CN102275967A - Method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials - Google Patents
Method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials Download PDFInfo
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- CN102275967A CN102275967A CN2011102094832A CN201110209483A CN102275967A CN 102275967 A CN102275967 A CN 102275967A CN 2011102094832 A CN2011102094832 A CN 2011102094832A CN 201110209483 A CN201110209483 A CN 201110209483A CN 102275967 A CN102275967 A CN 102275967A
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Abstract
The invention discloses a method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials. The method comprises the following steps of: adding sulfuric acid with mass concentration of 5-35% into ash residues generated by sintering dry-method desulfuration, soaking for 12h, and washing repeatedly by using clear water; and by using the preprocessed desulfuration ash residue with the whiteness of larger than or equal to 85% as the raw materials, adding a surface dispersant with the mass accounting for 0.1-5.0% of the mass of the ash residues and ammonium bicarbonate 2.05-2.30 times of the surface dispersant in to the raw materials, stirring, grinding for 10-60min in an airtight container at the room temperature, then adding a surface activating agent with the mass accounting for 0.5-5.0% of the mass of the ash residues, raising temperature to 80-120 DEG C, continuously grinding for 20-60 min, washing a calcium carbonate semi-finished product with the grain size of 0.03-1.0 mum obtained after cooling by using clean water in a barrel till no white precipitates are generated in washed liquid under the detection of a BaC12 solution, and drying filtered residues to obtain a nanoscale calcium carbonate product. The preparation method has the advantages of making use of the desulfurated ash residues, solving the problem of the ash yard pollution of the desulfurated ash residues, protecting ecological environment, saving energy, reducing the emission of carbon dioxide and having popularizing and practical values.
Description
Technical field
The present invention relates to a kind of is the method for feedstock production nano-calcium carbonate with the sintering desulfuration lime-ash, belongs to the solid waste environmental protection and utilizes the field.
Background technology
Superfine light calcium carbonate is a kind of novel ultrafine solids material that grows up in the later stage eighties in last century, now has been widely used in Industrial products such as rubber, plastics, papermaking, coating, printing ink as mineral filler.China has more than 400 families of Production of Light Calcium Carbonate enterprise now according to a preliminary estimate, nearly 3,000,000 tons of yearly capacity, and just increasing progressively with annual tempo more than 15%.The enterprise of present domestic calcium carbonate superfine powder industrial scale maximum is Guangdong Province Enping Gavin Chemical Industrial Enterprise Co., Ltd., and annual production has reached 350,000 tons.And with fastest developing speed be the grand Science and Technology Co., Ltd. in Shandong, corporate share 2006 has begun gross investment and has reached 5,000,000,000 yuan and produce 1000000 tons of nano-calcium carbonate engineerings per year after the U.S. successfully goes on the market.
At present the light calcium carbonate industrialized producing technology mainly contains: intermittently bubbling carbonizing method, multistage spray carbonation method, high-gravity reactive precipitation etc. continuously.The calcium carbonate granule that the shortcoming of these technologies is energy consumption height, produce is big, the market competitiveness a little less than, the enterprise of real profit is less.
At present, the sulfur removal technology that relates generally to of China's flue gas of sintering machine mainly contains dry method, semidrying and wet method.Dry process mainly contains activated coke absorption method, the flue gas circulating fluidized bed polycomponent dry method of LJS, ENS dry method, dense-phase tower method, the double-circulating fluid bed T method of GSCA, MEROS flue injection dry method, LEC Wingdale row control dry method; Wet processing mainly contains limestone-gypsum wet method, sulphur ammonium wet method, magnesium oxide wet method, two alkali lye wet method, ionic liquid wet method; Semidrying mainly contains NID flue circulation method, SDA rotary spraying technique.Various technologies all have relative merits, and it is serious that wherein sulphur ammonium wet method not only causes equipment corrosion, and the risk that has ammonia to reveal in the operation; And advantage such as the concrete operation cost of limestone-gypsum wet method is low, but producing a large amount of desulfurization ashs, its secondary resource utilization is to be badly in need of the difficult problem that solves.
