CN117699842A - Preparation method of active nano calcium carbonate - Google Patents
Preparation method of active nano calcium carbonate Download PDFInfo
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- CN117699842A CN117699842A CN202410041154.9A CN202410041154A CN117699842A CN 117699842 A CN117699842 A CN 117699842A CN 202410041154 A CN202410041154 A CN 202410041154A CN 117699842 A CN117699842 A CN 117699842A
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 106
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 35
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004359 castor oil Substances 0.000 claims abstract description 30
- 235000019438 castor oil Nutrition 0.000 claims abstract description 30
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 30
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical compound C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 108010010803 Gelatin Proteins 0.000 claims abstract description 24
- 229920000159 gelatin Polymers 0.000 claims abstract description 24
- 239000008273 gelatin Substances 0.000 claims abstract description 24
- 235000019322 gelatine Nutrition 0.000 claims abstract description 24
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 230000002087 whitening effect Effects 0.000 claims abstract description 19
- 238000002845 discoloration Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000000292 calcium oxide Substances 0.000 claims abstract description 16
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 77
- 238000003756 stirring Methods 0.000 claims description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000007822 coupling agent Substances 0.000 claims description 20
- 230000001105 regulatory effect Effects 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 15
- 239000011975 tartaric acid Substances 0.000 claims description 15
- 235000002906 tartaric acid Nutrition 0.000 claims description 15
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005282 brightening Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 150000004775 coumarins Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 8
- 239000000123 paper Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003064 anti-oxidating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method of active nano calcium carbonate, and belongs to the technical field of calcium carbonate. The preparation method comprises the following steps: the active nano calcium carbonate is prepared by adding gelatin modified castor oil anti-discoloration agent and 7-hydroxy-4-methylcoumarin modified whitening agent, adding water into quicklime to digest by using a carbonization method, reacting the generated calcium hydroxide slurry with carbon dioxide, filtering, washing, drying and sieving. The nano calcium carbonate prepared by the invention can enhance the strength of paper, improve the whiteness and ageing resistance of paper, and optimize the dispersibility of the calcium carbonate as filler.
Description
Technical Field
The invention belongs to the technical field of calcium carbonate, and relates to a preparation method of active nano calcium carbonate.
Background
Calcium carbonate is an important chemical raw material, has the characteristics of abundant and easily available raw materials, simple production process, excellent application performance and the like, and is widely applied to industries such as rubber, plastics, printing ink, papermaking, medicines, foods and the like as an inorganic filler. Calcium carbonate is one of the white pigment fillers with the largest demand in the paper industry at present, has the excellent performances of low price, moderate refractive index, high whiteness, good ink absorptivity and the like, and can gradually replace titanium dioxide and kaolin which are in shortage of resources as fillers.
The nano calcium carbonate has high light shielding property and high brightness, and can improve the whiteness and light shielding property of paper products. The granularity is fine and uniform, the abrasion to a paper machine is small, the produced paper product is more uniform and flat, and the paper product is widely applied in the paper industry. As one of the most promising fillers, nano calcium carbonate has been rapidly developed, and has been widely used in daily chemicals, foods, and construction industries, and has been increasingly playing an irreplaceable role in the fields of plastics, rubber, paper and ink. However, the research on nano calcium carbonate in China is relatively late, and most of functional nano calcium carbonate still depends on foreign import, so that the modification method and process of nano calcium carbonate are necessary to be thoroughly discussed and researched.
The untreated nano calcium carbonate has a large number of hydroxyl groups on the surface, has high surface polarity and poor compatibility with a high polymer matrix, and can cause poor interface bonding. Therefore, it is necessary to modify the nano calcium carbonate, change the surface characteristics of the nano calcium carbonate, weaken the acting force between particles, improve the dispersion degree of the nano calcium carbonate particles in the matrix, and increase the anti-discoloration capability, whitening capability and antioxidation capability of the calcium carbonate as a filler.
