CN100571847C - A kind of mineral carbonation fixation of C O 2The technology of co-producing calcium carbonate product - Google Patents
A kind of mineral carbonation fixation of C O 2The technology of co-producing calcium carbonate product Download PDFInfo
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Abstract
The invention provides a kind of mineral carbonation fixation of C O
2The technology of co-producing calcium carbonate product, may further comprise the steps: with the calcic solid waste or/and silicate ore pulverize, obtain solid particle, add acid medium in solid particle, stirred 30～120 minutes down at 60～80 ℃, cooled and filtered obtains the calcium ion leachate, add the calcic basic species in the calcium ion leachate, regulate pH=7～8, filter then, obtain the calcic material liquid; In the calcic material liquid, add organic solvent, stir, feed CO again
2Gas carries out carbonation reaction; With the reacting liquid filtering behind the carbonation reaction, get filtrate and solid product; With solid matter with deionized water washing and dry, obtain calcium carbonate; The present invention not only makes solid waste and greenhouse gases CO
2Get utilization, and the carbonate products that makes is the aragonitic precipitated calcium carbonate, can further reduces production costs to have favorable economic benefit.
Description
Technical field
The invention belongs to utilization of waste as resource, greenhouse gases CO
2Reduce discharging and the application technology as the second resource field, particularly a kind of calcic solid waste or ore of utilizing passes through mineral carbonation fixation of C O for raw material
2The technology of co-producing calcium carbonate product.
Background technology
Along with the consumption of a large amount of fossil energies, CO in the atmosphere
2The content cumulative year after year, by greenhouse gases CO
2Etc. the also more aggravation of caused greenhouse effects.International Technology circle is actively realized CO by the exploitation clean energy resource
2The source reduce discharging; Simultaneously also carrying out CO
2Catch on a large scale, store and fixing technical research and commerical test.
Mineral carbonation fixedly is CO
2The extensive storage and fixing important channel.Mineral carbonation fixedly is to have imitated occurring in nature CO
2The mineral absorption process, i.e. CO
2Ore reaction with containing alkalescence or alkaline earth oxide generates a series of like this processes of permanent, more stable carbonate.
CO
2The fixing raw material of mineral carbonation mainly contains the silicate ore of calcic magnesium, as be rich in magnesium alkaline-earth metal forsterite (Mg arranged
2SiO
4), serpentine (Mg
3Si
2(OH)
4), talcum (Mg
3Si
4O
10(OH)
2) etc., what be rich in the calcium alkaline-earth metal has a wollastonite (CaSiO
3) etc.Some is rich in the solid waste of calcium magnesium, also can be used as CO
2The raw material that mineral carbonation is fixing, as the incineration ashes of iron and steel slag, coal flying dust, discarded object, the mine tailing in discarded construction material and some the metal smelt process etc.
At present, CO
2The fixing process route of mineral carbonation can be divided into direct route and indirect route, mainly comprises:
1, direct dry method gas-solid carbonating: CO
2Direct and one step of the ore generation gas-solid reaction generation carbonate of gas.
2, direct wet method carbonating: CO
2Water-soluble formation carbon acid solution, under the carbonic acid effect, ore progressively dissolves and is settled out carbonate.
3, acetic acid is the roundabout process of medium: acetic acid leaches the calcium ion in the raw material and generates calcium acetate, and calcium acetate carries out a step carbonation reaction and generates CaCO
3And acetic acid.
4, caustic soda is the roundabout process of medium: adopt the calcium ions and magnesium ions in the caustic soda leaching raw material, carbonating absorbs CO
2Generate CaCO
3And NaCO
3, NaCO
3Causticization regeneration caustic soda recycles.
Above-mentioned 4 kinds of typical process routes all have its pluses and minuses.Directly dry method gas-solid carbonating technology route is directly simple, and course of reaction all is heat release, and reaction heat can utilize; Yet reaction rate is slow, the energy consumption height of whole process.Directly wet method carbonating technology route has improved reaction rate; Yet this process route needs a large amount of ores of digging, ore preprocessing process energy consumption height, and by the very difficult solution of it environmental problem that causes.Caustic soda is the roundabout process of medium, and ore does not generally need preprocessing process such as activation, makes energy consumption reduce; Yet reaction temperature height, time are long, alkaline consumption height, product separation difficulty.
