CN105417566A - Method for preparing nano calcium carbonate through full-automatic rotating pressure jet-carbonation technology - Google Patents
Method for preparing nano calcium carbonate through full-automatic rotating pressure jet-carbonation technology Download PDFInfo
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Abstract
The invention discloses a method for preparing nano calcium carbonate through a full-automatic rotating pressure jet-carbonation technology. According to the method for preparing the nano calcium carbonate through the full-automatic rotating pressure jet-carbonation technology, vacuum is produced through an ejector, kiln gas containing CO2 is absorbed rapidly and reacted with Ca(OH)2 rapidly, devices such as an air compressor and a stirrer are omitted, the reaction can be conducted at room temperature, the production cost is greatly reduced, rapid reaction is conducted on the condition that pressure exists simultaneously, the double effects of energy conservation and environmental protection are achieved, a carbonized crystal control agent is not added, energy conservation and environmental protection are achieved, and cubic nano calcium carbonate of which particle size distribution is narrow and the particle size is smaller than 100 nm is prepared.
Description
Technical field
The present invention relates to the technical field of a kind of preparation method of nano-calcium carbonate, particularly relate to a kind of method that full-automatic rotating pressure injection carbonization technology prepares nano-calcium carbonate.
Background technology
China is Calcium Carbonate resource and big producing country in the world, and at present, China's calcium carbonate industry overall throughput reaches 8,000,000 tons/year.But, statistical result showed, in China's calcium carbonate industry, the calcium carbonate with certain technical value added only accounts for 7% in product structure, wherein have 0.5% of the not enough ultimate production of kind of high added value, and external nano level superfine level calcium carbonate forms large-scale industrial production.
After entering 21 century, under the impact of calcium carbonate industry technology and capital abroad, just progressively and international joint.Superior and the specialized main trend having become recent industry development of application of scope of the enterprise maximization, product seriation, quality.
Guangdong Province is as maritime provinces, and along with reform and economic prominent flying are developed, Guangdong Province is the ground, staple market of domestic calcium carbonate supply and demand, as Guangdong Province's glass cement, electric wire industry year account for the over half of the whole nation by calcium carbonate demand.In the industry such as rubber, plastics, papermaking, footwear material, coating, needed for Guangdong Province, the dimensions of market of calcium carbonate product is also very large.
One of core technology that precipitated nanocrystals calcium carbonate is produced is carburizing reagent technology and equipment, because of production unit is different from technique can the particle of production different shapes and size.Carburizing reagent is a strong exothermal reaction, its energy consumption depends primarily on carbonization technology, different equipment, the calcium carbonate quality produced varies, the indices such as Carbonate Particle Size distribution, size, specific surface area, oil-absorption(number), hole body appearance OK, depend on the quality of carbonizing apparatus to a great extent.Carbonating tower is the key equipment of whole technique, and its operating parameter directly affects the quality of precipitated chalk product.
The production method of nano-calcium carbonate mainly contains both at home and abroad at present:
1. interval bubbling carbonation method
Interval bubbling carbonation method is that reaction solution is squeezed in tower, keeps certain liquid level, adopts air compressor machine or Root's blower, passes into CO2 mixed gas at the bottom of tower, and bubbling upwards, carries out carburizing reagent and generates calcium carbonate.The gas-to-liquid contact weak effect of this equipment, processing condition difficulty controls, and the granularity of product is uneven, and carbonization specific surface area is unstable, and carbonization time is long, easily produces parcel phenomenon, cause the product accumulation of salt in the surface soil, affect quality product in reaction process.
2. intermittent stirring formula carborization
Intermittent stirring formula carborization also claims autoclave carborization, is milk of lime is cooled to less than 25 DEG C by refrigerator, squeezes in carburizing reagent still, passes into CO2 gas mixture, under agitation carry out carburizing reagent at employing air compressor machine or Root's blower.Superfine CaCO-3 is prepared by controlling the condition intervals such as temperature of reaction, concentration, stirring velocity, additive.Current domestic nano-calcium carbonate producer, this band of most employing stirs, it is the improvement to bubbling carbonizing method, reaction is comparatively even, and this method facility investment is large, and the energy consumption that strong stirring needs is larger, operate more complicated, because churned mechanically tower diameter is than little, CO2 absorbs insufficient, and carbonization specific surface area is unstable.
