared by carbonic acid gas carbonation method to the technique of calcium carbonate crystal whisker, has that required equipment is simple, easy operation control and easily realize the advantages such as industrialization, embodied the value that large-scale industrial is produced.In order to realize the mass-producing synthesis of calcium carbonate crystal whisker, usually need to regulate and control the series of processes condition in carbonation, such as temperature of reaction, stirring velocity, CO
2pass into speed, and add chemical additives etc.
Chinese patent CN 101684570 A discloses a kind of preparation method of calcium carbonate crystal whisker of morphology controllable: employing unslaked lime is raw material, and bischofite is chemical additives, prepares calcium carbonate crystal whisker by the carbonation reaction of carbonic acid gas.Chinese patent CN 1442363 A discloses a kind of method preparing microwhisker like calcium carbonate: utilize supergravity reactor, under the existence of chemical additives, the method for microwhisker like calcium carbonate prepared by calcium hydroxide and carbon dioxide reaction.Chinese patent CN 101935865 A discloses a kind of preparation method of high length-diameter ratio calcium carbonate crystal whisker: employing unslaked lime is raw material, bischofite is chemical additives, calcium carbonate crystal whisker is prepared by the carbonation reaction of carbonic acid gas, then recycle mother liquor prepares calcium carbonate crystal whisker, thus completes the calcium carbonate crystal whisker product of multistage growth high length-diameter ratio.Although this type of chemical additives can realize the production of 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 sodium salicylate and ammonium nitrate to prepare the calcium carbonate nano whisker of high-quality.Technical problem to be solved be to provide a kind of easy and simple to handle, can the method for large-scale production nano-calcium carbonate calcium pyroborate.
The technical solution adopted for the present invention to solve the technical problems is:
Step one: take suitable quantity of water poplar acid sodium and ammonium nitrate and water-soluble, controlling mixing solutions concentration is 0.5% ~ 20%, can obtain binary compound chemical additives;
Step 2: by the binary compound chemical additives of above-mentioned sodium salicylate and ammonium nitrate and Ca (OH)
2slurry agitation mixes, under 30 ~ 90 ° of C, pass into CO
2gas carries out carbonation reaction, raises carbonation temperature, and reaction process adopts the pH change of pH meter monitoring system, when this pH value of solution reaches near 7, stops carbonation reaction;
Step 3: after reaction terminates, filtered by calcium carbonate product, wash with water, then through airflow drying, bake out temperature 50 ° of C ~ 120 ° C, can obtain nano-calcium carbonate crystal whisker products.
Step 4: the filtrate of the binary compound chemical additives containing sodium salicylate and ammonium nitrate is reclaimed, Reusability.
According to another embodiment of the invention, the concentration comprising sodium salicylate in described step one is further 0.5% ~ 20%, and the concentration of ammonium nitrate is 0.5% ~ 20%.
According to another embodiment of the invention, the usage quantity comprising the binary compound chemical additives of sodium salicylate and ammonium nitrate in described step 2 is further 4% ~ 15%.
According to another embodiment of the invention, Ca (OH) in described step 2 is comprised further
2slurries mass percent concentration is 9%.
According to another embodiment of the invention, the CO used in carbonating in described step 2 is comprised further
2gas can be pure CO
2gas, may also be CO
2with the mixed gas of air; According to pure CO
2calculate, its speed that passes in carbonic acid acidification reaction is 50 ~ 1600 mL min
-1.
According to another embodiment of the invention, comprising carbonation temperature in described step 2 is further under 20 ° of C ~ 90 ° C.
According to another embodiment of the invention, the pH comprised further in described step 2 at the end of carbonic acid acidification reaction is 6.5 ~ 8.5, and preferred pH is about 7.0.
The invention has the beneficial effects as follows:
1, the present invention is with the mixture of sodium salicylate and ammonium nitrate for binary compound chemical additives, successfully utilizes CO2 carbonic acid acidization to synthesize nano-calcium carbonate calcium pyroborate.
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 nano-calcium carbonate calcium pyroborate is produced.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of calcium carbonate nano whisker prepared by the binary compound chemical additives (concentration is 4%) of sodium salicylate and ammonium nitrate.
Fig. 2 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by sodium salicylate and ammonium nitrate binary compound chemical additives (concentration is 12%).
Fig. 3 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by sodium salicylate and ammonium nitrate binary compound chemical additives (concentration is 15%).