Disclosure of Invention
The invention aims to provide a preparation method of active nano calcium carbonate, which can obtain nano calcium carbonate which can be used as paper filler and has good anti-discoloration and antioxidation capabilities, high whiteness, no toxicity and paper strength enhancement.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the active nano calcium carbonate comprises the following steps:
pretreatment of quicklime: gradually dissolving quicklime with a little excessive amount of dilute hydrochloric acid, adding hydrogen peroxide, adjusting the pH of the solution to be slightly alkaline, fully stirring, standing, and filtering to obtain a purified calcium ion solution;
adding warm water into the calcium ion solution, fully stirring for 5 hours in a stirrer to obtain calcium hydroxide suspension, and filtering by using a standard sieve with 200 meshes;
pouring the filtered calcium hydroxide suspension into a jacketed reactor, and cooling the calcium hydroxide suspension by using circulating water to cool the solution in the reactor to normal temperature;
fully dissolving a modified anti-discoloration castor oil auxiliary agent and a modified whitening agent by using absolute ethyl alcohol, pouring the modified anti-discoloration castor oil auxiliary agent and the modified whitening agent into a jacketed reactor, introducing carbon dioxide gas under the stirring state of a stirrer for carbonization reaction, starting circulating water while stirring to keep the solution temperature in a reaction container at normal temperature, regulating the introducing rate and stirring speed of the carbon dioxide according to the solution temperature to control the reaction, and stopping the reaction when the pH value of a reaction system is 7.0-7.5 to obtain calcium hydroxide slurry;
and (3) aging, filtering, washing, drying and sieving the calcium hydroxide slurry to obtain the nano calcium carbonate.
As a preferable technical scheme of the invention, the preparation process of the modified anti-discoloration castor oil auxiliary agent is as follows:
dissolving gelatin by deionized water, stirring in a constant temperature water bath for 60min at 45 ℃ until the gelatin is completely dissolved, regulating the pH of the gelatin solution to 7-8 by using 10% sodium hydroxide solution by mass fraction, and preparing the gelatin solution into 20mg/mL to obtain solution A;
maintaining an anaerobic and anhydrous environment, dissolving a borate coupling agent in absolute ethyl alcohol under the protection of inert gas, fully and uniformly stirring, adding 2-3 times of castor oil active agent, and reacting for 2 hours at normal temperature by a microwave method to obtain a solution B;
mixing the solution A, B in equal volume, adding 1-1.5% of straight-chain sodium dodecyl benzene sulfonate, stirring for 3h at room temperature on a constant-temperature magnetic stirrer, and carrying out ultrasonic treatment to obtain the modified castor oil auxiliary agent.
As a preferable technical scheme of the invention, the preparation process of the modified whitening agent is as follows:
the modified coumarin fluorescent brightening agent is prepared by taking hexahydrophthalic anhydride as a crosslinking agent, introducing a 7-hydroxy-4-methylcoumarin fluorescent brightening agent, tartaric acid and triethoxysilane coupling agent into the same molecule, and hydrolyzing the mixture, wherein the specific preparation method is as follows:
dissolving hexahydrophthalic anhydride in dichloromethane, stirring for 20min, dropwise adding 7-hydroxy-4-methylcoumarin solution fully dissolved by dichloromethane under stirring, regulating the pH of the solution at normal temperature to be unchanged, adding tartaric acid, continuously regulating the pH to be 5-6, and steaming until the solution is completely volatilized; adding deionized water to dissolve the components completely, adding a triethoxysilane coupling agent under stirring, slowly heating to 90-95 ℃, reacting until the pH value is unchanged, cooling, standing and precipitating the mixed solution, and suction-filtering and drying to obtain a product, wherein the molar ratio of hexahydrophthalic anhydride to 7-hydroxy-4-methylcoumarin to tartaric acid to siloxane coupling agent is 1-1.5: 3: 1-2: 1.
as a preferable technical scheme of the invention, the mass fraction of the modified anti-discoloration castor oil auxiliary agent and the modified whitening agent is 1-2%.
As a preferable technical scheme of the invention, the temperature of the warm water is 30-45 ℃.
As a preferable technical scheme of the invention, the ratio of the quicklime to the warm water is 1:2 to 3.
As a preferable technical scheme of the invention, the rotating speed of the stirrer is 1000-2000 r/min, and the carbon dioxide introducing rate is 30-45L/min.
As a preferable technical scheme of the invention, the concentration of the calcium hydroxide in the calcium hydroxide slurry is 10-16 wt%.
As a preferable technical scheme of the invention, the calcium hydroxide slurry is aged, filtered, washed and dried, and then is ground by a ball mill and passes through a standard sieve with 200 meshes.
