CN1228246C - Method for prodn. of active nano calcium carbonate - Google Patents
Method for prodn. of active nano calcium carbonate Download PDFInfo
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- CN1228246C CN1228246C CN 02156883 CN02156883A CN1228246C CN 1228246 C CN1228246 C CN 1228246C CN 02156883 CN02156883 CN 02156883 CN 02156883 A CN02156883 A CN 02156883A CN 1228246 C CN1228246 C CN 1228246C
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Abstract
The present invention discloses a production method of active nanometer calcium carbonate. The method comprises the following steps of calcining 85 to 95 wt% of MgCO3 and 2 to 5 wt% of common limestone, adding water to quick lime produced after calcination for slaking reaction to produce coarse lime cream, purifying the coarse lime cream to obtain fine lime cream, adding crystallization control agents to the fine lime cream, leading in CO2 with the volume content of at least 55% for carbonization, activating carbonized slurry produced after carbonization by adding activating agents, and filtering, drying, pulverizing and sieving activated slurry produced after activation to obtain active nanometer calcium carbonate as finished products. The method has the advantages of simple technical process, low cost, no pollution to environment, uniform product granularity, high product activation rate more than or equal to 98%, and good dispersion property.
Description
Technical field
The present invention relates to a kind of production method of lightweight nano-calcium carbonate, the invention particularly relates to a kind of production method of active nano-calcium carbonate.
Background technology
Active nano-calcium carbonate belongs to a kind of of lightweight (precipitation) lime carbonate, the primary structure particle diameter≤100nm of " nanometer " expression lime carbonate, and " activity " expression product particle is that product particle has oleophilic properties through surface treatment.
The manufacture method of known lightweight (precipitation) lime carbonate is very high to the raw material limestone specification of quality: as to contain CaCO by weight
3〉=96.5%, MgCO
3≤ 1.46% (select from four of inorganic chemicals industry technology book series---the production and the application of lime carbonate.Hu Zhitong.The Inner Mongol People's Press.2001.4)。If the manufacturing nanometer grade calcium carbonate can be higher to the Wingdale specification of quality, this not only increases cost, and has limited the nano-calcium carbonate industrial expansion.And the useless ash breast that produces in the production process and contain CO
2Carbonization tail gas environment is had to a certain degree pollution, the product activation rate that known in addition activator and activating process make is low, dispersing property is not good enough, influences effect.
Summary of the invention
Main purpose of the present invention provides a kind of with weight ratio CaCO at the above-mentioned shortcoming that prior art exists
3For: 85～95%, MgCO
3For: 2～5% common lime stone and CO
2The gas of volume content 〉=55% is raw material, produces the method for active nano-calcium carbonate, and this method technological process is simple, cost is low, and the product granularity that makes is even.
Another object of the present invention is to and the solvay soda process soda ash combined producting, make that the waste gas and the waste residue that produce in the production process are utilized, can not produce pollution environment.
A further object of the invention is to improve the activation rate of product, improves its dispersing property.
The invention provides a kind of production method of active nano-calcium carbonate, it may further comprise the steps: (1) is with weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, adding temperature and be 40--90 ℃ water in the unslaked lime that calcining back generates carries out digestion reaction and generated the cinder breast in 5 seconds-30 minutes, refining ash breast and useless ash breast will be obtained after the described cinder milk extract system, it is 10 that described refining ash breast is converted into the weight ratio that contains CaO with useless grey breast: 1-1: 6, and the concentration of described refining ash breast is calculated as 4-20% to be converted into the weight ratio that contains CaO; (2) in described refining ash breast, add a kind of in aluminum chloride, Sodium hexametaphosphate 99 or the trisodium phosphate that accounts for the 0-2% of contained lime carbonate dry weight in the carbonization terminal point slip, and then feeding CO
2The gas of volume content 〉=55% carries out carbonization, and carbonization temperature is 5-25 ℃, and the reaction times is 40-120 minute; (3) the carbonization slip that makes after the carbonization being sent to activation procedure adding activator activates; (4) the activation slip that makes after will activating filter, wash, dry, pulverize, sieving makes the finished product active nano-calcium carbonate.
