CN104975348A - Method for producing nano calcium carboante whiskers based on sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent - Google Patents
Method for producing nano calcium carboante whiskers based on sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent Download PDFInfo
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- CN104975348A CN104975348A CN201510425661.3A CN201510425661A CN104975348A CN 104975348 A CN104975348 A CN 104975348A CN 201510425661 A CN201510425661 A CN 201510425661A CN 104975348 A CN104975348 A CN 104975348A
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Abstract
The invention relates to a method for producing nano calcium carboante whiskers based on a sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent. The preparation method is used for preparing the calcium carboante nano whiskers through a CO2 carbonation method by adopting Ca(OH)2 slurry as a raw material and a mixture of sodium butylnaphthalene sulfonate and sodium sulfate as the binary composite crystal form controlling agent. The method is characterized in that the sodium butylnaphthalene sulfonate and sodium sulfate binary composite crystal form controlling agent is used for controlled synthesis of the calcium carboante nano whiskers; and the filtrate containing sodium butylnaphthalene sulfonate and sodium sulfate can be recycled. The method has the advantages of simple production process method, simple operation, short synthesis period and the like, and is suitable for scaled industrial production of the nano calcium carboante whiskers.
Description
Technical field
The invention belongs to aragonitic nano-calcium carbonate calcium pyroborate field, be specifically related to a kind of method that binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate produces nano-calcium carbonate calcium pyroborate.
Background technology
Calcium carbonate material raw material is extensive, cheap, and be one of important source material during chemical industry is produced, it is widely used in the fields such as papermaking, plastic cement, daily-use chemical industry, makeup, ink.Calcium carbonate material has calcite, aragonite, vaterite three kinds of crystal formations.Wherein calcite is more stable at normal temperatures and pressures, but Aragonite Style Calcium Carbonate Whiskers is with its cheap cost, expensive SiC, potassium titanate crystal whisker and as a kind of type material can be replaced, have that heat-proof quality is good, intensity is high, modulus advantages of higher, and it is better with the consistency of matrix resin, processing and the mechanical property of infill system can be improved, and can improve and improve the matrix materials such as daily plastic.Therefore, have scholar for many years at the Composition and function of research aragonite calcium carbonate, therefore aragonite calcium carbonate is also widely used in the fields such as plastics, automobile and airplane parts position, electric parts manufacture, sintex, highly polished structure unit, chemical industry, the energy always.Due to one of main component that calcium carbonate is soil, and can decompose in acid condition, therefore easily degrade with the plastics that it is made, be beneficial to refuse treatment, there is important environment protection significance.
The method that Aragonite Style Calcium Carbonate Whiskers is prepared in current research mainly contains carbonation method, double decomposition, ureal antigen, Calcium hydrogen carbonate thermal degradation method.Many influence factors are had, as the pH value of temperature, solution, the amount ratio etc. of reactant, so how to select correct control agent to have become reaction whether successfully one of key element in the process preparing calcium carbonate aragonitic whisker.
Wherein, carbonation method has been used for preparing calcium carbonate crystal whisker product widely, and operational path is substantially as follows:
First calcite type calcium carbonate calcining is obtained active oxidation calcium powder, lime powder is fully digested, and adds about MgCl simultaneously
2solution obtains suspension liquid.Then suspension liquid fully stirred and be heated to 80 ° of about C, then passing into CO with certain flow
2gas carries out carbonation reaction, generates calcium carbonate crystal whisker.In experiment when pH value drops to below 7 or 7, can think that reaction terminates.And then by sedimentation and filtration, washing, dry at 100 ° of C, can calcium carbonate crystal whisker be obtained.Such as, 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, and bischofite is chemical additives, passes through CO
2carbonation reaction prepare calcium carbonate crystal whisker, then recycle mother liquor prepares calcium carbonate crystal whisker, thus completes the calcium carbonate crystal whisker of multistage growth high length-diameter ratio, and product diameter is 1 ~ 2 μm, and length is 10 ~ 40 μm.Although this type of chemical additives can realize the production of calcium carbonate crystal whisker, mostly the calcium carbonate crystal whisker in bibliographical information is micron-scale, fails to reach Nano grade.Therefore, the large-scale industrial how realizing the calcium carbonate crystal whisker of nano-scale is produced, and remains the focus 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 butylnaphthalenesulfonate and sodium sulfate 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.