The invention has the beneficial effects that:
(1) The castor oil has the anti-discoloration capability, is condensed with the borate coupling agent, increases the dispersibility and stability of the castor oil in the calcium carbonate, simultaneously adds gelatin to maintain the anti-discoloration and antioxidation capability of reducing castor oil molecules due to condensation, and adds linear sodium dodecyl benzene sulfonate to solve the problem that gelatin is easy to agglomerate, simultaneously maintains the alkaline environment of the auxiliary system, prevents the hydrolysis of components such as gelatin and the like, thereby obtaining the castor oil auxiliary with excellent anti-discoloration and antioxidation, preventing the yellowing and ageing problems of the calcium carbonate as paper in paper filler, and greatly improving the applicability and superiority of the nano calcium carbonate as paper filler.
(2) Further, in order to increase the whiteness of paper, a modified fluorescent brightening agent is added, a small-molecule coumarin compound is polymerized by a crosslinking agent, the optical activity of coumarin molecules is improved, 7-hydroxy-4-methylcoumarin is polymerized by the crosslinking agent, the hydroxyl at the 7-position can influence the movement of the absorption wavelength of the brightening agent due to reaction, tartaric acid is added to prevent hydrolysis in an alkaline environment, the whitening effect of the brightening agent is maintained, meanwhile, tartaric acid has good antioxidant capacity, and the brightening agent and calcium carbonate are combined to prepare modified nano calcium carbonate by a triethoxysilane coupling agent, so that the whiteness of paper is effectively improved. The modified nano particles have small particle size, large specific surface area and high chemical activity, and have excellent ultraviolet shielding performance, so that the light stability of the paper is improved, the yellowing inhibition effect on the paper is better, and the paper can be whitened to the greatest extent.
(3) The surface characteristics of the nano calcium carbonate are improved through the combined action of the additives, acting force among particles is weakened, the dispersion performance of the nano calcium carbonate is improved, the anti-discoloration performance of the nano calcium carbonate is enhanced, and meanwhile, the strength of paper is enhanced through the addition of the triethoxysilane coupling agent.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
Preparing a modified anti-discoloration castor oil auxiliary agent:
dissolving gelatin by deionized water, stirring in a constant temperature water bath for 60min at 45 ℃ until the gelatin is completely dissolved, regulating the pH of the gelatin solution to 7-8 by using 10% sodium hydroxide solution by mass fraction, and preparing the gelatin solution into 20mg/mL to obtain solution A;
maintaining an anaerobic and anhydrous environment, dissolving a borate coupling agent in absolute ethyl alcohol under the protection of inert gas, fully and uniformly stirring, adding 2 times of castor oil active agent, and reacting for 2 hours at normal temperature by a microwave method to obtain a solution B;
the solution A, B is mixed in equal volume, 1.5 percent of linear sodium dodecyl benzene sulfonate is added, the mixture is placed on a constant temperature magnetic stirrer and stirred for 3 hours at room temperature, and the modified castor oil auxiliary agent is obtained through ultrasonic treatment.
Preparing a modified whitening agent:
dissolving hexahydrophthalic anhydride in dichloromethane, stirring for 20min, dropwise adding 7-hydroxy-4-methylcoumarin solution fully dissolved by dichloromethane under stirring, regulating the pH of the solution at normal temperature to be unchanged, adding tartaric acid, continuously regulating the pH to be 5-6, and steaming until the solution is completely volatilized; adding deionized water to dissolve the components completely, adding a triethoxysilane coupling agent under stirring, slowly heating to 90 ℃, reacting until the pH value is unchanged, cooling, standing and precipitating the mixed solution, and carrying out suction filtration and drying to obtain a product, wherein the molar ratio of hexahydrophthalic anhydride to 7-hydroxy-4-methylcoumarin to tartaric acid to the siloxane coupling agent is 1:3:1.5:1.
