CN103274439B - A kind of method of oyster shells reprocessing cycle preparing nano calcium carbonate - Google Patents
A kind of method of oyster shells reprocessing cycle preparing nano calcium carbonate Download PDFInfo
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- CN103274439B CN103274439B CN201310271299.XA CN201310271299A CN103274439B CN 103274439 B CN103274439 B CN 103274439B CN 201310271299 A CN201310271299 A CN 201310271299A CN 103274439 B CN103274439 B CN 103274439B
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Abstract
The invention discloses a kind of method of oyster shells reprocessing cycle preparing nano calcium carbonate, the method directly utilizes oyster shells for raw material, no longer carry out Roasting-slaking operation, the great amount of carbon dioxide gas utilizing dissolving with hydrochloric acid oyster shells to produce carries out recovery and recycle, then obtains high whiteness and highly purified nano-calcium carbonate through ammoniacal liquor carbonization technique; The raw material oyster shells wide material sources that the present invention adopts, cost is low, has both solved the environmental pollution that oyster shells causes, has not produced secondary pollution again, has good popularizing application prospect.
Description
Technical field
The present invention relates to a kind of calcium carbonate nano raw powder's production technology, particularly a kind of method of oyster shells reprocessing cycle preparing nano calcium carbonate, belongs to the production technical field of nano material calcium carbonate.
Background technology
Nano-Calcium Carbonate refers to the ultrafine powder calcium carbonate of particle size between 1 ~ 200nm, is a kind of novel high-grade functional filling material.Nano-calcium carbonate is as a kind of abundant raw material source, low-cost nano material, due to the success of ultramicron and classification technique, and the developing of calcium carbonate surface chemical treatment method, premium properties and the use range of nano-calcium carbonate will be more wide, and quantity demand is increasing.Nano-calcium carbonate is one of inorganic nano-filler developed the earliest, become light filler important in multiple heavy chemicals industry, be widely used in all trades and professions such as plastics, papermaking, rubber, coating, ink, medicine, makeup, play the irreplaceable effect of other fillers.Because nano-calcium carbonate has excellent performance and purposes widely, the research and development of its preparation method and product innovation are received and payes attention to widely.In nano-calcium carbonate is produced, carburizing reagent workshop section is the core of whole technological process, and traditional nano-calcium carbonate is generally all adopted and obtained by calcining, digestion, carbonization, filtration by industrial raw material Wingdale, and cost is higher.
In recent years, the demand of nano-calcium carbonate rises year by year, and the preparation research of nano-calcium carbonate is one of Main way of the sector development.At present, people in various more efficient, the feasible preparation method of exploration, but also exist preparation costly, yield poorly and are difficult to the shortcomings such as industrialization, hindering the production of nano-calcium carbonate.
In coastland, because culture fishery is flourishing, oyster culture area, turnout and quantity sharply increase, and people, when edible oyster or processing shellfish, create a large amount of oyster shellss, current China is only confined to edible meat part for the processing of oyster shells, processing and utilization for oyster shells is few, causes this waste every year up to millions of ton, if do not made full use of, not only can cause serious impact to environment, and be a kind of serious wasting of resources.
At present, the utilization of waste material of oyster shells is only limitted to produce Wingdale or slaked lime etc.The physical property uneven due to oyster shells granularity and the factor such as the low chemical of lime content and process inconvenience, limit its utilization of waste material.The content of oyster shells calcium carbonate is up to more than 95%, and be the calcium source that a kind of natural, organism produces, be a kind of precious resources preparing the highly beneficial value of nano-calcium carbonate simultaneously.Patent CN98100447.4 high-temperature calcination after appropriate shell washing makes the shell aqueous solution, add ammonia chloride again and it is reacted into calcium chloride water, last calcium chloride water and the front carbonic acid ammonia generated that reacts are mixed and make calcium carbonate, again after filtration, dry and obtain nano-calcium carbonate, but calcining process used in this method adds energy consumption.In order to overcome the shortcoming of above-mentioned operation, the nano-calcium carbonate that the Gao Wenyan of Northwest University utilizes dissolving with hydrochloric acid oyster shells and carbonic acid ammonia replacement(metathesis)reaction technique to prepare size of particles and shape can arbitrarily to adjust, but a large amount of Cl that nano-calcium carbonate adsorbs
- , in production, use decantation to remove these Cl
- time often need a large amount of time and bath water, and the product cost producing different crystal forms is higher, not easily reaches a standard economically, seldom adopts both at home and abroad at present.