3. high-gravity carbonation method
The method of a kind of synthesis of nano calcium carbonate that high-gravity carbonation Fa Shi Beijing University of Chemical Technology's high gravity technology research centre is newly developed in recent years.It is for raw material with CO2 and Ca (OH) 2, according to the theory of molecular reaction, utilization rotates the gravity environment more much bigger than earth gravity acceleration produced, and molecular scale effectively controls carburizing reagent and crystallisation process, obtains the nano-powder calcium carbonate that granularity is little, be evenly distributed.Aqua calcis is cut into fine drop, brin and liquid film by the filler of high speed rotating, powerful centrifuge field makes calcium carbonate microparticle just hightail aqua calcis cannot continue to grow up once formation, the contact area of aqua calcis and carbon dioxide greatly increases and upgrades rapidly simultaneously, and speed of response is improved.But its technical sophistication, facility investment and energy consumption are comparatively large, and operation controls difficulty, often produce a collection ofly just to clean with nitric acid, and reaction unit is little, and throughput is little, and production cost is large.The single machine yield of hypergravity is 3000 tons/year, if continue to increase throughput, along with equipment size increases, capacity motor is too large.
4. multi-stage spray carborization
The basic step that multi-stage spray carborization prepares nm level CaCO_3 is: will be mixed with the concentration of processing requirement through refining lime cream soliquoid, add appropriate additive, pump in the spraying gun of multistage spray carbonation top of tower after abundant mixing, under the huge centrifugal action that high speed rotating produces, emulsion is atomized the droplet into fine particle size; Divided by tower bottom through the mixed gas mixed, drying contains the addition of C O2 and enter, be dispersed in tower through gas distributor, droplet carries out instantaneous reverse contact generation chemical reaction with gas and generates CaCO3 in tower.The granularity of the CaCO3 product prepared by multi-stage spray carborization is tiny and evenly, median size is within the scope of 30-40nm, and particulate crystal formation can regulable control.Weak point is that facility investment is comparatively large, and shower nozzle easily blocks, and technology is more complicated, and operation easier is large, and be not suitable for producing, industrial application is promoted and is restricted.
5. film dispersion micro-structured reactor carbonization
Grand Science and Technology Co., Ltd. of Tsing-Hua University and Shandong have developed the film preparing nano-calcium carbonate and disperses micro-structured reactor.With aperture be the mould material of several microns or tens microns as dispersion medium, promote carrying out fast of mass transfer and reaction by the mixing of strengthening microcosmic, make the calcium carbonate particle diameter of preparation little and be evenly distributed.Particle diameter and the crystal formation of product can be controlled preferably by regulation and control reactant concn, the flow of two-phase, pressure and other parameters.Because carbonization needs the air compressor machine of more than 0.4MPa to carry out carbonization, and the concentration of carbonization is lower, small volume, and output is lower, and it is high that the carbonization of film dispersion micro-structured reactor also exists cost, the problem of suitability for industrialized production difficulty.
Nano-calcium carbonate carbonization technology domestic at present also exists the features such as carbonization production cost is high, energy consumption is large, size distribution is wide, bad dispersibility, needs to develop that a kind of production cost is low, granularity is controlled at present, dispersed excellent carbonization technology.
Summary of the invention
The object of the invention is the shortcoming in order to overcome above-mentioned prior art, a kind of full-automatic rotating pressure injection carbonization technology is provided to prepare the method for nano-calcium carbonate, the method that this full-automatic rotating pressure injection carbonization technology prepares nano-calcium carbonate utilizes injector to produce vacuum, quick suction containing CO2 kiln gas fast and Ca (OH) 2 react, eliminate air compressor machine, the equipment such as agitator, reaction can be carried out at normal temperatures, greatly reduce production cost, the rapid reaction when there being pressure simultaneously, reach energy-conservation, the double effects of environmental protection, do not adding any carbonization crystal controlling agent, energy-conservation, environmental protection, prepared sizes narrowly distributing, granularity is less than the cubical nano-calcium carbonate of 100nm.