Technical solution problem of the present invention adopts following technical scheme:
Step one: take appropriate sodium butylnaphthalenesulfonate and sodium sulfate and water-soluble, controlling mixing solutions concentration is 0.5% ~ 20%, can obtain binary compound chemical additives;
Step 2: by above-mentioned sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives 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 containing sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives is reclaimed, Reusability.
According to another embodiment of the invention, the concentration comprising sodium butylnaphthalenesulfonate in described step one is further 0.5% ~ 20%, and the concentration of sodium sulfate is 0.5% ~ 20%.
According to another embodiment of the invention, the usage quantity comprising sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives 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 40 ~ 1400 mL min
-1.
According to another embodiment of the invention, comprising carbonation temperature in described step 2 is further 30 ° 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.
Compared with prior art, beneficial effect of the present invention is as follows:
1, the present invention is with the mixture of sodium butylnaphthalenesulfonate and sodium sulfate for binary compound chemical additives, successfully utilizes CO
2carbonation method has synthesized 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 butylnaphthalenesulfonate and sodium sulfate.
Fig. 2 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives (concentration is 12%).
Fig. 3 is transmission electron microscope (TEM) photo of calcium carbonate nano whisker prepared by sodium butylnaphthalenesulfonate and sodium sulfate 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 2.5L is refining
2slurries (mass percent concentration is 9%), 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 4%) containing sodium butylnaphthalenesulfonate and sodium sulfate is added.Then, capping still, opens electric stirring, passes into CO
2(flow velocity is 700 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 9%), 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 butylnaphthalenesulfonate and sodium sulfate 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 2.5L is refining
2slurries (mass percent concentration is 9%), 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 butylnaphthalenesulfonate and sodium sulfate 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 3.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.
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. produce a method for nano-calcium carbonate calcium pyroborate based on the binary compound chemical additives of sodium butylnaphthalenesulfonate and sodium sulfate, it is characterized in that, its method is as follows:
Step one: take appropriate sodium butylnaphthalenesulfonate and sodium sulfate and water-soluble, strength of solution is 0.5% ~ 20%, can obtain binary compound chemical additives;
Step 2: by above-mentioned sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives 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 containing sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives is reclaimed, Reusability.
2. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, it is characterized in that, in described step one, the concentration of sodium butylnaphthalenesulfonate is 0.5% ~ 20%, and the concentration of sodium sulfate is 0.5% ~ 20%.
3. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, it is characterized in that, in described step 2, the usage quantity of sodium butylnaphthalenesulfonate and sodium sulfate binary compound chemical additives is 4% ~ 15%.
4. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, it is characterized in that, Ca (OH) in described step 2
2slurries mass percent concentration is 9%.
5. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, it 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 40 ~ 1400 mL min
-1.
6. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, and it is characterized in that, in described step 2, carbonation temperature is 30 ° of C ~ 90 ° C.
7. the binary compound chemical additives based on sodium butylnaphthalenesulfonate and sodium sulfate according to claim 1 produces the method for nano-calcium carbonate calcium pyroborate, it is characterized in that, 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 |
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| US4157379A (en) * | 1976-04-16 | 1979-06-05 | Toyo Soda Manufacturing Co., Ltd. | Process for producing chain structured corpuscular calcium carbonate |
| US4824654A (en) * | 1988-03-17 | 1989-04-25 | Yabashi Industries Co., Ltd. | Process of producing needle-shaped calcium carbonate particles |
| 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 |
| 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 |
| 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 |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4157379A (en) * | 1976-04-16 | 1979-06-05 | Toyo Soda Manufacturing Co., Ltd. | Process for producing chain structured corpuscular calcium carbonate |
| US4824654A (en) * | 1988-03-17 | 1989-04-25 | Yabashi Industries Co., Ltd. | Process of producing needle-shaped calcium carbonate particles |
| 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 |
| 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 |
| 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 |
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| 王仲军: "针状纳米碳酸钙制备研究", 《非金属矿》 * |
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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 |
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Application publication date: 20151014 |