CN107814404A - A kind of production method of cube nano-calcium carbonate - Google Patents
A kind of production method of cube nano-calcium carbonate Download PDFInfo
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- CN107814404A CN107814404A CN201610821344.8A CN201610821344A CN107814404A CN 107814404 A CN107814404 A CN 107814404A CN 201610821344 A CN201610821344 A CN 201610821344A CN 107814404 A CN107814404 A CN 107814404A
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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Abstract
The invention discloses a kind of production method of cube nano-calcium carbonate, this method comprises the following steps：1) take lime stone and coke to be calcined in shaft kiln and produce calcium oxide and kiln gas；2) calcium hydroxide suspension of purification kiln gas and compound concentration for 5~15wt% is taken；3) it is aged after carrying out two-stage carbonization using supergravity reactor；4) it is modified at a temperature of 40~80 DEG C；5) filtering, dry, broken, classification, obtain cube nano-calcium carbonate.The production method production efficiency of the present invention is high, raw material sources are wide, cost is low, and the production method realizes the continuous production of nano-calcium carbonate, meanwhile the auxiliary agents such as chemical additives need not be added in production process granularity can be prepared in 10~80nm narrow particle size distribution and form, the cube nano-calcium carbonate of steady quality.
Description
Technical field
The present invention relates to technical field of nanometer material preparation.More particularly, to a kind of cube nano-calcium carbonate and its
Production method.
Background technology
Calcium carbonate has in all conglomeraties such as plastics, rubber, coating, ink, papermaking, silicone adhesive, automobile widely should
With.In recent years, with the continuous development of calcium carbonate nano and process for modifying surface so that the application value of calcium carbonate is expected to
To being greatly improved.Cube nano-calcium carbonate is added in plastics, rubber, paper as filler, can improve the machine of material
Tool performance, it has also become the maximum nano-calcium carbonate of application amount at present.Therefore, regular appearance, the nanometer of narrow particle size distribution are developed
Calcium carbonate industry production technology tool is of great significance.
The research and development of China's nano-calcium carbonate start from phase early 1980s, and production mainly uses following several sides
Method, including interval bubbling carbonation method, continuous pythagoras number, continuous multilevel spray carbonization, gravity Method, porous embrane method etc..
The production method of nano-calcium carbonate mainly has both at home and abroad at present：
1 interval bubbling carbonation method
Whether there is agitating device according in carbonators, the method is divided into general batch bubbling carbonizing method and stirring-type interval drum again
Steep carbonizatin method.Refined calcium hydroxide suspension and appropriate chemical additives are added in carbonators, is then passed through from bottom of towe
Carbon dioxide to pH value is changed into 7, just obtains calcium carbonate product.It is the method small investment, simple to operate, but produce discontinuous, automation
Degree is low, and Granularity Distribution is uneven, and average grain diameter is larger, and the poor repeatability of different batches of product.
2 continuous pythagoras numbers
The method is typically carbonized using two-stage or thtee-stage shiplock, and the calcium hydroxide suspension that will be refined is through first order carbonators
Carry out it is partially carbonized after obtain reaction mixture, added in stock tank after appropriate additive and enter back into second level carbonators carbonization
Obtain product or enter back into be carbonized in third level carbonators to obtain final products.Because carbonisation substep is carried out, using between level
Carry out surface-active-treatment, and carburizing temperature can be controlled by freezing, thus to the nucleation, growth course and surface of crystal formation at
Reason and Discrete control, can obtain less particle diameter and particle diameter distribution.Now, the domestic manufacturer for using the technology can root
Require to produce required crystal formation and grain by strictly controlling slurry concentration, carburizing temperature, additive types and dosage etc. according to user
The product in footpath.But the process conditions of this method are complicated, control difficulty is very big, needs also exist for adding the addition such as chemical additives
Agent, and the particle diameter of products obtained therefrom equally exists the problem of being distributed relatively poor and product poor repeatability, it is because carbon to trace it to its cause
Caused by microcosmic mixing is uneven in change tower.