At home and abroad there is no the method utilizing oyster shells reprocessing cycle preparing nano calcium carbonate, the present invention not only solves the severe contamination of oyster shells to environment, and turns waste into wealth, and has saved production cost, has good popularizing application prospect.
Summary of the invention
The object of the invention is to overcome the shortcoming existed in prior art, directly utilize oyster shells for raw material, no longer carry out Roasting-slaking operation, recovery is carried out and recycle to the great amount of carbon dioxide gas that dissolving with hydrochloric acid oyster shells produces, obtains high whiteness and highly purified nano-calcium carbonate.
The object of the invention is to be achieved through the following technical solutions, comprise the following steps:
(1) oyster shells carried out wash, dry, be crushed to granularity at 10 ~ 400 orders, obtain oyster shell powder;
(2) oyster shell powder of 50g ~ 200g is poured in there-necked flask, be 0.1mol/mL by 5ml ~ 10ml(volumetric molar concentration) hydrochloric acid soln put into dropping funnel, slow instillation there-necked flask, and at there-necked flask opposite side, carbon dioxide gas recovery apparatus is installed, reaction 0.5 ~ 1h;
(3) after oyster shell powder completely dissolve in there-necked flask, add the ammoniacal liquor that volumetric molar concentration is 1mol/mL, regulate pH to 7 ~ 8, after stirring, be passed in there-necked flask by the carbon dioxide that step (2) reaction is collected, the white precipitate obtained after reaction 0.5 ~ 1.5h filters;
(4) pure water of 50ml ~ 200ml is heated to 80 ~ 95 DEG C, wash three times to the white depositions of step (3) under agitation, oven dry can obtain nano-calcium carbonate.
In step (4), bake out temperature is 90 DEG C.
The invention has the beneficial effects as follows:
(1) utilize discarded oyster shells to turn waste into wealth, not only solve the severe contamination of oyster shells to environment, and turn waste into wealth, saved production cost;
(2) relatively simple, reproducible without high temperature, high pressure, condition of high vacuum degree, highly corrosive, technological process in whole technological process;
(3) employing the method easily removes the Cl on nano-calcium carbonate
- .
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
embodiment 1
Oyster shells is obtained 10 object oyster shell powders through washing, oven dry, pulverizing.The oyster shell powder of 50g is poured in there-necked flask, be that the hydrochloric acid soln of 0.1mol/mL puts into dropping funnel by 5ml volumetric molar concentration, slow instillation there-necked flask, and at there-necked flask opposite side, carbon dioxide gas recovery apparatus is installed, react after 30 minutes, add 1mol/mL ammoniacal liquor to it and regulate pH to 7.5, after stirring, the carbon dioxide of recovery is passed in there-necked flask and reacts after 40 minutes, filter and obtain white precipitate.Above-mentioned white precipitate being joined temperature is in the 50ml pure water of 95 DEG C, and agitator treating three times, oven dry can prepare nano-calcium carbonate.
embodiment 2
Oyster shells is obtained 100 object oyster shell powders through washing, oven dry, pulverizing.The oyster shell powder of 100g is poured in there-necked flask, be that the hydrochloric acid soln of 0.1mol/mL puts into dropping funnel by 10ml volumetric molar concentration, slow instillation there-necked flask, and at there-necked flask opposite side, carbon dioxide gas recovery apparatus is installed, react after 50 minutes, add 1mol/mL ammoniacal liquor to it and regulate pH to 8, after stirring, the carbon dioxide of recovery is passed in there-necked flask and reacts after 1 hour, filter the white precipitate obtained.Above-mentioned white precipitate being joined temperature is in the 100ml pure water of 90 DEG C, and agitator treating three times, oven dry can prepare nano-calcium carbonate.
embodiment 3
Oyster shells is obtained 300 object oyster shell powders through washing, oven dry, pulverizing.The oyster shell powder of 200g is poured in there-necked flask, be that the hydrochloric acid soln of 0.5mol/mL puts into dropping funnel by 4ml volumetric molar concentration, slow instillation there-necked flask, and at there-necked flask opposite side, carbon dioxide gas recovery apparatus is installed, react after 50 minutes, add 1mol/mL ammoniacal liquor to it and regulate pH to 7, after stirring, the carbon dioxide of recovery is passed in there-necked flask and reacts after 1.5 hours, filter the white precipitate obtained.Above-mentioned white precipitate being joined temperature is in the 200ml pure water of 90 DEG C, and agitator treating three times, oven dry can prepare nano-calcium carbonate.