Calendar year 2001, it is the indirect mineral carbonation process of medium with acetic acid that people such as Kakizawa have proposed, and its concrete steps are: at first utilize acetic acid to handle the wollastonite that process crushes and screens, thereby obtain calcium acetate solution; The gained calcium acetate solution directly and CO then
2Carbonation reaction takes place generate calcium carbonate and acetic acid.(Kakizawa M, Yamasaki A, Yanagisawa Y.A new CO
2Disposal process using artificial rock weathering of calcium silicate acceleratedby acetic acid.Energy, 2001,26 (4): 341-354.) owing to utilize weak acid to replace strong acid, the regeneration of medium is relatively easy, and energy consumption has reduced; Yet calcium carbonate can not in time separate with acetic acid, and back reaction is very strong, makes the maximum conversion rate of carbonation gained calcium less than 20%, this and get by thermodynamics under the same conditions and also have big gap between the equilibrium conversion calculated value.
Summary of the invention
The objective of the invention is to overcome existing CO
2Problems such as low, the acid media of calcium transformation ratio regeneration difficulty, high energy consumption, high financial cost in the mineral carbonation technique for fixing, particularly wet method indirect processes route, and be difficult to the defective of large-scale industrial application, thus a kind of mineral carbonation fixation of C O is provided
2The technology of co-producing calcium carbonate product.
Technical scheme of the present invention is as follows:
Mineral carbonation fixation of C O provided by the invention
2The technology of co-producing calcium carbonate product may further comprise the steps:
(1) with the calcic solid waste or/and silicate ore is pulverized, obtain solid particle;
(2) add the faintly acid medium in the solid particle that step (1) obtains, stirred 30～120 minutes down at 60～80 ℃, cooled and filtered obtains the calcium ion leachate;
The addition of described acid medium is to add 4.5-6ml in per 1 solid particle that restrains, and volume fraction is the acid medium aqueous solution of 11.1%-33.3%;
Described acid medium is acetic acid, propionic acid, lactic acid or citric acid;
(3) in the calcium ion leachate that step (2) obtains, add the calcic basic species, regulate pH=7～8 of described calcium ion leachate, filter then, obtain the calcic material liquid;
(4) in the calcic material liquid that step (3) obtains, add organic solvent, stir, feed CO again
2Gas carries out carbonation reaction;
Described calcic material liquid is 0.5～2 with the volume of organic solvent ratio;
(5), get filtrate and solid product with the reacting liquid filtering behind step (4) carbonation reaction;
(6) the solid matter with deionized water washing that step (5) is obtained is also dry, obtains calcium carbonate.
Mineral carbonation fixation of C O provided by the invention
2The technology of co-producing calcium carbonate product also can further comprise:
(7) organic facies on upper strata and the water-soluble liquid phase of lower floor are reclaimed in the rapid layering of filtrate that obtains of above-mentioned steps (5) respectively;
(8) organic facies that step (7) is reclaimed is carried out rectification under vacuum, organic solvent that obtains reclaiming and acid medium under 120-200 ℃; The organic solvent that is reclaimed is as the organic solvent of step (4); Institute's restored acid medium is as the acid medium of step (2); With
(9) the water-soluble liquid phase that step (7) is obtained is mixed with the described calcium ion leachate of step (2), carries out carbonation reaction.
Described calcic solid waste is wollastonite or/and silicate ore is iron and steel slag, carbide slag, coal flying dust, discarded cement, and the particle diameter of the solid particle of described calcic is the 50-200 order.
When described calcic solid waste is the iron and steel slag, in step of the present invention (3), also need in described calcium ion leachate, to add oxidant, make ferrous ion all be oxidized to iron ion, described oxidant is hydrogen peroxide, oxygen or air.
Described calcic basic species is lime powder, calcium hydroxide powder or milk of lime.
The described organic solvent of described step (4) is n-octyl alcohol, kerosene, tbp or trioctylphosphine oxygen phosphorus; The CO that feeds
2Gas is industrial tail gas of purifying through removal of impurities or the CO that contains foreign gas
2Mist; The condition of the carbonation reaction of described step (4) is: reaction temperature is 40～100 ℃, the CO of feeding
2Pressure be 10～50bar, speed of agitator is 100-1000rpm, the reaction time is 30～150 minutes.