the process for preparing the active nano calcium carbonate comprises the following steps:
pretreatment of quicklime: gradually dissolving quicklime with a little excessive amount of dilute hydrochloric acid, adding hydrogen peroxide, adjusting the pH of the solution to 7-8, fully stirring, standing, and filtering to obtain a purified calcium ion solution;
adding warm water at 35 ℃ into the calcium ion solution, wherein the ratio of the quicklime to the warm water is 1:2, fully stirring for 5 hours in a stirrer, wherein the rotating speed of the stirrer is 1500r/min, obtaining calcium hydroxide suspension, and filtering by using a standard sieve with 200 meshes;
pouring the filtered calcium hydroxide suspension solution into a jacketed reactor, and cooling the calcium hydroxide suspension solution by using circulating water to cool the solution in the reactor to normal temperature;
adding 1wt% of modified castor oil auxiliary agent and 1wt% of modified whitening agent, introducing carbon dioxide gas at a speed of 30L/min under the stirring state of a turbine stirrer to carry out carbonization reaction, keeping the temperature of the solution in a reaction container at normal temperature, regulating the introducing speed and stirring speed of the carbon dioxide to control the reaction, and stopping the reaction when the pH value of a reaction system is 7.0-7.5 to obtain calcium hydroxide slurry;
and (3) aging, filtering, washing and drying the calcium hydroxide slurry, grinding the calcium hydroxide slurry by a ball mill, and then sieving the calcium hydroxide slurry by a standard sieve with 200 meshes to obtain the nano calcium carbonate.
Example 2
Preparing a modified anti-discoloration castor oil auxiliary agent:
dissolving gelatin by deionized water, stirring in a constant temperature water bath for 60min at 45 ℃ until the gelatin is completely dissolved, regulating the pH of the gelatin solution to 7-8 by using 10% sodium hydroxide solution by mass fraction, and preparing the gelatin solution into 20mg/mL to obtain solution A;
maintaining an anaerobic and anhydrous environment, dissolving a borate coupling agent in absolute ethyl alcohol under the protection of inert gas, fully and uniformly stirring, adding 2 times of castor oil active agent, and reacting for 2 hours at normal temperature by a microwave method to obtain a solution B;
the solution A, B is mixed in equal volume, 1% of linear sodium dodecyl benzene sulfonate is added, the mixture is placed on a constant temperature magnetic stirrer and stirred for 3 hours at room temperature, and the modified castor oil auxiliary agent is obtained through ultrasonic treatment.
Preparing a modified whitening agent:
dissolving hexahydrophthalic anhydride in dichloromethane, stirring for 20min, dropwise adding 7-hydroxy-4-methylcoumarin solution fully dissolved by dichloromethane under stirring, regulating the pH of the solution at normal temperature to be unchanged, adding tartaric acid, continuously regulating the pH to be 5-6, and steaming until the solution is completely volatilized; adding deionized water to dissolve the components completely, adding a triethoxysilane coupling agent under stirring, slowly heating to 90 ℃, reacting until the pH value is unchanged, cooling, standing and precipitating the mixed solution, and carrying out suction filtration and drying to obtain a product, wherein the molar ratio of hexahydrophthalic anhydride to 7-hydroxy-4-methylcoumarin to tartaric acid to the siloxane coupling agent is 1.5:3:2:1.
the process for preparing the active nano calcium carbonate comprises the following steps:
pretreatment of quicklime: gradually dissolving quicklime with a little excessive amount of dilute hydrochloric acid, adding hydrogen peroxide, adjusting the pH of the solution to 7-8, fully stirring, standing, and filtering to obtain a purified calcium ion solution;
in S41, warm water at 35 ℃ is added, and the ratio of the quicklime to the warm water is 1:2, fully stirring for 5 hours in a stirrer, wherein the rotating speed of the stirrer is 1500r/min, obtaining calcium hydroxide suspension, and filtering by using a standard sieve with 200 meshes;
pouring the solution of S42 into a jacketed reactor, and cooling the solution by using circulating water to cool the solution in the reactor to normal temperature;
adding 1.5wt% of modified castor oil auxiliary agent and 1.5wt% of modified whitening agent, introducing carbon dioxide gas at a speed of 30L/min under the stirring state of a turbine stirrer to carry out carbonization reaction, keeping the temperature of the solution in a reaction container at normal temperature, regulating the introducing speed and stirring speed of carbon dioxide to control the reaction, and stopping the reaction when the pH value of a reaction system is 7.0-7.5 to obtain calcium hydroxide slurry;
and (3) aging, filtering, washing and drying the calcium hydroxide slurry, grinding the calcium hydroxide slurry by a ball mill, and then sieving the calcium hydroxide slurry by a standard sieve with 200 meshes to obtain the nano calcium carbonate.