The desulfurization ash main chemical compositions of metallurgy industry is CaSO
3And CaSO
4, also contain CaCO
3, Ca (OH)
2, also containing a certain amount of elemental sulfur, this has just determined desulfurization ash to have with the plaster of paris different physicochemical properties.Under the situation of water, calcium sulfate is a kind of good activity excitant, and complicated chemical reaction will take place the component in the desulfurization ash.Owing to contain higher Ca, S in the desulfurization ash, through washing, then desulfurization ash does not contain a spot of Cl to desulfurization material
-, and CaCl
2Also a kind of good activity excitant concerning desulfurization ash, chemical reaction will take place in lime-ash under this condition, the lime-ash particle surface is lost by aquation, the generating portion hydrated product, as C-S-H gel, Aft, AFm etc., make lime-ash not have due pozzolanic activity, its comprehensive utilization is affected.
What is more important, desulfurization ash contains too high calcium sulfite composition, and it is directly used in the brickmaking of building the road, concrete admixture and plaster of Paris becomes impossiblely, has caused the desulfurization ash bulk deposition in the countryside, form the ash field of numerous serious environment pollution, taken a large amount of good farmlands.According to incompletely statistics, the sintering desulfuration lime-ash that the whole nation more than 100 tame iron and steel enterprises abandon exceedes hundred million tons, and these desulfurization ashs of what use is made of become a great problem of China steel enterprise.
Once had enterprise to adopt phosphogypsum and ammoniacal liquor, ammonium hydrogencarbonate to react productive target product ammonium sulfate, byproduct is the lower macrobead lime carbonate of economic worth.The calcium carbonate granule that this production technique is produced is big, and is similar with the difficult problem that the method for leading to carbonic acid gas prepares lime carbonate to present market.It is the method for feedstock production calcium carbonate superfine powder that peace micro industry university " a kind of is the method for feedstock production superfine light calcium carbonate with the gypsum " (200710021709.X) has proposed with calcium sulfate, it is the method for feedstock production calcium carbonate superfine powder that Anhui University of Technology " a kind of method of producing calcium carbonate superfine powder and volatile salt simultaneously " (201010532199.4) has proposed with calcium hydroxide, resemble process, industrial gypsum acid is insoluble, impurity reaches the not enough problem of whiteness more but all avoided, and is not strong to the actual production directive significance.
Summary of the invention
The object of the present invention is to provide and a kind ofly can effectively utilize the sintering desulfuration lime-ash, solve the cindery ash of sintering desulfuration pollute and save the energy, what reduce CO2 emissions is the method for feedstock production nano-calcium carbonate with the sintering desulfuration lime-ash.
For achieving the above object, the technical solution used in the present invention is: of the present invention a kind of be the preparation that the method for feedstock production nano-calcium carbonate is divided into cindery pre-treatment of sintering desulfuration and nano-calcium carbonate with the sintering desulfuration lime-ash.
The lime-ash raw material that produces with sintering dry desulphurization is put into container, and the adding mass concentration is 5～35% sulfuric acid in this container, and adding vitriolic quality is 1～3 times of sintering desulfuration lime-ash quality, soaks 12h.Desulfurization ash after soaking is washed 1～3 time with clear water repeatedly, remove residual calcium carbonate granule, calcium hydroxide particle and part iron, manganese and magnesium ion etc. in the desulfurization ash, the initial whiteness that guarantees desulfurization ash becomes the pretreatment desulfurizing lime-ash more than or equal to 85%.
Get the pretreatment desulfurizing lime-ash that contains mass concentration 1～5% water and put into container, the surface dispersant that in container, adds pretreatment desulfurizing lime-ash solid masses 0.1～5.0%, the bicarbonate of ammonia solid or the soluble carbon hydrochlorate that add 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses again, stir, in encloses container, grind 10～60min for 5～35 ℃ in room temperature, adding quality again is the lime carbonate surfactant of pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after the cooling is the lime carbonate work in-process of 0.03～1.0 μ m.These lime carbonate work in-process are used clear water agitator treating 1～3 time in washing beck, until washing lotion BaCl
2The no white precipitate of solution check is done baking with filter residue, obtains the nanometer grade calcium carbonate product.
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride monopalmitate, sorbitan monostearate or Sodium dodecylbenzene sulfonate (also can be selected from wherein several, in identical weight ratio).
Surfactant is selected from: stearic acid, titanic acid ester, aluminic acid ester, phosphate coupling agent or silane coupling agent (also can be selected from wherein several, in identical weight ratio).
Adopt that as above technical scheme provides a kind of with the sintering desulfuration lime-ash be the feedstock production nano-calcium carbonate method compared with prior art, technique effect is:
1. can effectively utilize sintering desulfuration lime-ash (or burning slag), protect ecotope;
2. save the energy;
3. reduced Carbon emission;
4. economic benefit and social benefit are obvious.