3 multi-stage spray carbonizatin methods
The basic step of multi-stage spray preparation of nanometer calcium carbonate by carbonization is：Prepared by refined calcium hydroxide suspension
Into the concentration of technological requirement, appropriate additive is added, is pumped into after fully mixing in the atomizer of multistage spray carbonation top of tower, in height
Under huge centrifugal action caused by speed rotation, slurries are atomized the droplet for fine particle size；Contain titanium dioxide after purification
Carbon gas is entered by bottom of towe, is dispersed in through gas distributor in tower, and droplet carries out instantaneous reverse contact in tower with gas
Generation chemical reaction generation calcium carbonate.The granularity of the calcium carbonate product prepared by multi-stage spray carbonizatin method is tiny and uniform, average
Particle diameter can be with adjustment control in 30-40nm scopes, particulate crystal formation.Shortcoming is that equipment investment is larger, and shower nozzle easily blocks, technology
More complicated, operation difficulty is larger, promotes its commercial Application and is restricted.
4 perforated membrane microreactor carbonizatin methods
Tsing-Hua University have developed the scattered micro-structural of film for preparing nano-calcium carbonate with Shandong magnificence Science and Technology Co., Ltd.
Reactor.By the use of the membrane material that aperture is several microns or tens microns as decentralized medium, promote mass transfer by strengthening microcosmic mixing
With the quick progress of reaction, make the calcium carbonate particle diameter of preparation small and be evenly distributed.By regulating and controlling slurry concentration, gas-liquid flow, pressure
The parameters such as power can preferably control the particle diameter and crystal formation of product.But because the size of membrane material is too small, it is careless slightly during operation
The concentration of calcium hydroxide slurry is relatively low when may block membrane material because of fouling, therefore be carbonized, and uses intermittently operated side
Formula, therefore the problems such as operating process is complicated, and cost is high be present.
5 high-gravity carbonation methods
Hypergravity ERC of Beijing University of Chemical Technology develops gravity Method production nano-calcium carbonate new technology, utilizes
The Elevated Gravity more much bigger than terrestrial gravitation acceleration caused by rotation, greatly enhance transmittance process between gas-liquid two-phase and
Micro mixing, and carbonation reaction and crystallization process can effectively be controlled by the modulation of technological parameter, it is prepared
The nano-calcium carbonate powder that granularity is small, is evenly distributed.However, because nano-calcium carbonate is easy to the fouling on filler, therefore transporting
Equipment must just be cleaned after row a period of time, not only increase the workload of worker, and operating process is also relatively multiple
It is miscellaneous.
Therefore it is, it is necessary to a kind of new, the above-mentioned insufficient method for preparing nano-calcium carbonate can be overcome.
The content of the invention
First purpose of the present invention is to provide a kind of production method of cube nano-calcium carbonate, this method production effect
Rate is high, and raw material sources are wide, and cost is low, safety and environmental protection, and the production method realizes the continuous production of nano-calcium carbonate, together
When, need not add in production process the auxiliary agents such as chemical additives granularity can be prepared in 10~80nm narrow particle size distribution and
The cube nano-calcium carbonate of form, steady quality.
Second object of the present invention is to provide the cube nano-calcium carbonate that aforementioned production method produces to obtain.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of production method of cube nano-calcium carbonate, comprises the following steps：
1) take lime stone and coke to be calcined in shaft kiln and produce calcium oxide and kiln gas；
2) by the cooling of above-mentioned kiln gas, dedusting and desulfurization, the purification kiln gas that gas concentration lwevel is 15~40% is obtained；With above-mentioned
Calcium oxide is raw material, and compound concentration is 5~15wt% calcium hydroxide suspension；
3) be carbonized workshop section：In equipment start-up, calcium hydroxide suspension obtained by step 2) is led to after heat exchanger first
Cross feed pump to be pumped into the first stirred tank supporting with one-level supergravity reactor, when the material in the first stirred tank reaches pre-
Stop feed pump after determining volume, then the material in the first stirred tank is pumped into one-level supergravity reactor and connect with purification kiln gas
Touch and carry out carburizing reagent, the pH for being recycled to slurry in one-level supergravity reactor is 8~12, afterwards, foregoing one-level carbonizer
Section enters continuous running status, reopens feed pump, at the same by the slurry in one-level supergravity reactor according to feed pump
Same flow is pumped into two level supergravity reactor, and is contacted and occurred with the purification kiln gas from one-level supergravity reactor
Reaction, the slurry for leaving two level supergravity reactor flows into the second supporting stirred tank, when slurry reaches pre- in the second stirred tank
If being started the cycle over after volume, circulation slurry mixes with the slurry from one-level supergravity reactor and in two level supergravity reactor
In continue carburizing reagent, the pH controls of slurry are 6.8~7 in two level supergravity reactor, the slurry in the second stirred tank
After material reaches predetermined, the slurry in two level supergravity reactor is sent into aging tank progress according to input quantity identical amount
Ageing, said second carbonization workshop section initially enter continuous running status, wherein, one-level supergravity reactor and two level hypergravity are anti-
The temperature of device is answered to control at 10~50 DEG C；
4) slurry after ageing is pumped into modified tank, it is modified at a temperature of 40~80 DEG C；
5) modified slurry is filtered, is dry, be broken, classification, obtaining cube nano-calcium carbonate calcium product.