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment 1
Get the Ca (OH) that 3.3 L are refining
2slurries (mass percent concentration is 9%), put into the stainless steel cauldron that volume is 5 L.Then, the solution (based on the quality of the calcium carbonate that calcium hydroxide complete reaction generates, usage quantity is 4%) containing sodium salicylate and ammonium nitrate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 600 mL min to gas
-1), raise carbonation temperature to 30 ° 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 under 50 ° of C, can prepare nano-calcium carbonate crystal whisker products.Finally, use scanning electron microscope (SEM) constitutional features such as pattern, size to calcium carbonate product to test, SEM result as shown in Figure 1.This product has obvious one dimension Nano structure feature, and its diameter is 40 ~ 50 nm, and length is 500 ~ 800 nm, thus has larger length-to-diameter ratio 10 ~ 20.
Embodiment 2
Get the Ca (OH) that 2.5L is refining
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 12%) containing sodium salicylate and ammonium nitrate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 900 mL min to gas
-1), raise carbonation temperature to 80 ° 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 under 120 ° of C, can prepare nano-calcium carbonate crystal whisker products.Finally, adopt transmission electron microscope (TEM) to carry out the test of the constitutional features such as pattern, size of calcium carbonate product, TEM result as shown in Figure 2.This product has obvious one dimension Nano structure feature, and its diameter is 20 ~ 30 nm, and length is 200 ~ 300 nm, has larger length-to-diameter ratio 10 ~ 15.
Embodiment 3
Get the Ca (OH) that 3.5 L are refining
2slurries (mass percent concentration is 13%), 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 15%) containing sodium salicylate and ammonium nitrate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 900 mL min to gas
-1), raise carbonation temperature to 90 ° 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 under 110 ° of C, can prepare nano-calcium carbonate crystal whisker products.Finally, adopt transmission electron microscope (TEM) to carry out the test of the constitutional features such as pattern, size of calcium carbonate product, TEM result as shown in Figure 3.This product has obvious one dimension Nano structure feature, and its diameter is 30 ~ 40 nm, and length is 250 ~ 400 nm, has larger length-to-diameter ratio 10 ~ 12.
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 (7)
1. utilize the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare a method for nano-calcium carbonate calcium pyroborate, it is characterized in that, its method is as follows:
Step one: take suitable quantity of water poplar acid sodium and ammonium nitrate and water-soluble, controlling mixing solutions concentration is 0.5% ~ 20%, can obtain binary compound chemical additives;
Step 2: by the binary compound chemical additives of above-mentioned sodium salicylate and ammonium nitrate and Ca (OH)
2slurry agitation mixes, under 30 ~ 90 ° of C, pass into CO
2gas carries out carbonation reaction, raises carbonation temperature, and reaction process adopts the pH change of pH meter monitoring system, when this pH value of solution reaches near 7, stops carbonation reaction;
Step 3: after reaction terminates, filtered by calcium carbonate product, wash with water, then through airflow drying, bake out temperature 50 ° of C ~ 120 ° C, can obtain nano-calcium carbonate crystal whisker products;
Step 4: the filtrate of the binary compound chemical additives containing sodium salicylate and ammonium nitrate is reclaimed, Reusability.
2. the method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, it is characterized in that, in described step one, the concentration of sodium salicylate is 0.5% ~ 20%, and the concentration of ammonium nitrate is 0.5% ~ 20%.
3. the method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, it is characterized in that, in described step 2, the usage quantity of the binary compound chemical additives of sodium salicylate and ammonium nitrate is 4% ~ 15%.
4. the method utilizing the binary compound chemical additives of sodium butylnaphthalenesulfonate and sodium sulfate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, is characterized in that, Ca (OH) in described step 2
2slurries mass percent concentration is 9%.
5. the method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, is characterized in that, the CO used in carbonating in described step 2
2gas can be pure CO
2gas, may also be CO
2with the mixed gas of air; According to pure CO
2calculate, its speed that passes in carbonic acid acidification reaction is 50 ~ 1600 mL min
-1.
6. the method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, is characterized in that, in described step 2, carbonation temperature is 30 ° of C ~ 90 ° C.