Characteristics of the present invention are to utilize a large amount of iron and steel slags and other calcic solid waste or the calcic silicate ore that produces in the steel smelting procedure, absorb the CO that discharges in the industrial process
2Gas makes CO
2Combine the formation stable calcium carbonate with the calcium ion in the raw material, thereby with greenhouse gases CO
2Be converted into more stable carbonate form and store, play extensive minimizing CO
2The purpose of discharging.The present invention not only makes solid waste and greenhouse gases CO
2Get utilization, and can integrated a part of industrial exhaust heat, the energy consumption of whole technical process effectively reduced.
The present invention utilizes the leaching process of weak acid for medium, in the carbonation reaction process, by introducing organic solvent, makes the weak acid that generates enter organic facies from water, has strengthened the carburizing reagent crystallization process, makes calcium transformation ratio increase substantially.And used acid medium, organic solvent can recycling uses, and add organic solvent realization response isolation integral in carbonation reaction, strengthened carbonation CO
2Absorption, a conversion ratio of calcium ion reaches more than 40%.
In addition, the carbonate products that the present invention makes is the aragonitic precipitated calcium carbonate, can be widely used in can further reducing production costs in rubber, plastics, papermaking and the industry such as coating, printing ink, has favorable economic benefit.
Process application of the present invention can make one ton of iron and steel slag absorb 0.2～0.3 ton of CO in the processing of steel smelting procedure iron and steel slag
2Gas is produced 0.8～0.9 ton of aragonitic precipitated calcium carbonate simultaneously, has better industrial application prospects.
Description of drawings
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD) of gained aragonitic precipitated calcium carbonate among the embodiment 1;
Fig. 2 is the stereoscan photograph of gained aragonitic precipitated calcium carbonate among the embodiment 1.
The specific embodiment
The used mineral carbonation fixation of C of the present invention O
2Raw material mainly be calcic solid waste or ore, as the iron and steel slag, carbide slag, coal flying dust, waste cement, wollastonite etc., iron and steel slag wherein, carbide slag, the calcium oxide content in the wollastonite is higher, generally more than 35%, has sufficient calcium source and absorbs CO
2Also contain other impurity in these raw materials simultaneously,, also contain a large amount of sila matter ions in the wollastonite as also containing foreign ions such as magnesium, iron, aluminium, silicon in the iron and steel slag.
When acid medium leached, except calcium, the magnesium in the calcic solid waste, iron, aluminium, silicon plasma were also together leached, thereby needed to add some additives, so that these foreign ions are precipitated out earlier.Add oxidant among the present invention, the divalence ferrous ion is changed into ferric ion, and add the calcic basic species, be used for the pH value of regulator solution, foreign ions such as iron, aluminium, silicon are precipitated separate out.For fear of introducing other foreign ions, the used oxidant of the present invention is a hydrogen peroxide, and used calcic basic species is calcium oxide powder, calcium hydroxide powder, milk of lime etc.Because the solubility product of magnesium carbonate is bigger, magnesium ion is not easy to form carbonate when carbonization, be 145 ℃ as magnesium acetate generation thermodynamics of Carbonization Reaction allowable temperature.Thereby the foreign ion of calcium ion leachate mainly is iron, aluminium, silicon etc., and when the pH=7-8 of leachate, foreign ions such as a large amount of iron, aluminium, silicon precipitation is separated out.
Adopt among the present invention and in calcic material liquid carbonation, add organic solvent, make the acid medium that generates enter in the organic facies, and a part of acid medium has also formed metastable compound with organic solvent, thereby reduced the activity of acid medium, reduced the solubilizing reaction intensity between calcium carbonate and the acid medium, strengthened generating separating of acid medium and calcium carbonate in the carbonation reaction, the conversion ratio of calcium ion also can increase substantially thus.
The used organic solvent boiling point of the present invention is all higher, and the boiling point of acid medium is then relatively low, thereby can reclaim acid medium and organic solvent by organic facies is carried out rectification under vacuum.The temperature of rectification under vacuum generally is lower than 200 ℃, thereby can integrated a part of industrial exhaust heat.Boiling point under used part organic solvent of the present invention and the acid medium standard state is as shown in table 1:
Table 1, the boiling point under part organic solvent and the acid medium standard state:
| Organic solvent | Boiling point (℃) | Acid medium | Boiling point (℃) |
| Tributyl phosphate trioctylphosphine oxygen phosphorus kerosene n-octyl alcohol | 289 130(0.05mmHg) 180～310 195.28 | Acetic acid lactic acid propionic acid citric acid | 118 122 144.1 153 |
The present invention will be further explained and explanation below in conjunction with embodiment:
Embodiment 1.