Further, in step 2), the compound method of calcium hydroxide suspension is：By calcium oxide obtained by step 1) through removal of impurities
Afterwards plus 40~70 DEG C of hot water digest, and wherein the mass ratio of calcium oxide and hot water is 1:4~7, then 6~12 are aged after screening and removing impurities
Hour, then remove the gred and be diluted with water after suspension separator, obtain the calcium hydroxide suspension that concentration is 5~15wt%.
Further, in step 3), one-level supergravity reactor and the slurry being pumped into two level supergravity reactor are pumped into
Material and/or material and purification kiln gas independently for current contacting or counter current contacting, be preferably counter current contacting.
Further, in step 3), the choosing of the one-level supergravity reactor and two level supergravity reactor independently
From high gravity rotating packed bed or with the supergravity reactor from pressurization, for example, Publication No.：CN104511235A
Disclosed in from supercharging RPB device, Publication No.：Low pressure drop nano-micro structure disclosed in CN102120172A is filled out
Expect rotating bed super gravity device.
Further, in step 3), the hypergravity of the one-level supergravity reactor and two level supergravity reactor is horizontal
Respectively 30~500.
Preferably, in certain specific embodiments of the invention, the one-level supergravity reactor and two level hypergravity
The horizontal hypergravity of reactor is respectively 30~500.
In the present invention, the horizontal definition of hypergravity is：
In formula：
β：Hypergravity is horizontal
ω：Angular speed, s-1
rm：Rotor mean radius, m
N：Rotating speed, rpm
rin：Rotor inside radius, m
rout：Rotor outer radius, m
g：Acceleration of gravity, ms-2。
Further, in step 3), in the packing layer of the one-level supergravity reactor and two level supergravity reactor
Filler is modified nickel foam filler, and the processing procedure of the modified nickel foam filler includes：By nickel foam filler successively 40~
Soaked in 70 DEG C of sodium hydroxide solution, dilution heat of sulfuric acid, after being cleaned by ultrasonic in ethanol solution, by nickel foam filler
It is 0.01~0.05molL to be placed in concentration-11- myristyl phosphoric acid ethanol solution in soak 40~60 hours, its
In, soaking temperature is 50 DEG C, further takes out, dries, obtains modified nickel foam filler.
Preferably, in certain specific embodiments of the invention, the processing procedure of the modified nickel foam filler includes：
(1) nickel foam filler is immersed into 0.5~1.5molL-1Sodium hydroxide solution in, using heating water bath to 40~
70 DEG C, 30min~60min is incubated, deionized water rinsing is used three times after nickel foam filler is taken out；
(2) after the nickel foam filler after flushing is air-dried, dilute H is immersed2SO4In solution, heating water bath to 40~70 is utilized
DEG C, 20min~40min is incubated, deionized water rinsing is used three times after nickel foam filler is taken out；
(3) after the nickel foam filler after flushing is air-dried, it is put into ethanol solution, it is super to it using ultrasonic instrument
Sound 10min~30min；
(4) it is 0.01molL to be directly placed into concentration after nickel foam filler is taken out-1~0.05molL-11- 14
Soaked 40~60 hours in the ethanol solution of alkyl phosphoric acid, keep it in 50 DEG C with heating water bath always therebetween；
(5) the nickel foam filler after taking-up processing, naturally dry in atmosphere after being cleaned using ethanol solution, must change
Property nickel foam filler.
Further, in step 4), the step of the modification includes：Slurry after ageing is pumped into modified tank, heated up
To 40~80 DEG C of temperature, surfactant, stirring insulation 1~3 hour are added, then stand insulation 1~3 hour.
Preferably, the addition of the surfactant is 2~6% of the stock quality after ageing.