Embodiment
Below in conjunction with embodiment the specific embodiment of the present invention is described in further detail.
Described a kind of be the preparation that the method for feedstock production nano-calcium carbonate comprises cindery pre-treatment of sintering desulfuration and nano-calcium carbonate with the sintering desulfuration lime-ash.
Described sintering desulfuration lime-ash is the waste residue that sintering dry desulphurization produces, with the sintering desulfuration lime-ash is raw material, and this raw material is put into container, and the adding mass concentration is 5～35% sulfuric acid in this container, the sulfuric acid quality that adds is 1～3 times of sintering desulfuration lime-ash quality (weight), soaks 12h.Desulfurization ash after soaking repeatedly with clear water washing 1～3 time, is removed residual calcium carbonate granule, calcium hydroxide particle and iron, manganese, magnesium ion in the desulfurization ash, and the initial whiteness that guarantees desulfurization ash becomes the pretreatment desulfurizing lime-ash more than or equal to 85%.
Get water content (wt) 1～5% and put into container through pretreated desulfurization ash, add the surface dispersant of pretreatment desulfurizing lime-ash solid masses 0.1～5.0% in container, the effect of dispersion agent is to make the calcium carbonate granule of generation not reunite even particle size distribution.The bicarbonate of ammonia solid or the soluble carbon hydrochlorate that add 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses again, stir, in encloses container, grind 10～60min for 5～35 ℃ in room temperature, adding quality again is the lime carbonate surfactant of pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after the cooling is the lime carbonate work in-process of 0.03-1.0 μ m, the lime carbonate work in-process that with this particle diameter are 0.03～1.0 μ m (micron) are used BaCl with clear water agitator treating 1～3 time in washing beck until filtrate
2The no white precipitate of solution check with filter residue oven dry (the best is an oven drying at low temperature), obtains nanometer (nm) level calcium carbonate product.
When above-mentioned reaction is carried out, separate out the ammonium sulphite crystal closing in the tail gas introducing condenser of overflowing in the close container, perhaps can obtain ammonium sulfate product through the strong oxide treatment of air pressurized.
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride list palmitic acid lipid, sorbitan monostearate or Sodium dodecylbenzene sulfonate.
Surfactant is selected from: stearic acid, titanic acid ester, aluminic acid ester, phosphate coupling agent or silane coupling agent.
Embodiment 1: take by weighing the sintering desulfuration ash ground-slag 1000g of Hubei steel enterprise, the sulfuric acid (H with 5%
2SO
4) 2000ml soaks 12h, adds water and stirs, and gets the slip washing on upper strata 80% at every turn, filter, repeat 3 times, filter residue adds Sodium dodecylbenzene sulfonate 1g, processing industry ammonium hydrogencarbonate solid 600g, stirring the back, to add the water washing filter 23 after with the little barreling mill of experiment 60min inferior, washs to filtrate and use BaCl
2The no white precipitate of solution check, drying obtains the nano level light calcium carbonate, the about 0.10 μ m of product cut size, collection filtrate adds dilute sulphuric acid adjusting PH and obtains ammonium sulphite for neutral back evaporate to dryness.
Embodiment 2: take by weighing the sintering desulfuration ash ground-slag 1000g of Hunan steel enterprise of China water chestnut group, the sulfuric acid (H with 5%
2SO
4) 3000ml soaks 12h, adding water stirs, get the slip washing on upper strata 80% at every turn, filter, repeat 3 times, add 200g industry calcium oxide to filter residue again, and add 1g anhydrous sorbitol acid anhydride mono laurate fat and 600g industrial carbonic acid hydrogen ammonia solid, after adding 20% ammoniacal liquor 50ml above-mentioned material being stirred, grind 20min again with adding the 5g silane coupling agent behind the little barreling mill of the experiment 30min.Add water washing filter 23 time, wash to filtrate and use BaCl
2The no white precipitate of solution check, drying obtains superfine light calcium carbonate, the about 0.03 μ m of product cut size.In above-mentioned reaction, the tail gas that reaction is produced with the way oxidation of pressure oxidation after again evaporate to dryness obtain ammonium sulfate product.