Described activation procedure is the dispersion agent that adds the dry weight 0.1～10% that accounts for lime carbonate in the slip at the carbonization slip earlier, after stirring 10～30 minutes, the modified resin acid that adds the dry weight 0.1～10% that accounts for lime carbonate in the slip again, continue to stir 30～120 minutes, the temperature of reactivation process is 40～80 ℃.
Adopting general Wingdale in the inventive method is raw material, utilizes CO
2The gas of volume content 〉=55% carries out the grey newborn carbonization of essence, add crystal controlling agent in the smart ash breast before carbonization, carbonization is effective, even particle size distribution, granularity≤80nm has reduced production cost, simultaneously since can with the solvay soda process soda ash combined producting, so useless ash breast that produces in the production process and useless tail gas can return the utilization of system alkali system, can not pollute environment.Another advantage of the present invention is that activation procedure of the present invention adopts compound activator, i.e. modified resin acid generates a kind of lipophilic compound with the dispersion agent reaction, and the firm surface that is coated on calcium carbonate granule makes product activation rate 〉=98%, good dispersity.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment and embodiment.
The raw material limestone of making active nano-calcium carbonate adopts general Wingdale, and (weight ratio is CaCO
3: 90～92%, MgCO
3: 3.0～4.5%) be raw material, the Wingdale and the solvay soda process soda ash combined producting that can adopt ammonia alkali legal system soda ash to use, this Wingdale contains MgCO
3, Fe
2O
3, SiO
2More Deng impurity, these impurity must be removed in " refining step ".The process for purification of known technology just promptly removes SiO with the swirler desanding
2, all the other impurity can't be removed.The present invention utilizes following principle: Wingdale is in calcination process, and impurity and CaO generate stodgy vitreum---XCaOAl
2O
3, YCaOFe
2O
3, ZCaOSiO
2Deng, to meet at " refining step " unslaked lime and water, fierce digestion reaction takes place in moment, and reaction heat is enough to make the boiling of ashing water, because CaO changes into Ca (OH)
2The time, volume increases, and unslaked lime moment splits, and ashing water takes advantage of a favourable situation to enter in the crack, thereby has quickened the carrying out of reaction.If impurity is contained in certain part in the Wingdale, must form vitreum herein, this vitreum digestion rate is extremely slow, so, can make with extra care the ash breast with the method for control digestion time.According to Wingdale quality and customer requirements, everyly in 5 seconds-30 minutes, be generally in 1～10 minute, do not participate in the unslaked lime of digestion reaction, be considered as waste product without exception, drain into outside the system, this material is called useless ash breast, thereby obtains refining ash breast.The extremely slow vitreum of digestion rate is not only contained in useless grey Ruzhong, also contains the CaO that is coated by vitreum in a large number.These CaO only under the condition that prolongs digestion time, could be digested.It is 10 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast: 1-1: 6, be generally 1: 2-1: 5, the concentration of refining ash breast is calculated as 4-20% to be converted into the weight ratio that contains CaO, so to drain for self-existent lime carbonate factory be unacceptable to Duo useless grey breast, cost will increase much on the one hand, simultaneously, the useless ash breast of discharging is with contaminate environment, but method provided by the invention can with the solvay soda process soda ash combined producting, useless grey breast can be sent to " lime slaking machine " further digestion of soda ash production system, is sent to ammonia still process then and recycles.
Add the crystal controlling agent account for the 0-2% of contained lime carbonate dry weight in the carbonization terminal point slip in the carbonation process of the inventive method in the carbonization slip, what described crystal controlling agent can be in aluminum chloride, Sodium hexametaphosphate 99 or the trisodium phosphate is a kind of.