The technical solution adopted for the present invention to solve the technical problems is: a kind of full-automatic rotating pressure injection carbonization technology prepares the method for nano-calcium carbonate, comprises the following steps:
(1) calcination stage: make calcium oxide after being calcined in fully automatic environmental-friendly shaft kiln by Wingdale, by the ashing of revolution digestion machine, obtains raw slurry, and raw slurry is by vibratory screening apparatus, and after the thick slag of refining removing, raw slurry carries out ageing, and regulates temperature and the concentration of raw slurry;
(2) carbonation stage: pump in full-automatic rotating pressure injection carbonizing plant and carry out, when being reacted to pH value and being 7-8, the raw ageing of starching through 8-24 hour that carbonization is good, then carry out secondary carbonization;
(3) size of Nano particles of calcium carbonate and the size of BET measurement specific surface area is measured with laser fineness gage; after transmission electron microscope observing pattern and median size; then by slush pump, the ripe slurry of carbonization is squeezed into activation pot; after being heated to 60 ~ 80 DEG C, add the surface active modifier dissolved, by the slurry after coated getting well; squeeze into full automatic pressure filter with pump and be filtered to water content 38%-42%; adopt three layers of chain band loft drier again, when moisture is at 5-10%, pass into hot blast and pulverize;
(4) enter subordinate again to pulverize, moisture content of finished products drops to less than 0.5%, after two-stage series connection is pulverized, and product, classification, packaging.
Further, full-automatic rotating pressure injection carbonizing plant in step (2) is made up of jet mixer, liquid storage tower, spraying cycle pump, injector, reaction tower, CO2 kiln gas pipe, and injector comprises pipe connecting, trunnion and nozzle, pipe connecting pipe connecting is connected with CO2 kiln gas pipe; Jet mixer is made up of receiving chamber, nozzle, mixing section and diffuser casing.
Further, the carbonation stage technique of the full-automatic rotating pressure injection carbonizing plant in step (2) is:
(1), after regulating the Pressure, Concentration, Temperature of Ca (OH) 2, liquid storage tower is pumped into;
(2) slurry in liquid storage tower, is extracted out by spraying cycle pump, and through plate-type heat exchanger, reduce the temperature in slurry, through calcium hydroxide slurry pipeline, entering jet mixer calcium oxide enters gas-liquid mixed chamber by heavy caliber shower nozzle at a high speed, forms high-speed jet; In gas-liquid mixed chamber, produce powerful negative pressure simultaneously, enter diffuser-, thus suction chamber pressure is reduced, form vacuum, a large amount of CO2 gas is sucked in gas-liquid hybrid chamber; Under the acting in conjunction of powerful negative pressure and high-speed jet, the CO2 gas sucked in gas-liquid hybrid chamber is sheared, pulverizes, emulsification; Strong turbulent flow changes again pressure gradient between the two film of gas-liquid and concentration gradient, simultaneously negative pressure and intensive shear and stirring impels two membrane interface HF oscillation, bubble diameter is significantly reduced, and bubbles number sharply increases, and increases the specific surface area of bubble, greatly reduces resistance to mass transfer; In the expansion segment of diffuser-, the kinetic energy of mixing jet is pressure, and final CO2 gas under high pressure incorporates rapidly in slurry, and then gas liquid mixture hightails gas-liquid mixed chamber and enters carbonation reaction tower;
(3) in carbonation reaction tower, there is flow deflector, gas liquid mixture is under the effect of flow deflector, with opposite direction, mutual spacing, there is the jet of input angle, be injected in reaction tower, make the fluid in reaction tower become ternary rotational shear simultaneously turbulent flow, regular high shear rotary eddy current is at reaction tower internal circulation flow, complete carburizing reagent, unnecessary kiln gas tail gas is discharged through the top of reaction tower simultaneously, when the slurries of reaction tower are full, slurries from upflow tube, then are back to liquid storage tower;
(4) cyclical operation and so forth, until PH=7-8, reaches processing requirement, stops carbonization, plasma discharge.