Embodiment 3: take by weighing dried sintering desulfuration lime-ash 100g and industrial hydrogen calcium oxide 100g that Hunan steel enterprise of China water chestnut group produces, adding water 300ml and Sodium dodecylbenzene sulfonate 1.0g stirs, add sodium bicarbonate solid 210g again, stir the 90min after-filtration, collect filtrate and add dilute sulphuric acid and regulate PH for neutral back and add under the situation of forced oxidation, evaporate to dryness reclaims S-WAT.Filtrate water repetitive scrubbing to filtrate is used BaCl
2, the no white precipitate of solution check, drying obtains superfine light calcium carbonate, granularity 1 μ m.
Method of the present invention is suitable for various chemical gypsums such as power plant desulfurization gypsum, phosphogypsum, fluorgypsum, citric acid gypsum equally.
Claims (3)
1. one kind is the method for feedstock production nano-calcium carbonate with the sintering desulfuration lime-ash, it is characterized in that: the lime-ash raw material that produces with sintering dry desulphurization is put into container, the adding mass concentration is 5～35% sulfuric acid in this container, adding vitriolic quality is 1～3 times of desulfurization ash quality, soak 12h, desulfurization ash after soaking is washed 1～3 time with clear water repeatedly, remove residual calcium carbonate granule, calcium hydroxide particle and iron, manganese and magnesium ion in the desulfurization ash, the initial whiteness of desulfurization ash becomes the pretreatment desulfurizing lime-ash more than or equal to 85%;
Get the pretreatment desulfurizing lime-ash that contains mass concentration 1～5% water and put into container, the surface dispersant that in container, adds pretreatment desulfurizing lime-ash solid masses 0.1～5.0%, the bicarbonate of ammonia solid or the soluble carbon hydrochlorate that add 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses again, stir, in encloses container, grind 10～60min for 5～35 ℃ in room temperature, adding quality again is the lime carbonate surfactant of pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after the cooling is the lime carbonate work in-process of 0.03～1.0 μ m; These lime carbonate work in-process are used clear water agitator treating 1～3 time in washing beck, with the no white precipitate of BaCl2 solution check,, obtain the nanometer grade calcium carbonate product the filter residue oven dry until washing lotion; Described
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride monopalmitate, sorbitan monostearate or Sodium dodecylbenzene sulfonate;
Surfactant is selected from: stearic acid, titanic acid ester, aluminic acid ester, phosphate coupling agent or silane coupling agent.
2. according to claim 1 a kind of be the method for feedstock production nano-calcium carbonate with the sintering desulfuration lime-ash, it is characterized in that: when producing the nano-calcium carbonate calcium product, the tail gas of overflowing from sealed vessel can be introduced and separate out the ammonium sulphite crystal in the condenser, perhaps obtains ammonium sulfate product through the strong oxide treatment of air pressurized.
3. according to claim 1 a kind of be the method for feedstock production nano-calcium carbonate with the sintering desulfuration lime-ash, it is characterized in that: if pretreated sintering desulfuration lime-ash water-content (wt) is greater than 15%, the industrial calcium oxide or the calcium hydroxide that add sintering desulfuration lime-ash solid masses 10～20% participate in the preparation section of nano-calcium carbonate together.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849773A (en) * | 2012-09-10 | 2013-01-02 | 宜都市惠宜陶瓷有限公司 | Method for manufacturing industrial filling material by using waste gypsum mold |
| CN105967214A (en) * | 2016-06-24 | 2016-09-28 | 张文凯 | Method for preparing spherical nanometer calcium carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN101538060A (en) * | 2009-05-05 | 2009-09-23 | 贵州西洋肥业有限公司 | Method for producing light calcium carbonate and coproducing hydrogen sulfide by using crude calcium sulfide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN102112637A (en) * | 2008-05-30 | 2011-06-29 | 阿尔托大学基金会 | Method of producing calcium carbonate from waste and byproducts |
-
2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN102112637A (en) * | 2008-05-30 | 2011-06-29 | 阿尔托大学基金会 | Method of producing calcium carbonate from waste and byproducts |
| CN101538060A (en) * | 2009-05-05 | 2009-09-23 | 贵州西洋肥业有限公司 | Method for producing light calcium carbonate and coproducing hydrogen sulfide by using crude calcium sulfide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849773A (en) * | 2012-09-10 | 2013-01-02 | 宜都市惠宜陶瓷有限公司 | Method for manufacturing industrial filling material by using waste gypsum mold |
| CN105967214A (en) * | 2016-06-24 | 2016-09-28 | 张文凯 | Method for preparing spherical nanometer calcium carbonate |
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