Example 3
Preparing a modified anti-discoloration castor oil auxiliary agent:
dissolving gelatin by deionized water, stirring in a constant temperature water bath for 60min at 45 ℃ until the gelatin is completely dissolved, regulating the pH of the gelatin solution to 7-8 by using 10% sodium hydroxide solution by mass fraction, and preparing the gelatin solution into 20mg/mL to obtain solution A;
maintaining an anaerobic and anhydrous environment, dissolving a borate coupling agent in absolute ethyl alcohol under the protection of inert gas, fully and uniformly stirring, adding 2 times of castor oil active agent, and reacting for 2 hours at normal temperature by a microwave method to obtain a solution B;
the solution A, B is mixed in equal volume, 1.2 percent of linear sodium dodecyl benzene sulfonate is added, the mixture is placed on a constant temperature magnetic stirrer and stirred for 3 hours at room temperature, and the modified castor oil auxiliary agent is obtained through ultrasonic treatment.
Preparing a modified whitening agent:
dissolving hexahydrophthalic anhydride in dichloromethane, stirring for 20min, dropwise adding 7-hydroxy-4-methylcoumarin solution fully dissolved by dichloromethane under stirring, regulating the pH of the solution at normal temperature to be unchanged, adding tartaric acid, continuously regulating the pH to be 5-6, and steaming until the solution is completely volatilized; adding deionized water to dissolve the components completely, adding a triethoxysilane coupling agent under stirring, slowly heating to 90 ℃, reacting until the pH value is unchanged, cooling, standing and precipitating the mixed solution, and carrying out suction filtration and drying to obtain a product, wherein the molar ratio of hexahydrophthalic anhydride to 7-hydroxy-4-methylcoumarin to tartaric acid to the siloxane coupling agent is 1:3:1:1.
preparing active nano calcium carbonate:
pretreatment of quicklime: gradually dissolving quicklime with a little excessive amount of dilute hydrochloric acid, adding hydrogen peroxide, adjusting the pH of the solution to 7-8, fully stirring, standing, and filtering to obtain a purified calcium ion solution;
adding warm water at 35 ℃ into the calcium ion solution, wherein the ratio of the quicklime to the warm water is 1:2, fully stirring for 5 hours in a stirrer, wherein the rotating speed of the stirrer is 1500r/min, obtaining calcium hydroxide suspension, and filtering by using a standard sieve with 200 meshes;
pouring the solution of the calcium hydroxide suspension into a jacketed reactor, and cooling the solution by using circulating water to cool the solution in the reactor to normal temperature;
adding 2wt% of modified castor oil auxiliary agent and 1wt% of modified whitening agent, introducing carbon dioxide gas at a speed of 30L/min under the stirring state of a turbine stirrer to carry out carbonization reaction, keeping the temperature of the solution in a reaction container at normal temperature, regulating the introducing speed and stirring speed of the carbon dioxide to control the reaction, and stopping the reaction when the pH value of a reaction system is 7.0-7.5 to obtain calcium hydroxide slurry;
and (3) aging, filtering, washing and drying the calcium hydroxide slurry, grinding the calcium hydroxide slurry by a ball mill, and then sieving the calcium hydroxide slurry by a standard sieve with 200 meshes to obtain the nano calcium carbonate.
Comparative example 1
This comparative example 1 differs from example 1 in that no modified anti-tarnish castor oil adjuvant was added and the other operations were identical.
Comparative example 2
This comparative example 2 differs from example 1 in that no modified whitening agent was added, and the other operations were the same.
Comparative example 3
This comparative example 3 differs from example 1 in that the modified whitening agent prepared was not added tartaric acid, and the rest of the operations were the same.
Comparative example 4
The nano calcium carbonate is selected from some commercial nano calcium carbonate.
The nano calcium carbonate obtained in the above examples 1 to 3 and comparative examples 1 to 4 was subjected to performance test, the test method is as follows, and the results are shown in Table 1.
Whiteness: the whiteness measuring analyzer is adopted for measuring, the whiteness measuring analyzer is a light-pass Bo whiteness color measuring instrument YQ-Z-48B, the technical performance accords with JB/T9327-1999 whiteness measuring standard, and the measuring result is displayed digitally.