The carbonation process of the inventive method utilizes volume content CO
2〉=55% gas carries out the carbonization of smart ash breast, the hypomere gas that this carbonization usefulness gas can adopt the system washing tower (for removing CO2) to use, and what the carbonization of independent lime carbonate factory was used is the kiln gas in limestone kiln, this kiln gas volume content is CO
230-36%.Method provided by the invention can with the solvay soda process soda ash combined producting, carbonization tail gas can return the soda ash production system, is sent to carbonation process and recycles after pressurization.
Active nano-calcium carbonate is to carry out surface-treated to product particle.Known activation method is that the carbonization slip is warming up to about 60 ℃ under agitation condition, adds activator again, and activator is that surface treatment agent mainly contains resinous acid, lipid acid, titanic acid ester, aluminic acid ester etc., and then continues stir about 1 hour, but activation effect is not good enough.Activating technology provided by the invention carries out wet-process activation for utilizing compound activator, promptly in the carbonization slip, add earlier 0.1～10% the dispersion agent that accounts for lime carbonate dry weight in the slip, through stirring 10～30 minutes, add 0.1～10% the modified resin acid account for lime carbonate dry weight in the slip again, continue to stir 30～120 minutes, the temperature of reactivation process is controlled at 40～80 ℃, activation results is that modified resin acid generates a kind of lipophilic compound, the firm surface that is coated on calcium carbonate granule with the dispersion agent reaction.Described dispersion agent is that molecular weight is a kind of in 7000 low molecular weight polyacrylate or the polyacrylic acid-acrylate-co-polymer of sulfonate.Described modified resin acid is a kind of in rosin pentaerythritol ester or the esterase.
Embodiment 1
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 40 ℃ of hot water digests for 6 liters, digest and make the cinder breast after 8 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 1: 2.2 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 8.20% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, in described refining ash breast, add 0.5% the Sodium hexametaphosphate 99 that accounts for contained lime carbonate dry weight in the carbonization terminal point slip, feeding CO
2Volume content is 55% carbon dioxide gas, carbonization temperature is controlled at 15 ℃, reaction times is 40 minutes, make the carbonization slip, carbonized stock is put into activator, is warming up to 60 ℃ under agitation condition, adds 1% the titanic acid ester account for lime carbonate dry weight in the slip, continue to stir after 100 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 90%, and dispersing property is general.
Embodiment 2
The weight ratio CaCO that ammonia alkali legal system alkali is used
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 60 ℃ of hot water digests for 6 liters, make the cinder breast after digesting for 5 seconds, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, and it is 1: 6.0 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 4.0% to be converted into the weight ratio that contains CaO, get smart grey newborn 500ml and be put in the carbonizer, feed the hypomere gas that ammonia alkali legal system washing tower (for removing CO2) is used, its CO
2Volume content is 70%, carbonization temperature is controlled at 25 ℃, reaction times is 120 minutes, make the carbonization slip, carbonized stock is put into activator, is warming up to 80 ℃ under agitation condition, adds the lipid acid that accounts for lime carbonate dry weight 5% in the slip, continue to stir after 120 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 91%, and dispersing property is general.
Embodiment 3
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 90 ℃ of hot water digests for 6 liters, digest and make the cinder breast after 15 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 4: 1.01 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 12.90% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, in described refining ash breast, add 1% the alchlor that accounts for contained lime carbonate dry weight in the carbonization terminal point slip, feeding CO
2Volume content is 65% carbon dioxide gas, carbonization temperature is controlled at 5 ℃, reaction times is 50 minutes, make the carbonization slip, carbonized stock is put into activator, is warming up to 50 ℃ under agitation condition, adds the lipid acid that accounts for lime carbonate dry weight 3% in the slip, continue to stir after 30 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 91%, and dispersing property is general.