The feature of full-automatic pressure rotary-jet carbonization technology is
(1) have excellent mass-and heat-transfer performance, energy consumption is low, and technique is simple, and less investment is easy to maintenance, is convenient to the advantages such as maximization industrial production, and have higher building reason volume transmission quality coefficient, lower unit consumption of energy, equipment energy consumption reduces relatively, and running cost reduces;
(2) because this reaction operates under 0.2-0.6MPa at pressure, because reaction pressure improves, CO2 dissolution rate is in the liquid phase increased, accelerate speed of response, shorten the reaction times, improve production efficiency, be conducive to the even refinement of product pellet, power saving 30 ~
50%, energy consumption is low, is easy to operate and control;
(3) traditional carbonization carburizing reagent is the raw slurry of 10-20m3, and these research and development once can be starched by the raw of carbonization 30-50m3, can improve plant capacity;
(4) by the interchanger of external placed type, reduce the reaction heat of system, can quality be improved;
(5) owing to adopting special nozzle, liquid atomizing effect is good, adds gas liquid interfacial area, adds CO2 uptake factor, decreases the content of CO2 in emission, decreases the impact on environment;
(6) owing to adopting guide plate, spray the kinetic energy produced and have stronger shearing force to material, make the nanoparticle of generation even, dispersiveness improves, and reduces agglomeration;
(7) novel process does not need to add any crystal control agent when carbonization, and the purity of product is improved; Product granularity is little, and specific surface area is large, and crystal formation is cubic type, good product dispersibility, and oil-absorption(number) is low, constant product quality;
(8) containing one group or two groups of flow deflectors, slurries are rotated in spray tower.The fluid of splash head ejection, by flow deflector, can carry out the stirring of stereoscopic and omnibearing, make it keep regular rotating vortex at reaction tower internal circulation flow to reaction solution;
(9) test shows that full-automatic pressure rotary-jet carbonization technology by obtained finely dispersed cubic nanometer calcium carbonate, can improve gloss, dispersiveness, weathering resistance and sticking power for coating; Wear resistance and viscosity stability can be improved for lubricating oil; Thixotropy, sticking power, tensile strength and elongation can be improved for seal gum; Wear resistance, tensile strength and elongation can be improved for rubber; While can improving dimensional stability and processing characteristics during plastics, improve shock strength, hardness, Elastic deflection intensity.
Utilize high-order self-priming kiln gas carbonization technique, save the cost of investment of compressor, utilize recycle pump to take out slurry, force outer circulation, in high-order self-sucking device, liquid falls and the negative pressure of generation, and self-priming cellar for storing things gas carries out carbonization.High-order self-priming kiln gas technique, adopts stock pump circulation that milk of lime is fallen from high-order self-sucking device, produces negative pressure, carry out Self inhaling.This method eliminates air compressor machine, equipment is simplified, design adopts novel injection carbonizer, improve CO2 have higher assimilated efficiency, enhance the mass-transfer efficiency of CO2, by and tower body outside be provided with cooling plate open type device or, the intensification of reaction system is taken away by the interchanger of outer circulation, make temperature rise in whole reaction process, variation range is little, and product crystalline form is consistent.This design both can reach the object of cooling, eliminate again the utility appliance of tower inside, avoid inner wall of tower in carbonization process scab and affect heat transfer efficiency, the calcium carbonate being conducive to preparing small particle size improves quality product to a certain extent, improves the utilization ratio of kiln gas.Gas-liquid-solid three-phase height mixes, and solves traditional carborization, and there is mass transfer slow, the shortcoming that contact efficiency is low, shortens the reaction times.
Further, the kiln gas treatment process that the calcination stage in step (1) produces comprises the following steps:
(1) stack gas of the shaft kiln of calcined limestone adopts water jacket, utilizes kiln tail used heat, heating hot water, carries out digesting and saponification reaction; Kiln gas adopts wet-dry change to combine multistage dedusting, to improve efficiency of dust collection;
(2) kiln gas containing CO2 is from the Base top contact of calcining kiln, and after gravitational dust collection, be sent to sieve-tray tower washing, gas passes into by the bottom of tower, and the acid stronger gases such as SO2, with containing CaO about 0.7% liming spray, wash away by tower top.Then through bubble dust collector and the water-and-oil separator that coke is housed, the gas of purification enters surge tank, after compressor compression, be sent to carbonization workshop section.
In sum, full-automatic rotating pressure injection carbonization technology of the present invention prepares the method for nano-calcium carbonate compared with traditional calcium carbonate production technique, technique is improved, technological equipment investment cost is reduced, equipment yield is high, the automatic control of technique, effectively recycle energy medium, Ru Shui and heat etc., be conducive to reducing production cost, Control platform, improve and stabilize quality product.Also tool has the following advantages:
(1) fully automatic environmental-friendly shaft kiln calcination technology, because shaft kiln adopts twin-stage bell cloth, Tashan Mountain ash discharging gear, A.T.C, the good seal performance of kiln, reduces the leakage of kiln gas; Ash discharge, charging can not stop air blast, improve the throughput of kiln, compare traditional limestone kiln, and energy-conservation more than 10% CO2 concentration reaches 35-42%, and can shorten carbonization time, Activity of Lime reaches more than 300mlHCl, and this can reduce costs 30 yuan/ton.