Calcic solid waste in the present embodiment is selected the iron and steel slag for use, and the main component in the iron and steel slag is :～45% CaO ,～10%MgO ,～20% SiO
2,～20% FeO and～5% other impurity, specific embodiment is as follows:
1) with the iron and steel slag by mechanical crushing and sieve 50 order particle diameters, obtain the iron and steel solid impurity particle;
2) get iron and steel solid impurity particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 60 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last the 40ml glacial acetic acid is slowly added in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 60 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, add 1: 3H
2O
2(distilled water of the pure hydrogen peroxide of 1 volumetric analysis and 3 times of volumes) 2 milliliters make that the ferrous ion in the calcium ion leachate is oxidized to iron ion, simultaneously add calcium oxide powder under constantly stirring, and make PH=～7 of filtrate, filter the calcic material liquid; Filter residue can be used as the raw materials for metallurgy of the pig iron through washing;
4) measure above-mentioned calcic material liquid 150ml, add equal-volume n-octyl alcohol (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 60 ℃, insulation then, and be 300 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 40bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 8.70 grams; By the X-ray diffraction analysis (XRD) of Fig. 1, described as can be known calcium carbonate product is an aragonitic, is spherical by the described as can be known calcium carbonate product of the stereoscan photograph of Fig. 2;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.78mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 150 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of acetic acid reclaims the acetic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Acetic acid after the recovery can mix with glacial acetic acid, is used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a n-octyl alcohol, can be used for above-mentioned steps 4) additive of carbonisation; Like this, acetic acid and n-octyl alcohol can obtain reclaiming and recycling;
9) water that step 7) is obtained and above-mentioned steps 2) the calcium ion leachate that obtains mixes, can proceed carbonation reaction, thereby reach recycling of water.
Above-mentioned steps 3) the calcic material liquid that obtains mainly contains a large amount of calcium acetates, and calcium acetate solution is at CO
2Following reaction takes place during the pressurized carbon acidifying:
Ca(CH
3COO)
2(aq)+CO
2(g)+H
2O(l)→CaCO
3↓+2CH
3COOH(aq)
Above-mentioned being reflected on the thermodynamics is feasible, and carbonic acid can cement out the acetic acid in the calcium acetate, generates calcium carbonate.But because the calcium carbonate that generates can not separate immediately with acetic acid, thereby make the conversion ratio of calcium ion less than 20%, the acetic acid medium can not recycle and reuse.Adopt in the present embodiment and in the calcium acetate solution carbonation, add n-octyl alcohol, make the acetic acid that generates enter in the organic facies, thereby reduced the activity of acetate ion, reduced the ionization equilibrium constant of acetic acid, strengthened generating separating of acetic acid and calcium carbonate in the carbonation reaction, the conversion ratio of calcium ion is also by bringing up to more than 40% less than 20%.
Embodiment 2.
Calcic solid waste in the present embodiment is selected the iron and steel slag for use, and the main component in the iron and steel slag is :～45% CaO ,～10%MgO ,～20% SiO2 ,～20% FeO and～5% other impurity, specific embodiment is as follows:
1) with the iron and steel slag by mechanical crushing and sieve 100 order particle diameters, obtain the iron and steel solid impurity particle;
2) get iron and steel solid impurity particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last 20ml is analyzed pure lactic acid and slowly add in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 120 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, constantly aerating oxygen and stirring makes that the ferrous ion in the calcium ion leachate is oxidized to iron ion, adds calcium hydroxide powder simultaneously, makes PH=～7 of filtrate, filter the calcic material liquid; Filter residue can be used as the raw materials for metallurgy of the pig iron through washing;
4) measure above-mentioned calcic material liquid 150ml, add 2 times of volume tributyl phosphates (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 80 ℃, insulation then, and be 500 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 50bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 8.10 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained lactic acid concn is 0.75mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 160 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, concentration of lactic acid reclaims the lactic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Lactic acid after the recovery can with analyze pure lactic acid and mix, be used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a tributyl phosphate, can be used for above-mentioned steps 4) additive of carbonisation; Like this, lactic acid and tributyl phosphate can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Adopt in the present embodiment and in the calcium lactate solution carbonation, add tributyl phosphate, make the lactic acid and the tributyl phosphate that generate form complex compound and enter in the organic facies in the lump, thereby reduced the activity of lactate ion, reduced the ionization equilibrium constant of lactic acid, strengthened generating separating of lactic acid and calcium carbonate in the carbonation reaction, the conversion ratio of calcium ion is also by bringing up to more than 40% less than 20%.