Embodiment 4
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 60 ℃ of hot water digests for 3.7 liters, digest and make the cinder breast after 30 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 10: 1.0 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 20.0% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, in described refining ash breast, add 2% the trisodium phosphate that accounts for contained lime carbonate dry weight in the carbonization terminal point slip, feeding CO
2Volume content is 70% carbon dioxide gas, carbonization temperature is controlled at 10 ℃, reaction times is 100 minutes, make the carbonization slip, carbonized stock is put into activator, is warming up to 40 ℃ under agitation condition, adds the aluminic acid ester that accounts for lime carbonate dry weight 10% in the slip, continue to stir after 60 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 95%, and dispersing property is general.
Embodiment 5
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 70 ℃ of hot water digests for 6 liters, digest and make the cinder breast after 8 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 1: 2.2 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 8.20% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, in described refining ash breast, add 2% the Sodium hexametaphosphate 99 that accounts for contained lime carbonate dry weight in the carbonization terminal point slip, feeding CO
2Volume content is 55% carbon dioxide gas, carbonization temperature is controlled at 5 ℃, reaction times is 50 minutes, make the carbonization slip, carbonized stock is put into activator, be warming up to 50 ℃, add the molecular weight account for lime carbonate dry weight 0.1% in the slip and be 7000 low molecular weight polyacrylate, stirred 30 minutes, add the rosin pentaerythritol ester that accounts for lime carbonate dry weight 2% in the slip again, continue to stir after 30 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 98%, and dispersing property is good.
Embodiment 6
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 50 ℃ of hot water digests for 6 liters, make the cinder breast after digesting for 5 seconds, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, and it is 1: 6.0 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, and the concentration of refining ash breast is calculated as 4.0% to be converted into the weight ratio that contains CaO, get smart grey newborn 500ml and be put in the carbonizer, feed CO
2Volume content is 70% carbon dioxide gas, carbonization temperature is controlled at 10 ℃, reaction times is 100 minutes, make the carbonization slip, carbonized stock is put into activator, be warming up to 40 ℃, add the molecular weight account for lime carbonate dry weight 5% in the slip and be 7000 low molecular weight polyacrylate, stir after 20 minutes, add the esterase that accounts for lime carbonate dry weight 10% in the slip again, continue to stir after 60 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 98%, and dispersing property is good.
Embodiment 7
The weight ratio CaCO that ammonia alkali legal system alkali is used
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 40 ℃ of hot water digests for 6 liters, digest and make the cinder breast after 15 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 4: 1.01 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 12.90% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, adding accounts for 1.5% alchlor of contained lime carbonate dry weight in the carbonization terminal point slip in described refining ash breast, feed the hypomere gas that ammonia alkali legal system washing tower (for removing CO2) is used, its CO
2Volume content is 70%, carbonization temperature is controlled at 25 ℃, reaction times is 120 minutes, makes the carbonization slip, and carbonized stock is put into activator, be warming up to 80 ℃, add the polyacrylic acid-acrylate-co-polymer of sulfonate that accounts for lime carbonate dry weight 10% in the slip, stir after 10 minutes, add the rosin pentaerythritol ester that accounts for lime carbonate dry weight 0.1% in the slip again, continue to stir after 120 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 99%, and dispersing property is good, and is pollution-free.
Embodiment 8
With weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, get 1 kilogram of unslaked lime after the calcining, adding 60 ℃ of hot water digests for 3.7 liters, digest and make the cinder breast after 30 minutes, the cinder breast is crossed 400 mesh sieves and is made smart ash breast and useless ash breast, it is 10: 1.0 that smart ash breast is converted into the weight ratio that contains CaO with useless grey breast, the concentration of refining ash breast is calculated as 20.0% to be converted into the weight ratio that contains CaO, getting smart grey newborn 500ml is put in the carbonizer, in described refining ash breast, add 0.5% the trisodium phosphate that accounts for contained lime carbonate dry weight in the carbonization terminal point slip, feeding CO
2Volume content is 75% carbon dioxide gas, carbonization temperature is controlled at 15 ℃, reaction times is 40 minutes, make the carbonization slip, carbonized stock is put into activator, be warming up to 60 ℃, add the polyacrylic acid-acrylate-co-polymer of sulfonate that accounts for lime carbonate dry weight 1% in the slip, stirred 30 minutes, add the esterase that accounts for lime carbonate dry weight 5% in the slip again, continue to stir after 100 minutes and make activated material, activated material after filtration, washing, dry, pulverize, sieving makes active nano-calcium carbonate.This product granularity is even, and activation rate is 98%, and dispersing property is good.