Preferably, the surfactant is selected from stearic acid, odium stearate, dioctyl phthalate, palmitic acid, glycerine
One kind in ester, silane coupler, titanate coupling agent or with the several of arbitrary proportion mixing.
Further, in step 5), the filtering refers to use press filtration or centrifugal filtration, obtains 40~50wt% of water content
Filtration product；The drying includes carrying out filtration product one-level drying and secondary drying so that the water content of press filtration product
It is down to below 0.5wt%.
The present invention cube nano-calcium carbonate that also protection is obtained using aforementioned production method.
Further, the granularity of the cube nano-calcium carbonate is 10~80nm, is cube nano-calcium carbonate.
Unless otherwise specified, the raw material used in the present invention can be commercially available or by this area routine by commercially available
Means obtain.
Unless otherwise specified, any scope described in the present invention include any numerical value between end value and end value and
Any subrange that any number between end value or end value is formed.
Beneficial effects of the present invention are as follows：
1. the production method of the present invention employs special modified nickel foam filler, efficiently avoid in hypergravity reaction
Obtained calcium carbonate slurry in the fouling on filler surface, solve the problems, such as that batch cleaning must be carried out because of fouling, save
Time, improve production efficiency.
2. in the present invention by the way of two-stage carbonization, pH in carbonisation is declined into process and stabilization process respectively two
Carried out in individual supergravity reactor, realize continuous production, reduced Batch Process charging, the non-cutting time of discharging, improve
Production efficiency, meanwhile, obtained product quality is stable, overcomes the shortcomings that properties of product between different batches have differences, makes
Obtaining cost reduces.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the technological process of production of cube nano-calcium carbonate in the present invention.
Fig. 2 shows the transmission electron microscope picture for the cube nano-calcium carbonate that the embodiment of the present invention 2 is prepared.
Fig. 3 shows the size distribution plot for the cube nano-calcium carbonate that the embodiment of the present invention 2 is prepared.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
The technological process of production of cube nano-calcium carbonate is as shown in Figure 1 in the present invention：
Lime stone and coke are subjected to high-temperature calcination in shaft kiln, calcined product calcium oxide and kiln gas is obtained, kiln gas is passed through
Cooling, dedusting and desulfurization, obtain the purification kiln gas of the carbon dioxide containing finite concentration；Calcium oxide is then transported to after reciprocating sieve cleans
Workshop section is digested, the calcium hydroxide suspension obtained after digestion is pumped into carbonization workshop section after refined, curing.By calcium hydroxide slurry
Contact and react in the I and II supergravity reactor filled with modified nickel foam filler successively with purification kiln gas, make
PH decline processes must be reacted and stabilization process is carried out in different supergravity reactors respectively, nano-calcium carbonate slurry is prepared
Nano-calcium carbonate powder product is obtained after material, then surface treated, filtering, drying, broken and classification.
The supergravity reactor used in the embodiment of the present invention can be for example, Publication No.：CN2221437A middle promulgated by the State Council
The high gravity rotating packed bed of conventional structure disclosed in bright patent application, Publication No.：CN104511235A Chinese invention
The RPB device having from function of increasing pressure disclosed in patent application.And the packing layer of the supergravity reactor of the present invention
In be filled with modified nickel foam filler.
Embodiment 1
The preparation of modified nickel foam filler, step are as follows：
(1) nickel foam filler is immersed into 1.0molL-1Sodium hydroxide solution in, using heating water bath to 60 DEG C, insulation
45min, deionized water rinsing is used three times after nickel foam filler is taken out；
(2) after the nickel foam filler after flushing is air-dried, dilute H is immersed2SO4In solution, using heating water bath to 60 DEG C, protect
Warm 25min, deionized water rinsing is used three times after nickel foam filler is taken out；
(3) after the nickel foam filler after flushing is air-dried, it is put into ethanol solution, it is super to it using ultrasonic instrument
Sound 15min；
(4) it is 0.03molL to be directly placed into concentration after nickel foam filler is taken out-11- myristyl phosphoric acid it is anhydrous
Soaked 45 hours in ethanol solution, keep it in 50 DEG C with heating water bath always therebetween；
(5) the nickel foam filler after taking-up processing, naturally dry in atmosphere after being cleaned using ethanol solution, must change
Property nickel foam filler.
After measured, before modified nickel foam filler surface and the contact angle of water is 108.5 °, and modified modification foam
The contact angle of nickel filler surface and water can be extended to about 150 °.