Embodiment 3.
Calcic solid waste in the present embodiment is selected carbide slag for use, and the content of main component is in the carbide slag :～65% CaO, and～35% other impurity, specific embodiment is as follows:
1) with carbide slag by mechanical crushing and sieve 150 order particle diameters, obtain the carbide slag particle;
2) get carbide slag particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last 80ml is analyzed pure propionic acid and slowly add in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 30 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, under constantly stirring, adds milk of lime, make PH=～7 of filtrate, filter the calcic material liquid;
4) measure above-mentioned calcic material liquid 150ml, add equal-volume n-octyl alcohol (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 80 ℃, insulation then, and be 500 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 10bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 30 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 6.80 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.60mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 160 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of propionic acid reclaims the propionic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Propionic acid after the recovery can with analyze pure propionic acid and mix, be used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a n-octyl alcohol, can be used for above-mentioned steps 4) additive of carbonisation; Like this, propionic acid and n-octyl alcohol can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Embodiment 4.
Calcic raw material in the present embodiment is a wollastonite, and the content of main component is in the wollastonite :～35% CaO ,～60% SiO
2And～other impurity of 5%, specific embodiment is as follows:
1) with wollastonite by mechanical crushing and sieve 200 order particle diameters, obtain the wollastonite particle;
2) get wollastonite particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last 80ml is analyzed pure citric acid and slowly add in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 90 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, under constantly stirring, adds calcium oxide powder, make PH=～7 of filtrate, filter the calcic material liquid;
4) measure above-mentioned calcic material liquid 150ml, add equal-volume trioctylphosphine oxygen phosphorus (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 40 ℃, insulation then, and be 500 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 50bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 7.26 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.68mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 200 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of citric acid reclaims the citric acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Citric acid after the recovery can with analyze pure citric acid and mix, be used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a trioctylphosphine oxygen phosphorus, can be used for above-mentioned steps 4) additive of carbonisation; Like this, citric acid and trioctylphosphine oxygen phosphorus can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Embodiment 5.
Calcic solid waste in the present embodiment is selected the coal flying dust for use, and the main component in the coal flying dust is :～20%CaO and～80% other impurity, specific embodiment is as follows:
1) with the coal flying dust by mechanical crushing and sieve 200 order particle diameters, obtain coal flying dust particle;
2) get coal flying dust particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 60 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last the 80ml glacial acetic acid is slowly added in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 60 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, under constantly stirring, adds calcium hydroxide powder, make PH=～7 of filtrate, filter the calcic material liquid;
4) measure above-mentioned calcic material liquid 150ml, add 2 times of volume kerosene (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 60 ℃, insulation then, and be 300 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 40bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 5.70 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.48mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 150 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of acetic acid reclaims the acetic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Acetic acid after the recovery can mix with glacial acetic acid, is used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a kerosene, can be used for above-mentioned steps 4) additive of carbonisation; Like this, acetic acid and kerosene can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Embodiment 6.
Calcic raw material in the present embodiment is discarded cement, and the content of main component is in the waste cement :～30%CaO and～other magazines of 70%, specific embodiment is as follows:
1) with waste cement by mechanical crushing and sieve 50 order particle diameters, obtain the waste cement particle;
2) get waste cement particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last the 20ml glacial acetic acid is slowly added in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 60 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, under constantly stirring, adds calcium oxide powder, make PH=～7 of filtrate, filter the calcic material liquid;
4) measure above-mentioned calcic material liquid 150ml, add equal-volume tributyl phosphate (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 100 ℃, insulation then, and be 500 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 50bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 150 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 4.80 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.45mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 160 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of acetic acid reclaims the acetic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Acetic acid after the recovery can mix with glacial acetic acid, is used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a tributyl phosphate, can be used for above-mentioned steps 4) additive of carbonisation; Like this, acetic acid and tributyl phosphate can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Embodiment 7.