Claims (4)
1. the production method of an active nano-calcium carbonate is characterized in that it may further comprise the steps:
(1) with weight ratio CaCO
3For: 85～95%, MgCO
3For: 2～5% common lime stone calcining, adding temperature and be 40--90 ℃ water in the unslaked lime that calcining back generates carries out digestion reaction and generated the cinder breast in 5 seconds-30 minutes, refining ash breast and useless ash breast will be obtained after the described cinder milk extract system, it is 10 that described refining ash breast is converted into the weight ratio that contains CaO with useless grey breast: 1-1: 6, and the concentration of described refining ash breast is calculated as 4-20% to be converted into the weight ratio that contains CaO;
(2) in described refining ash breast, add a kind of in aluminum chloride, Sodium hexametaphosphate 99 or the trisodium phosphate that accounts for the 0-2% of contained lime carbonate dry weight in the carbonization terminal point slip, and then feeding CO
2The gas of volume content 〉=55% carries out carbonization, and carbonization temperature is 5-25 ℃, and the reaction times is 40-120 minute;
(3) the carbonization slip that makes after the carbonization being sent to activation procedure adding activator activates;
(4) the activation slip that makes after will activating filter, wash, dry, pulverize, sieving makes the finished product active nano-calcium carbonate.
2. the production method of active nano-calcium carbonate according to claim 1, it is characterized in that: described Wingdale is the common lime stone that ammonia alkali legal system alkali is used.
3. the production method of active nano-calcium carbonate according to claim 1 and 2 is characterized in that: the CO that described carbonization is used
2Gas is the hypomere gas that ammonia alkali legal system washing tower (for removing CO2) is used.
4. the production method of active nano-calcium carbonate according to claim 1, it is characterized in that: described activation procedure is that the molecular weight that adds earlier the dry weight 0.1～10% that accounts for lime carbonate in the slip in the carbonization slip is a kind of in 7000 low molecular weight polyacrylate or the polyacrylic acid-acrylate-co-polymer of sulfonate, after stirring 10～30 minutes, add a kind of in the rosin pentaerythritol ester of the dry weight 0.1～10% account for lime carbonate in the slip or the esterase again, continue to stir 30～120 minutes, the temperature of reactivation process is 40～80 ℃.
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|---|---|---|---|
| CN 02156883 CN1228246C (en) | 2002-12-20 | 2002-12-20 | Method for prodn. of active nano calcium carbonate |
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|---|---|---|---|
| CN 02156883 CN1228246C (en) | 2002-12-20 | 2002-12-20 | Method for prodn. of active nano calcium carbonate |
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| CN1228246C true CN1228246C (en) | 2005-11-23 |
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| CN102964880B (en) * | 2012-11-29 | 2014-04-23 | 辽宁艾海滑石有限公司 | Modified talcum for papermaking coating and preparation method thereof |
| CN103289448A (en) * | 2013-03-14 | 2013-09-11 | 河南工业大学 | Preparation method of ultrawhite, easily dispersible and high stability powder special for water-based paint |
| CN105621379A (en) * | 2016-04-13 | 2016-06-01 | 四川绵竹市盘龙矿物质有限责任公司 | Improved three-stage neutralization crystallization method in feed-grade calcium hydrogen phosphate production technique |
| CN110697752A (en) * | 2019-09-22 | 2020-01-17 | 佛山市展华科技有限公司 | Modification method of nano calcium carbonate |
| CN113353962A (en) * | 2021-06-10 | 2021-09-07 | 襄阳兴发化工有限公司 | Method for preparing active nano calcium carbonate at normal temperature and high concentration |
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