In certain embodiments of the present invention, the concentration of above-mentioned sodium hydroxide solution is for example, can be 0.5molL-1、
0.8mol·L-1、1.2mol·L-1、1.5mol·L-1, the performance of obtained modified nickel foam filler is modified with above-mentioned gained steeps
Foam nickel carrier performance is close.
In certain embodiments of the present invention, above-mentioned steps (1) and step (2) bath temperature are for example, can distinguish
Stand alone as 40 DEG C, 50 DEG C, 60 DEG C, the performance of obtained modified nickel foam filler and above-mentioned gained modified nickel foam carrier performance phase
Closely.
Embodiment 2
A kind of production method of cube nano-calcium carbonate, its step are as follows：
1) calcine：Lime stone and coke in mass ratio 9.8:1 calcines in shaft kiln high temperature, obtains calcium oxide and kiln gas；
2) kiln gas purification and digestion, refined：
Kiln gas is cooled, dedusting and desulfurization, obtain the purification kiln gas that gas concentration lwevel is 35%；
The calcium oxide obtained, after removal of impurities, digested with 70 DEG C of hot water of its 5 times of quality, then after screening and removing impurities it is old
Change 6 hours, then removed the gred after suspension separator separates and be diluted with water to obtain the calcium hydroxide suspension that concentration is 7wt%；
3) two-stage is carbonized：Above-mentioned calcium hydroxide suspension is pumped into after heat exchanger by feed pump overweight with one-level
In the first supporting stirred tank of power reactor, stop feed pump after the material in the first stirred tank reaches predetermined, then will
The one-level hypergravity that material in first stirred tank is pumped into the modified nickel foam filler prepared filled with embodiment 1 rotates filling
In bed, with the purification kiln gas current contacting being passed through from the air inlet of one-level high gravity rotating packed bed and carrying out carburizing reagent,
It is 10 DEG C to control the temperature in packed bed, and horizontal hypergravity is 150, and the pH for being recycled to slurry in packed bed is 8, afterwards, foregoing
One-level carbonization workshop section (including one-level high gravity rotating packed bed and the first supporting stirred tank) initially enters continuous running status,
Feed pump is reopened, while the slurry in one-level high gravity rotating packed bed is pumped into according to the flow same with feed pump and filled out
In the two level high gravity rotating packed bed of the modified nickel foam filler prepared filled with embodiment 1, and with being revolved from one-level hypergravity
Turn the purification kiln gas current contacting of packed bed and react, then slurry leaves two level high gravity rotating packed bed, and inflow is matched somebody with somebody
Set the second stirred tank, open the circulation pump starts the cycle over after material reaches preset vol in the second stirred tank, circulation slurry with
Slurry from one-level high gravity rotating packed bed mixes and continues carburizing reagent in two level high gravity rotating packed bed,
Temperature in adults power RPB is 10 DEG C, and horizontal hypergravity is 150, and adjustment circular flow revolves two level hypergravity
The pH controls for turning slurry in packed bed are 6.8, after the slurry in stirred tank reaches predetermined, by two level supergravity reactor
In part size according to input quantity identical amount be sent into aging tank be aged, said second carbonization workshop section (include two level
High gravity rotating packed bed and the second supporting stirred tank) initially enter continuous running status；
4) it is modified：Slurry after ageing is pumped into modified tank, is warming up to 80 DEG C, adds stock quality percentage 4%
Surfactant stearic acid, stirring insulation 2 hours, then 2 hours are stood, obtain modified slurry；
5) by modified slurry is filtered, dry, crushing and classification, packaging, nano-calcium carbonate powder is obtained.
Continuous dosing is after 12 hours in step 3), and through analysis, the utilization rate of carbon dioxide is up to 78%, through transmission electron microscope analysis
Understand, the nano-calcium carbonate powder size now obtained is 9~10nm or so, and gained nano-calcium carbonate crystal formation is cube.
Continuous dosing is after 72 hours in step 3), and through analysis, the utilization rate of carbon dioxide still maintains 78%.Such as Fig. 2
It is shown, understood through transmission electron microscope tem analysis, gained nano-calcium carbonate crystal formation is cube, the nano-calcium carbonate calcium powder now obtained
Body size is 10nm or so, and Size Distribution is as shown in Figure 3.