Calcic raw material in the present embodiment is a wollastonite, and the content of main component is in the wollastonite :～35% CaO ,～60% SiO
2And～other magazines of 5%, specific embodiment is as follows:
1) with wollastonite by mechanical crushing and sieve 150 order particle diameters, obtain the wollastonite particle;
2) get wollastonite particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last the 40ml glacial acetic acid is slowly added in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 60 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, under constantly stirring, adds calcium oxide powder, make PH=～7 of filtrate, filter the calcic material liquid;
4) measure above-mentioned calcic material liquid 150ml, add 0.5 times of volume trioctylphosphine oxygen phosphorus (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; In autoclave, feed purity and be 99.5% CO2 gas, discharge the air in the still, heat above-mentioned calcic material liquid to 80 ℃, insulation then, and be 100 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 50bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 7.76 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.72mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 120 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of acetic acid reclaims the acetic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Acetic acid after the recovery can mix with glacial acetic acid, is used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a trioctylphosphine oxygen phosphorus, can be used for above-mentioned steps 4) additive of carbonisation; Like this, acetic acid and trioctylphosphine oxygen phosphorus can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Calcic solid waste in the present embodiment is selected the iron and steel slag for use, and the main component in the iron and steel slag is :～45% CaO ,～10%MgO ,～20% SiO2 ,～20% FeO and～5% other impurity, specific embodiment is as follows:
1) with the iron and steel slag by mechanical crushing and sieve 200 order particle diameters, obtain the iron and steel solid impurity particle;
2) get iron and steel solid impurity particle 40 grams that step 1) obtains, pack in the 250ml three hole flasks, add the 160ml deionized water then, above-mentioned three hole flasks are put into 80 ℃ of water-baths of magnetic agitation, and settle the straight run condenser pipe thereon, at last the 40ml glacial acetic acid is slowly added in the above-mentioned three hole flasks as leaching medium, begin to leach reaction, reaction was kept 120 minutes, stop to filter after the water-bath, obtain the calcium ion leachate,, obtain the PH=3-5 of described calcium ion leachate through measuring;
3) above-mentioned calcium ion leachate is placed the 250ml conical flask, constantly bubbling air and stirring makes that the ferrous ion in the calcium ion leachate is oxidized to iron ion, adds calcium hydroxide powder simultaneously, makes PH=～7 of filtrate, filter the calcic material liquid; Filter residue can be used as the raw materials for metallurgy of the pig iron through washing;
4) measure above-mentioned calcic material liquid 150ml, add equal-volume tributyl phosphate (analyzing pure) and, put into autoclave in the lump as the additive of carbonisation; Feeding purity is 99.5% CO in autoclave
2Gas is discharged the air in the still, heats above-mentioned calcic material liquid to 80 ℃, insulation then, and be 1000 rpms with rotating speed and begin to stir, in still, feed CO simultaneously again
2Gas makes CO
2Dividing potential drop reach 40bar, reaction picks up counting.Constantly in still, feed CO in the course of reaction
2Gas is to keep the constant pressure in the still; After reaction is kept 60 minutes, stop heating and stirring;
5) all mixtures behind the described autoclave internal reaction of discharge, and, obtain filtrate and solid product through the filter filtration;
6) with above-mentioned steps 4) the solid matter with deionized water washing that obtains after filtering three times, then 100 ℃ dry 12 hours down, get final product calcium carbonate product, weight is 8.69 grams;
7) above-mentioned steps 4) in filter the rapid layering of filtrate obtain, obtain organic facies and water after the separation; Organic facies is utilized standard NaOH drips of solution setting analysis, and obtaining contained acetate concentration is 0.82mol/l;
8) measure above-mentioned steps 7) isolated organic facies 100ml, put into the 250ml flask, in oil bath, carry out rectification under vacuum, in temperature is 180 ℃, when pressure is 50mmHg, keeps rectifying 2 hours, cooling then, through standard NaOH drips of solution setting analysis, the concentration of acetic acid reclaims the acetic acid that obtains in the distillation process simultaneously less than 0.02mol/l in the residual as can be known organic facies.Acetic acid after the recovery can mix with glacial acetic acid, is used for above-mentioned steps 2) the leaching medium; Residual organic facies main component is a tributyl phosphate, can be used for above-mentioned steps 4) additive of carbonisation; Like this, acetic acid and tributyl phosphate can obtain reclaiming and recycling;
9) water and above-mentioned steps 2 that step (7) is obtained) the calcium ion leachate that obtains mixes, and can proceed carbonation reaction, thereby reach recycling of water.