From the test data, the whiteness and the antioxidation capability of the nano calcium carbonate can be effectively improved by adding the anti-discoloration castor oil auxiliary agent and the modified whitening agent in the preparation process.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (9)
1. A preparation method of active nano calcium carbonate is characterized in that: the preparation method comprises the following steps:
s11, pretreatment of quicklime: gradually dissolving quicklime with a little excessive amount of dilute hydrochloric acid, adding hydrogen peroxide, adjusting the pH of the solution to be slightly alkaline, fully stirring, standing, and filtering to obtain a purified calcium ion solution;
s12, adding warm water into the calcium ion solution, fully stirring for 5 hours in a stirrer to obtain calcium hydroxide suspension, and filtering by using a standard sieve with 200 meshes;
s13, pouring the filtered calcium hydroxide suspension into a jacketed reactor, and cooling the calcium hydroxide suspension by using circulating water to cool the solution in the reactor to normal temperature;
s14, fully dissolving the modified anti-discoloration castor oil auxiliary agent and the modified whitening agent by using absolute ethyl alcohol, pouring the mixture into a jacketed reactor, introducing carbon dioxide gas under the stirring state of a stirrer for carbonization reaction, starting circulating water while stirring to keep the solution temperature in a reaction container at normal temperature, regulating the introducing rate and stirring speed of the carbon dioxide according to the solution temperature to control the reaction, and stopping the reaction when the pH value of a reaction system is 7.0-7.5 to obtain calcium hydroxide slurry;
and S15, aging, filtering, washing, drying and sieving the calcium hydroxide slurry to obtain the nano calcium carbonate.
2. The method for preparing active nano calcium carbonate according to claim 1, wherein: the preparation process of the modified anti-discoloration castor oil auxiliary agent comprises the following steps:
s21, dissolving gelatin by deionized water, stirring in a constant-temperature water bath at 45 ℃ for 60min until the gelatin is completely dissolved, regulating the pH of the gelatin solution to 7-8 by using 10% sodium hydroxide solution, and preparing the gelatin solution into 20mg/mL to obtain solution A;
s22, maintaining an anaerobic and anhydrous environment, dissolving a borate coupling agent in absolute ethyl alcohol under the protection of inert gas, fully and uniformly stirring, adding 2-3 times of castor oil active agent, and reacting for 2 hours at normal temperature by using a microwave method to obtain a solution B;
s23, mixing the solution A, B in equal volume, adding 1-1.5% of linear sodium dodecyl benzene sulfonate, placing on a constant temperature magnetic stirrer, stirring for 3 hours at room temperature, and carrying out ultrasonic treatment to obtain the modified castor oil auxiliary agent.
3. The method for preparing active nano calcium carbonate according to claim 1, wherein: the preparation process of the modified whitening agent comprises the following steps:
the modified coumarin fluorescent brightening agent is prepared by taking hexahydrophthalic anhydride as a crosslinking agent, introducing a 7-hydroxy-4-methylcoumarin fluorescent brightening agent, tartaric acid and triethoxysilane coupling agent into the same molecule, and hydrolyzing the mixture, wherein the specific preparation method is as follows:
dissolving hexahydrophthalic anhydride in dichloromethane, stirring for 20min, dropwise adding 7-hydroxy-4-methylcoumarin solution fully dissolved by dichloromethane under stirring, regulating the pH of the solution at normal temperature to be unchanged, adding tartaric acid, continuously regulating the pH to be 5-6, and steaming until the solution is completely volatilized; adding deionized water to dissolve the components completely, adding a triethoxysilane coupling agent under stirring, slowly heating to 90-95 ℃, reacting until the pH value is unchanged, cooling, standing and precipitating the mixed solution, and suction-filtering and drying to obtain a product, wherein the molar ratio of hexahydrophthalic anhydride to 7-hydroxy-4-methylcoumarin to tartaric acid to siloxane coupling agent is 1-1.5: 3: 1-2: 1.
4. the method for preparing active nano calcium carbonate according to claim 1, wherein: the mass fraction of the modified anti-discoloration castor oil auxiliary agent and the modified whitening agent is 1-2%.
5. The method for preparing active nano calcium carbonate according to claim 1, wherein: the temperature of the warm water is 30-45 ℃.
6. The method for preparing active nano calcium carbonate according to claim 1, wherein: the ratio of the quicklime to the warm water is 1:2 to 3.
7. The method for preparing active nano calcium carbonate according to claim 1, wherein: the rotating speed of the stirrer is 1000-2000 r/min, and the carbon dioxide introducing speed is 30-45L/min.
8. The method for preparing active nano calcium carbonate according to claim 1, wherein the concentration of calcium hydroxide in the calcium hydroxide slurry is 10 to 16wt%.
9. The method for preparing active nano calcium carbonate according to claim 1, wherein the obtained calcium hydroxide slurry is aged, filtered, washed, dried, and ground by a ball mill and then passes through a 200-mesh standard sieve.
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