(2) utilize the waste heat of shaft kiln, heating water, obtained hot water digestion, control digestion temperature and reach more than 90 DEG C, the lime white that such hot water digests out, activity is high, particle thin, pulping rate is high, and slag is few, improves the utilization ratio of lime.Adopt the slurry that hot water digests out, digestion thoroughly, is not easy the accumulation of salt in the surface soil after carbonization.
(3) production method and device owing to adopting full-automatic pressure rotary-jet carbonization technology to produce nano-calcium carbonate.Be designed to the reactor of 30-50m3, achieve less energy-consumption and high benefit.Compared with traditional carbonization mode, the reaction times shortens about 30-50%, and the volume productivity effect of nano-calcium carbonate improves 50%, one ton of product and can save 50 yuan/ton.
(4) secondary carbonization is adopted, secondary in-situ treatment process of surface treatment, when a carbonization is to pH=9-10, add after press filtration water stirs, ageing together, reunite during prevention from decaying, because have certain treatment agent in press filtration water, nano-calcium carbonate is made once to carry out surface treatment, prevent the discharge of waste water, when depositing, can not reunite, after being stored in certain hour simultaneously, pass into CO2 carbonization again, make pH≤7 of calcium carbonate water slurry, add from the press filtration water water film dedusting again, reclaim the fine particle in tail gas, and improve the activation temperature of ripe slurry, after nano-calcium carbonate fully disperses, add the lipid acid mixed solution that saponification is good, reduce the oil-absorption(number) more than 10% of product, make the oil-absorption(number) of product at 25-30ml/100g, between the pH=8-9 of product, improve the dispersiveness of Nano particles of calcium carbonate, improve the quality of nano-calcium carbonate, save surface treatment agent more than 25 yuan/ton.
(5) adopt the diaphragm filter press of Large Copacity 400m2, have level of automation high, output is large, makes filter cake moisture reduce by 5%, reduces the features such as energy consumption for drying, reduce labor strength, the stability between improving batch.
(6) traditional method drying adopts two layers of dry case of chain band, heat utilization efficiency, my corporate makeover existing is three layers of drying case of chain, improve the utilization ratio of hot blast, pulverize when traditional method is and moisture is dried to 0.5% because drying materials to 0.5% time, material can be hardening, particle aggregation is serious, and when causing pulverizing, energy consumption is large, has point white point do not fallen apart in product.Now this project need dry 5-10% at nano-calcium carbonate, from three layers of drying case of chain out after, enter one-level pulverize, pass into hot blast simultaneously, because nano-calcium carbonate material is when there being moisture, material loosening, easy pulverizing, and can not pulverizer be glued, improve dispersion of particles, particle is after pulverizing simultaneously, enters two grade pulverization, only need pass into hot blast in pulverizer, moisture just can be made to be reduced to less than 0.5%, before material is not also reunited, just start depolymerization, there is the function of original position depolymerization.From drying product out, nanoparticle recovery rate oneself reach more than 95%.Comparing other equipment is that after drying, nanometer product is reunited, then the flow process of depolymerization, there is production cost low, product offspring is little, and fine powder content is high, for having good mechanical property and dispersiveness during client, the advantage of having improved the quality of products, make the oven dry output of a production line from 2.5 tons/year, bring up to 50,000 tons/year, 40 kgs/tonne, coal can be saved, power consumption 20KW/ ton, this makes oven dry cost reduce by more than 50 yuan/ton.
(7) traditional pulverizer is the pulverizer of diameter 600mm, the pulverizer of diameter 1100mm is redesigned into through my company, to change high speed winnowing machine be grading machine is low pressure gale amount winnowing machine, beats powder and changes negative pressure into and beat powder, improve quantity and quality by original malleation.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that a kind of full-automatic rotating pressure injection carbonization technology of the present embodiment 1 prepares the method for nano-calcium carbonate.