Claims (5)
1, a kind of mineral carbonation fixation of C O
2The technology of co-producing calcium carbonate product may further comprise the steps:
(1) with the calcic solid waste or/and silicate ore is pulverized, obtain solid particle, the particle diameter of described solid particle is the 50-200 order;
(2) in the solid particle that step (1) obtains, add acid medium, stirred 30～120 minutes down, filter and obtain the calcium ion leachate at 60～80 ℃;
The addition of described acid medium is to add 4.5-6ml in per 1 solid particle that restrains, and volume fraction is the acid medium aqueous solution of 11.1%-33.3%;
Described acid medium is acetic acid, propionic acid, lactic acid or citric acid;
(3) in the calcium ion leachate that step (2) obtains, add the calcic basic species, regulate pH=7～8 of described calcium ion leachate, filter then, obtain the calcic material liquid;
Described calcic solid waste is or/and silicate ore is that iron and steel slag, carbide slag, coal flying dust, discarded cement are or/and wollastonite;
Or/and silicate ore when being the iron and steel slag, also needs to add oxidant to described calcium ion leachate, make ferrous ion all be oxidized to iron ion when described calcic solid waste, described oxidant is hydrogen peroxide, oxygen or air;
(4) in the calcic material liquid that step (3) obtains, add organic solvent, stir, feed CO again
2Gas carries out carbonation reaction; Described organic solvent is n-octyl alcohol, kerosene, tributyl phosphate or trioctylphosphine oxygen phosphorus;
Described calcic material liquid is 0.5～2 with the volume of organic solvent ratio;
(5), get filtrate and solid product with the reacting liquid filtering behind step (4) carbonation reaction;
(6) the solid matter with deionized water washing that step (5) is obtained is also dry, obtains calcium carbonate.
2, by the described mineral carbonation fixation of C of claim 1 O
2The technology of co-producing calcium carbonate product is characterized in that, also comprises:
(7) organic facies on upper strata and the water-soluble liquid phase of lower floor are reclaimed in the rapid layering of filtrate that obtains of above-mentioned steps (5) respectively;
(8) organic facies that step (7) is reclaimed is carried out rectification under vacuum, organic solvent that obtains reclaiming and acid medium under 120-200 ℃; The organic solvent that is reclaimed is as the organic solvent of step (4); Institute's restored acid medium is as the acid medium of step (2); With
(9) the water-soluble liquid phase that step (7) is obtained is mixed with the described calcium ion leachate of step (2), carries out carbonation reaction.
3, by claim 1 or 2 described mineral carbonation fixation of C O
2The technology of co-producing calcium carbonate product is characterized in that, the described calcic basic species in the described step (3) is lime powder, calcium hydroxide powder or milk of lime.
4, by claim 1 or 2 described mineral carbonation fixation of C O
2The technology of co-producing calcium carbonate product is characterized in that, the CO that described step (4) feeds
2Gas is industrial tail gas of purifying through removal of impurities or the CO that contains foreign gas
2Mist.
5, by claim 1 or 2 described mineral carbonation fixation of C O
2The technology of co-producing calcium carbonate product is characterized in that, the condition of the carbonation reaction of described step (4) is: reaction temperature is 40～100 ℃, the CO of feeding
2Pressure be 10～50bar, speed of agitator is 100-1000 rpm, the reaction time is 30～150 minutes.
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| CN101575179B (en) * | 2008-05-05 | 2012-02-01 | 中国科学院过程工程研究所 | Method for converting calcium and/or magnesium elements in steel slag or scruff into carbonate |
| KR101173063B1 (en) * | 2010-11-24 | 2012-08-13 | 기아자동차주식회사 | Method of fixing carbon dioxide comprising a step of recycling the used extraction solvent |
| KR101251264B1 (en) * | 2010-11-30 | 2013-04-10 | 현대자동차주식회사 | Method of fixing carbon dioxide |
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