7. the method utilizing the binary compound chemical additives of sodium salicylate and ammonium nitrate to prepare nano-calcium carbonate calcium pyroborate according to claim 1, it is characterized in that, the pH in described step 2 at the end of carbonic acid acidification reaction is 6.5 ~ 8.5, and preferred pH is about 7.0.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543959A (en) * | 2015-12-30 | 2016-05-04 | 常州合肥工业大学研究院 | Method for synthesizing calcium carbonate nanowhiskers based on potassium biphthalate and potassium sulfate |
| CN105543975A (en) * | 2015-12-30 | 2016-05-04 | 常州合肥工业大学研究院 | Method for synthesizing calcium carbonate nanocrystal whiskers on basis of sodium carboxymethyl cellulose and potassium chloride |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330039A (en) * | 2001-08-03 | 2002-01-09 | 上海卓越纳米新材料股份有限公司 | Industrial process for preparing nm-class active calcium carbonate |
| CN1429772A (en) * | 2001-12-31 | 2003-07-16 | 纳米材料科技有限公司 | Method for preparing calcium carbonate with actual forms |
| CN101229926A (en) * | 2007-10-11 | 2008-07-30 | 河北科技大学 | Preparation method of styliform nano calcium carbonate |
| CN101475199A (en) * | 2009-01-21 | 2009-07-08 | 山东海泽纳米材料有限公司 | Industrial preparation of calcium carbonate nano bead string |
| CN101684570A (en) * | 2009-09-22 | 2010-03-31 | 成都市蜀阳硼业化工有限公司 | Method for preparing calcium carbonate crystal whisker with controllable shape |
| CN101914312A (en) * | 2010-08-20 | 2010-12-15 | 常州碳酸钙有限公司 | Preparation method of nano activated calcium carbonate for coating |
| CN101935865A (en) * | 2010-09-08 | 2011-01-05 | 中国科学院青海盐湖研究所 | Preparation method of high length-diameter ratio calcium carbonate whiskers |
| CN102372300A (en) * | 2010-08-10 | 2012-03-14 | 上海华明高技术（集团）有限公司 | Preparation method of needle-like nano calcium carbonate |
| RU2489355C2 (en) * | 2011-07-05 | 2013-08-10 | Алексей Гаврилович Мешандин | Method for synthesis of finely dispersed calcium carbonate |
| CN103806088A (en) * | 2014-03-10 | 2014-05-21 | 常州碳酸钙有限公司 | Method for preparing calcium carbonate whisker by taking triethanolamine as aid |
| CN103834997A (en) * | 2014-03-10 | 2014-06-04 | 常州碳酸钙有限公司 | Method for preparing calcium carbonate whisker from saccharose by assisting hydrothermal process |
-
2015
- 2015-07-20 CN CN201510425703.3A patent/CN104975339A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330039A (en) * | 2001-08-03 | 2002-01-09 | 上海卓越纳米新材料股份有限公司 | Industrial process for preparing nm-class active calcium carbonate |
| CN1429772A (en) * | 2001-12-31 | 2003-07-16 | 纳米材料科技有限公司 | Method for preparing calcium carbonate with actual forms |
| CN101229926A (en) * | 2007-10-11 | 2008-07-30 | 河北科技大学 | Preparation method of styliform nano calcium carbonate |
| CN101475199A (en) * | 2009-01-21 | 2009-07-08 | 山东海泽纳米材料有限公司 | Industrial preparation of calcium carbonate nano bead string |
| CN101684570A (en) * | 2009-09-22 | 2010-03-31 | 成都市蜀阳硼业化工有限公司 | Method for preparing calcium carbonate crystal whisker with controllable shape |
| CN102372300A (en) * | 2010-08-10 | 2012-03-14 | 上海华明高技术（集团）有限公司 | Preparation method of needle-like nano calcium carbonate |
| CN101914312A (en) * | 2010-08-20 | 2010-12-15 | 常州碳酸钙有限公司 | Preparation method of nano activated calcium carbonate for coating |
| CN101935865A (en) * | 2010-09-08 | 2011-01-05 | 中国科学院青海盐湖研究所 | Preparation method of high length-diameter ratio calcium carbonate whiskers |
| RU2489355C2 (en) * | 2011-07-05 | 2013-08-10 | Алексей Гаврилович Мешандин | Method for synthesis of finely dispersed calcium carbonate |
| CN103806088A (en) * | 2014-03-10 | 2014-05-21 | 常州碳酸钙有限公司 | Method for preparing calcium carbonate whisker by taking triethanolamine as aid |
| CN103834997A (en) * | 2014-03-10 | 2014-06-04 | 常州碳酸钙有限公司 | Method for preparing calcium carbonate whisker from saccharose by assisting hydrothermal process |
Non-Patent Citations (1)
| Title |
|---|
| 王农等: "添加剂对纳米碳酸钙形貌与粒度的影响", 《无机盐工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543959A (en) * | 2015-12-30 | 2016-05-04 | 常州合肥工业大学研究院 | Method for synthesizing calcium carbonate nanowhiskers based on potassium biphthalate and potassium sulfate |
| CN105543975A (en) * | 2015-12-30 | 2016-05-04 | 常州合肥工业大学研究院 | Method for synthesizing calcium carbonate nanocrystal whiskers on basis of sodium carboxymethyl cellulose and potassium chloride |
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Application publication date: 20151014 |