Embodiment
Embodiment 1
A kind of full-automatic rotating pressure injection carbonization technology described by the present embodiment 1 prepares the method for nano-calcium carbonate, as shown in Figure 1, comprises the following steps:
(1) calcination stage: make calcium oxide after being calcined in fully automatic environmental-friendly shaft kiln by Wingdale, by the ashing of revolution digestion machine, obtains raw slurry, and raw slurry is by vibratory screening apparatus, and after the thick slag of refining removing, raw slurry carries out ageing, and regulates temperature and the concentration of raw slurry;
(2) carbonation stage: pump in full-automatic rotating pressure injection carbonizing plant and carry out, when being reacted to pH value and being 7-8, the raw ageing of starching through 8-24 hour that carbonization is good, then carry out secondary carbonization;
(3) size of Nano particles of calcium carbonate and the size of BET measurement specific surface area is measured with laser fineness gage; after transmission electron microscope observing pattern and median size; then by slush pump, the ripe slurry of carbonization is squeezed into activation pot; after being heated to 60 ~ 80 DEG C, add the surface active modifier dissolved, by the slurry after coated getting well; squeeze into full automatic pressure filter with pump and be filtered to water content 38%-42%; adopt three layers of chain band loft drier again, when moisture is at 5-10%, pass into hot blast and pulverize;
(4) enter subordinate again to pulverize, moisture content of finished products drops to less than 0.5%, after two-stage series connection is pulverized, and product, classification, packaging.
Full-automatic rotating pressure injection carbonizing plant in this step (2) is made up of jet mixer, liquid storage tower, spraying cycle pump, injector, reaction tower, CO2 kiln gas pipe, and injector comprises pipe connecting, trunnion and nozzle, pipe connecting pipe connecting is connected with CO2 kiln gas pipe; Jet mixer is made up of receiving chamber, nozzle, mixing section and diffuser casing.
The carbonation stage technique of the full-automatic rotating pressure injection carbonizing plant in this step (2) is:
(1), after regulating the Pressure, Concentration, Temperature of Ca (OH) 2, liquid storage tower is pumped into;
(2) slurry in liquid storage tower, is extracted out by spraying cycle pump, and through plate-type heat exchanger, reduce the temperature in slurry, through calcium hydroxide slurry pipeline, entering jet mixer calcium oxide enters gas-liquid mixed chamber by heavy caliber shower nozzle at a high speed, forms high-speed jet; In gas-liquid mixed chamber, produce powerful negative pressure simultaneously, enter diffuser-, thus suction chamber pressure is reduced, form vacuum, a large amount of CO2 gas is sucked in gas-liquid hybrid chamber; Under the acting in conjunction of powerful negative pressure and high-speed jet, the CO2 gas sucked in gas-liquid hybrid chamber is sheared, pulverizes, emulsification; Strong turbulent flow changes again pressure gradient between the two film of gas-liquid and concentration gradient, simultaneously negative pressure and intensive shear and stirring impels two membrane interface HF oscillation, bubble diameter is significantly reduced, and bubbles number sharply increases, and increases the specific surface area of bubble, greatly reduces resistance to mass transfer; In the expansion segment of diffuser-, the kinetic energy of mixing jet is pressure, and final CO2 gas under high pressure incorporates rapidly in slurry, and then gas liquid mixture hightails gas-liquid mixed chamber and enters carbonation reaction tower;
(3) in carbonation reaction tower, there is flow deflector, gas liquid mixture is under the effect of flow deflector, with opposite direction, mutual spacing, there is the jet of input angle, be injected in reaction tower, make the fluid in reaction tower become ternary rotational shear simultaneously turbulent flow, regular high shear rotary eddy current is at reaction tower internal circulation flow, complete carburizing reagent, unnecessary kiln gas tail gas is discharged through the top of reaction tower simultaneously, when the slurries of reaction tower are full, slurries from upflow tube, then are back to liquid storage tower;
(4) cyclical operation and so forth, until PH=7-8, reaches processing requirement, stops carbonization, plasma discharge.