Claims (3)
1. a method for oyster shells reprocessing cycle preparing nano calcium carbonate, is characterized in that: comprise the steps:
(1) oyster shells carried out wash, dry, be crushed to granularity at 10 ~ 400 orders, obtain oyster shell powder;
(2) oyster shell powder of 50g ~ 200g is poured in there-necked flask, the hydrochloric acid soln after metering is put into dropping funnel, slowly instills there-necked flask, and at there-necked flask opposite side, carbon dioxide gas recovery apparatus is installed, reaction 0.5 ~ 1h;
(3) after oyster shell powder completely dissolve in there-necked flask, add a certain amount of ammoniacal liquor, regulate pH to 7 ~ 8, after stirring, be passed in there-necked flask by the carbon dioxide that step (2) reaction is collected, the white precipitate obtained after reaction 0.5h ~ 1.5h filters;
(4) pure water of 50mL ~ 200mL is heated to 80 ~ 95 DEG C, wash three times to the white depositions of step (3) under agitation, oven dry can obtain nano-calcium carbonate; Described bake out temperature is 90 DEG C;
The amount of the hydrochloric acid soln after described metering is 5mL ~ 10mL.
2. the method for a kind of oyster shells reprocessing cycle preparing nano calcium carbonate according to claim 1, is characterized in that: the volumetric molar concentration of the hydrochloric acid soln after described metering is 0.1mol/mL.
3. the method for a kind of oyster shells reprocessing cycle preparing nano calcium carbonate according to claim 1, is characterized in that: a certain amount of ammoniacal liquor described in step (3) refers to that the volumetric molar concentration adding ammoniacal liquor is 1mol/mL, and consumption is for regulating pH to 7 ~ 8.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044821A (en) * | 2016-07-19 | 2016-10-26 | 陈毅忠 | Method for preparing nanometer calcium carbonate by virtue of oyster shells |
| CN107929313B (en) * | 2017-11-21 | 2021-02-19 | 上海金城素智药业有限公司 | Natural oyster calcium carbonate preparation for preventing and treating calcium deficiency and preparation method thereof |
| CN108298918A (en) * | 2018-04-10 | 2018-07-20 | 朱文杰 | The preparation method of maritime concrete is corroded in a kind of salt resistance |
| CN108997785A (en) * | 2018-08-03 | 2018-12-14 | 李远奖 | A kind of preparation method of the nano modification conch meal with durable antibiotic |
| CN109938039A (en) * | 2019-04-19 | 2019-06-28 | 泉州师范学院 | A kind of preparation method and antibacterial applications of CaO/ZnO composite nano materials |
| CN110589864A (en) * | 2019-09-27 | 2019-12-20 | 泉州师范学院 | Method for preparing oyster nano calcium carbonate by taking trypsin as crystal form control agent |
| CN111921486A (en) * | 2020-07-09 | 2020-11-13 | 内江师范学院 | Nano calcium carbonate and preparation method and application thereof |
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|---|---|---|---|---|
| CN102583482A (en) * | 2012-02-14 | 2012-07-18 | 浙江大学 | Preparation method of flake-shaped aragonite calcium carbonate |
| CN102874857A (en) * | 2012-09-10 | 2013-01-16 | 浙江大学 | Method for preparing sheet-shaped calcium carbonate by thermally decomposing shell through hydrothermal process |
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Patent Citations (2)
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|---|---|---|---|---|
| CN102583482A (en) * | 2012-02-14 | 2012-07-18 | 浙江大学 | Preparation method of flake-shaped aragonite calcium carbonate |
| CN102874857A (en) * | 2012-09-10 | 2013-01-16 | 浙江大学 | Method for preparing sheet-shaped calcium carbonate by thermally decomposing shell through hydrothermal process |
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| 添加剂条件下氯化钙制备纳米碳酸钙;陈敏等;《合肥工业大学学报（自然科学版）》;20070930;第30卷(第9期);第1128-1130页 * |
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