Embodiment 3
Embodiment 2 is repeated, difference is, in step 3), one-level high gravity rotating packed bed and two level hypergravity rotary filling
The temperature for filling bed is 25 DEG C, and hypergravity level is 100, after the pH value of slurry is 11 in one-level high gravity rotating packed bed again
Into continuous running status, the pH value for controlling slurry in two level high gravity rotating packed bed is 6.9, wherein, two hypergravity rotations
It is counter current contacting to turn gas-liquid contact in packed bed, and remaining condition is constant.Continuous dosing 12 hours and continuous dosing be after 72 hours,
The utilization rate of carbon dioxide is 85%.Through transmission electron microscope analysis, and obtained nano-calcium carbonate powder crystal formation is cube, chi
It is very little in 40nm or so.
Embodiment 4
Embodiment 3 is repeated, difference is, in step 2), it is 30% to purify gas concentration lwevel in kiln gas；Calcium hydroxide hangs
The concentration of supernatant liquid is 15wt%；In step 3), gas-liquid contact is counter current contacting in one-level high gravity rotating packed bed, and two level is overweight
Gas-liquid contact is current contacting in power RPB, and remaining condition is constant.Continuous dosing 12 hours and continuous dosing 72 hours
Afterwards, the utilization rate of carbon dioxide is 82%.Through transmission electron microscope analysis, and obtained nano-calcium carbonate powder crystal formation is cube
Shape, size is in 55nm or so.
Embodiment 5
Repeat embodiment 2, difference is, in step 3), in one-level high gravity rotating packed bed in temperature be 35 DEG C, surpass
Gravity horizontal is 80, and the pH value of slurry enters back into continuous running status after being 9, and the temperature in two level high gravity rotating packed bed is
35 DEG C, horizontal hypergravity is 80, and the pH value for controlling slurry is 6.9 states, wherein, the gas-liquid in one-level high gravity rotating packed bed connects
Touch as current contacting, the gas-liquid contact in one-level high gravity rotating packed bed is counter current contacting, and remaining condition is constant.Continuous dosing
After 72 hours, the utilization rate of carbon dioxide is 80% for 12 hours and continuous dosing.Through transmission electron microscope analysis, and obtained nanometer
Calcium carbonate powder crystal formation is cube, and size is in 60nm or so.
Embodiment 6
Embodiment 3 is repeated, difference is, in step 2), it is 33% to purify gas concentration lwevel in kiln gas；Calcium hydroxide hangs
The concentration of supernatant liquid is 12wt%；In step 3), the temperature in one-level high gravity rotating packed bed is 38 DEG C, controls the pH value of slurry
For 9, the temperature in two level high gravity rotating packed bed is 38 DEG C, and remaining condition is constant.Continuous dosing 12 hours and continuous dosing
After 72 hours, the utilization rate of carbon dioxide is 82%.Through transmission electron microscope analysis, and obtained nano-calcium carbonate powder crystal formation is
Cube, size is in 80nm or so.
Comparative example 1
Embodiment 2 is repeated, difference is, in step 3), one-level high gravity rotating packed bed and two level hypergravity rotary filling
The filler filled in bed is unmodified nickel foam filler, and remaining condition is constant, continuous dosing 12 hours, the nano-calcium carbonate of generation
The fouling on filler of calcium slurry, equipment need to be cleaned, the utilization rate of carbon dioxide is only 65%.