The feature of full-automatic pressure rotary-jet carbonization technology is
(1) have excellent mass-and heat-transfer performance, energy consumption is low, and technique is simple, and less investment is easy to maintenance, is convenient to the advantages such as maximization industrial production, and have higher building reason volume transmission quality coefficient, lower unit consumption of energy, equipment energy consumption reduces relatively, and running cost reduces;
(2) because this reaction operates under 0.2-0.6MPa at pressure, because reaction pressure improves, CO2 dissolution rate is in the liquid phase increased, accelerate speed of response, shorten the reaction times, improve production efficiency, be conducive to the even refinement of product pellet, power saving 30 ~
50%, energy consumption is low, is easy to operate and control;
(3) traditional carbonization carburizing reagent is the raw slurry of 10-20m3, and these research and development once can be starched by the raw of carbonization 30-50m3, can improve plant capacity;
(4) by the interchanger of external placed type, reduce the reaction heat of system, can quality be improved;
(5) owing to adopting special nozzle, liquid atomizing effect is good, adds gas liquid interfacial area, adds CO2 uptake factor, decreases the content of CO2 in emission, decreases the impact on environment;
(6) owing to adopting guide plate, spray the kinetic energy produced and have stronger shearing force to material, make the nanoparticle of generation even, dispersiveness improves, and reduces agglomeration;
(7) novel process does not need to add any crystal control agent when carbonization, and the purity of product is improved; Product granularity is little, and specific surface area is large, and crystal formation is cubic type, good product dispersibility, and oil-absorption(number) is low, constant product quality;
(8) containing one group or two groups of flow deflectors, slurries are rotated in spray tower.The fluid of splash head ejection, by flow deflector, can carry out the stirring of stereoscopic and omnibearing, make it keep regular rotating vortex at reaction tower internal circulation flow to reaction solution;
(9) test shows that full-automatic pressure rotary-jet carbonization technology by obtained finely dispersed cubic nanometer calcium carbonate, can improve gloss, dispersiveness, weathering resistance and sticking power for coating; Wear resistance and viscosity stability can be improved for lubricating oil; Thixotropy, sticking power, tensile strength and elongation can be improved for seal gum; Wear resistance, tensile strength and elongation can be improved for rubber; While can improving dimensional stability and processing characteristics during plastics, improve shock strength, hardness, Elastic deflection intensity.
Utilize high-order self-priming kiln gas carbonization technique, save the cost of investment of compressor, utilize recycle pump to take out slurry, force outer circulation, in high-order self-sucking device, liquid falls and the negative pressure of generation, and self-priming cellar for storing things gas carries out carbonization.High-order self-priming kiln gas technique, adopts stock pump circulation that milk of lime is fallen from high-order self-sucking device, produces negative pressure, carry out Self inhaling.This method eliminates air compressor machine, equipment is simplified, design adopts novel injection carbonizer, improve CO2 have higher assimilated efficiency, enhance the mass-transfer efficiency of CO2, by and tower body outside be provided with cooling plate open type device or, the intensification of reaction system is taken away by the interchanger of outer circulation, make temperature rise in whole reaction process, variation range is little, and product crystalline form is consistent.This design both can reach the object of cooling, eliminate again the utility appliance of tower inside, avoid inner wall of tower in carbonization process scab and affect heat transfer efficiency, the calcium carbonate being conducive to preparing small particle size improves quality product to a certain extent, improves the utilization ratio of kiln gas.Gas-liquid-solid three-phase height mixes, and solves traditional carborization, and there is mass transfer slow, the shortcoming that contact efficiency is low, shortens the reaction times.
The kiln gas treatment process that calcination stage in this step (1) produces comprises the following steps:
(1) stack gas of the shaft kiln of calcined limestone adopts water jacket, utilizes kiln tail used heat, heating hot water, carries out digesting and saponification reaction; Kiln gas adopts wet-dry change to combine multistage dedusting, to improve efficiency of dust collection;
(2) kiln gas containing CO2 is from the Base top contact of calcining kiln, and after gravitational dust collection, be sent to sieve-tray tower washing, gas passes into by the bottom of tower, and the acid stronger gases such as SO2, with containing CaO about 0.7% liming spray, wash away by tower top.Then through bubble dust collector and the water-and-oil separator that coke is housed, the gas of purification enters surge tank, after compressor compression, be sent to carbonization workshop section.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to technical scheme of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.
Claims (4)
1. full-automatic rotating pressure injection carbonization technology prepares a method for nano-calcium carbonate, it is characterized in that, comprises the following steps:
(1) calcination stage: make calcium oxide after being calcined in fully automatic environmental-friendly shaft kiln by Wingdale, by the ashing of revolution digestion machine, obtains raw slurry, and raw slurry is by vibratory screening apparatus, and after the thick slag of refining removing, raw slurry carries out ageing, and regulates temperature and the concentration of raw slurry;
(2) carbonation stage: pump in full-automatic rotating pressure injection carbonizing plant and carry out, when being reacted to pH value and being 7-8, the raw ageing of starching through 8-24 hour that carbonization is good, then carry out secondary carbonization;
(3) size of Nano particles of calcium carbonate and the size of BET measurement specific surface area is measured with laser fineness gage; after transmission electron microscope observing pattern and median size; then by slush pump, the ripe slurry of carbonization is squeezed into activation pot; after being heated to 60 ~ 80 DEG C, add the surface active modifier dissolved, by the slurry after coated getting well; squeeze into full automatic pressure filter with pump and be filtered to water content 38%-42%; adopt three layers of chain band loft drier again, when moisture is at 5-10%, pass into hot blast and pulverize;
(4) enter subordinate again to pulverize, moisture content of finished products drops to less than 0.5%, after two-stage series connection is pulverized, and product, classification, packaging.