Comparative example 2
Embodiment 2 is repeated, difference is, the modified nickel foam filler of one-level high gravity rotating packed bed is changed to unmodified
Nickel foam filler.Remaining condition is constant, continuous dosing 15 as a child, nano-calcium carbonate slurry fouling on filler of generation,
Equipment need to be cleaned, utilization rate of carbon dioxide is low, below 70%.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (9)
1. a kind of production method of cube nano-calcium carbonate, it is characterised in that comprise the following steps：
1) take lime stone and coke to be calcined in shaft kiln and produce calcium oxide and kiln gas；
2) by the cooling of above-mentioned kiln gas, dedusting and desulfurization, the purification kiln gas that gas concentration lwevel is 15~40% is obtained；With above-mentioned oxidation
Calcium is raw material, and compound concentration is 5~15wt% calcium hydroxide suspension；
3) be carbonized workshop section：In equipment start-up, first by calcium hydroxide suspension obtained by step 2) after heat exchanger by entering
Material pump is pumped into the first stirred tank supporting with one-level supergravity reactor, when the material in the first stirred tank reaches predetermined body
Stop feed pump after product, then the material in the first stirred tank is pumped into one-level supergravity reactor and contacted simultaneously with purification kiln gas
Carburizing reagent is carried out, the pH for being recycled to slurry in one-level supergravity reactor is 8~12, and afterwards, foregoing one-level carbonization workshop section enters
Enter continuous running status, reopen feed pump, while by the slurry in one-level supergravity reactor according to same with feed pump
Flow be pumped into two level supergravity reactor, and contact and occur anti-with the purification kiln gas from one-level supergravity reactor
Should, the slurry for leaving two level supergravity reactor flows into the second supporting stirred tank, when slurry reaches default in the second stirred tank
Started the cycle over after volume, circulation slurry mixes with the slurry from one-level supergravity reactor and in two level supergravity reactor
Continue carburizing reagent, the pH controls of slurry are 6.8~7 in two level supergravity reactor, the slurry in the second stirred tank
It is after reaching predetermined, the slurry in two level supergravity reactor is old according to aging tank progress is sent into input quantity identical amount
Changing, said second carbonization workshop section initially enters continuous running status, wherein, one-level supergravity reactor and the reaction of two level hypergravity
The temperature of device is controlled at 10~50 DEG C；
4) slurry after ageing is pumped into modified tank, it is modified at a temperature of 40~80 DEG C；
5) modified slurry is filtered, is dry, be broken, classification, obtaining cube nano-calcium carbonate calcium product.
2. production method according to claim 1, it is characterised in that in step 2), the preparation side of calcium hydroxide suspension
Method is：Calcium oxide obtained by step 1) is added to 40~70 DEG C of hot water digestion after removal of impurities, the mass ratio of wherein calcium oxide and hot water is
1:4~7, then be aged 6~12 hours after screening and removing impurities, then remove the gred and be diluted with water after suspension separator, obtain concentration
For 5~15wt% calcium hydroxide suspension.
3. production method according to claim 1, it is characterised in that in step 3), be pumped into one-level supergravity reactor
With the slurry and/or material that are pumped into two level supergravity reactor with purification kiln gas being connect for current contacting or adverse current independently
Touch, be preferably counter current contacting.
4. production method according to claim 1, it is characterised in that in step 3), the one-level supergravity reactor and
Two level supergravity reactor is independently selected from high gravity rotating packed bed or with the supergravity reactor from pressurization；
Preferably, it is respectively 30~500 that the hypergravity of the one-level supergravity reactor and two level supergravity reactor is horizontal, more preferably
For 50~150.
5. production method according to claim 1, it is characterised in that in step 3), the one-level supergravity reactor and
Filler in the packing layer of two level supergravity reactor is modified nickel foam filler, the processing procedure of the modified nickel foam filler
Including：It will be soaked in nickel foam the filler successively sodium hydroxide solution at 40~70 DEG C, dilution heat of sulfuric acid, it is molten then at absolute ethyl alcohol
After being cleaned by ultrasonic in liquid, it is 0.01~0.05molL that nickel foam filler is placed in into concentration-11- myristyl phosphoric acid it is anhydrous
Soaked 40~60 hours in ethanol solution, wherein, soaking temperature is 50 DEG C, further takes out, dries, obtains modified nickel foam filler.
6. production method according to claim 1, it is characterised in that in step 4), the step of the modification includes：Will be old
Slurry after change is pumped into modified tank, after being warming up to 40~80 DEG C of temperature, adds surfactant, and stirring is incubated 1~3 hour,
Insulation is stood again 1~3 hour；Preferably, the addition of the surfactant is 2~6% of the stock quality after ageing；More
Preferably, the surfactant is selected from stearic acid, odium stearate, dioctyl phthalate, palmitic acid, glyceride, silane
One kind in coupling agent, titanate coupling agent or with the several of arbitrary proportion mixing.
7. production method according to claim 1, it is characterised in that in step 5), the filtering refer to using press filtration or
Centrifugal filtration, obtain 40~50wt% of water content filtration product；The drying include to filtration product carry out one-level dry and
Secondary drying so that the water content of press filtration product is down to below 0.5wt%.
8. the cube nano-calcium carbonate that production method as claimed in claim 1 obtains.
9. cube nano-calcium carbonate according to claim 8, it is characterised in that the granularity of the nano-calcium carbonate is 10
~80nm.
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