2. a kind of full-automatic rotating pressure injection carbonization technology according to claim 1 prepares the method for nano-calcium carbonate, it is characterized in that, full-automatic rotating pressure injection carbonizing plant in step (2) is made up of jet mixer, liquid storage tower, spraying cycle pump, injector, reaction tower, CO2 kiln gas pipe, and injector comprises pipe connecting, trunnion and nozzle, pipe connecting pipe connecting is connected with CO2 kiln gas pipe; Jet mixer is made up of receiving chamber, nozzle, mixing section and diffuser casing.
3. a kind of full-automatic rotating pressure injection carbonization technology according to claim 2 prepares the method for nano-calcium carbonate, and it is characterized in that, the carbonation stage technique of the full-automatic rotating pressure injection carbonizing plant in step (2) is:
(1), after regulating the Pressure, Concentration, Temperature of Ca (OH) 2, liquid storage tower is pumped into;
(2) slurry in liquid storage tower, is extracted out by spraying cycle pump, and through plate-type heat exchanger, reduce the temperature in slurry, through calcium hydroxide slurry pipeline, entering jet mixer calcium oxide enters gas-liquid mixed chamber by heavy caliber shower nozzle at a high speed, forms high-speed jet; In gas-liquid mixed chamber, produce powerful negative pressure simultaneously, enter diffuser-, thus suction chamber pressure is reduced, form vacuum, a large amount of CO2 gas is sucked in gas-liquid hybrid chamber; Under the acting in conjunction of powerful negative pressure and high-speed jet, the CO2 gas sucked in gas-liquid hybrid chamber is sheared, pulverizes, emulsification; Strong turbulent flow changes again pressure gradient between the two film of gas-liquid and concentration gradient, simultaneously negative pressure and intensive shear and stirring impels two membrane interface HF oscillation, bubble diameter is significantly reduced, and bubbles number sharply increases, and increases the specific surface area of bubble, greatly reduces resistance to mass transfer; In the expansion segment of diffuser-, the kinetic energy of mixing jet is pressure, and final CO2 gas under high pressure incorporates rapidly in slurry, and then gas liquid mixture hightails gas-liquid mixed chamber and enters carbonation reaction tower;
(3) in carbonation reaction tower, there is flow deflector, gas liquid mixture is under the effect of flow deflector, with opposite direction, mutual spacing, there is the jet of input angle, be injected in reaction tower, make the fluid in reaction tower become ternary rotational shear simultaneously turbulent flow, regular high shear rotary eddy current is at reaction tower internal circulation flow, complete carburizing reagent, unnecessary kiln gas tail gas is discharged through the top of reaction tower simultaneously, when the slurries of reaction tower are full, slurries from upflow tube, then are back to liquid storage tower;
(4) cyclical operation and so forth, until PH=7-8, reaches processing requirement, stops carbonization, plasma discharge.
4. a kind of full-automatic rotating pressure injection carbonization technology according to claim 1 prepares the method for nano-calcium carbonate, it is characterized in that, the kiln gas treatment process that the calcination stage in step (1) produces comprises the following steps:
(1) stack gas of the shaft kiln of calcined limestone adopts water jacket, utilizes kiln tail used heat, heating hot water, carries out digesting and saponification reaction; Kiln gas adopts wet-dry change to combine multistage dedusting, to improve efficiency of dust collection;
(2) kiln gas containing CO2 is from the Base top contact of calcining kiln, sieve-tray tower washing is sent to after gravitational dust collection, gas passes into by the bottom of tower, tower top sprays with containing CaO about 0.7% liming, the acid stronger gases such as SO2 are washed away, then through bubble dust collector and the water-and-oil separator that coke is housed, the gas of purification enters surge tank, after compressor compression, be sent to carbonization workshop section.
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