The Essential Chemical Industry - online search Calcium carbonate “Three types of ale carbonate-contaning rock are excavated and used by industy. They are Imestone, chalk and dolomite Limestone and chalk ate both forms of calcium carbonate and dolomite fsa mixture of calcium and magnesium cartonatas. Al. © CACO, have impurities such as clay but some rocks are over 97% purs. Limestone and other products derived rom Rare used extensively inthe constucton industry and to neutralse acidic compounds ina variety of contexts. In the chemical industy, large quantites of mestone are heated to ce 1500 Kt frm calcium oxide, known as quckme: caCos(s) —> Ca0(8) + CO) Water can be added to Ime to form calcium hydroxide. The process is known as slaking’. Sold calelum hydroxide is known as slaked lime or hydrated Ime, and solutons and suspensions in water as mik of ime. ‘Tho torm lime is often used to cover quiclimo, staked lie (hydrated limo) and mik of Ie. Fora particular use, an appropfate choice is made rom tye four: Imestone, quicklme, slaked Ime or mik of ime. In many uses, Ime reacts more {quickly than Imestone butis more expensive, because a high temperature is requited to produce it om imestone. Uses of limestone and lime Figure 1 Principal ures of limestone and time. ‘The principal uses, by far, ofmestore and Ime are inthe constuction industy and cement making. They ae also used inthe chemical and rmetallrgicalindusties ang in agreuture (On a wortdwide basis, te proportons of Ime used in alferent ndustres are + 60% metallurgy (mainly stel manutacture Umeta/stel himitsteel sg formation and is use in the blast furnace Umetalsivonemlablast furnace 25% construction for example, ts used witn asphalt in read paving, to stabilze sols and in making merar and plaster) 15% for chemical and industrial ues (for example to make bleaches used in the manufactur of paper, to make precipitated calcium carbonate, fine ponder used in costings for paper and paints, and in refining sugar to remove cleat impurities) and for environment uses (or example ‘wth soda ash by both municipal authorities and industry ta sften water (remove calcium and magnesium lon) in the treatment of sewage to remove clloial particles an in fue gas desulfurization chemicalsicalciumcarbonate mie ge) However, these proportions vary widely from country to county. For example inthe US, the proportions ars+ 389 metallurgy (mainly steel manufacture} + 308 environmental uses {for examole, with soda ash, by bth municipal authorities and industry to soften water (remove calcium and magnesium lonsh in the treatment af sewage, to remove colloidal particles and in fue gas desuturlaton 22% chemical and industrial uses (or examle to rake bleaches used in the manufacture of paper, to make precipitated calelum carbonate, a fe ponder used in coatings for paper and paints and in efning sugar to remove calloial impurities) + 8% construction uses (or example, its used with asphalin road paving, stabilize soils and in making mortar and plaster) Dao he US Cal 2012 ‘The uses are descrbed below n more detail in lors of aiferent ndusties. In the construction industry Limestone has be $n used as a building material since the Stone Ago. Indeed, the largestuse of limestone an the various forms of ime is stl in the constricton dusty, partculary in road buiking and bulking projects, fom vastin size, bridges and skyscrapers, to houses. Large ms of calcium carbone are ofon used where sizeable quanites of aggregate are needed, for example forthe foundations of roads. Lime i offen used to make sol ror. Itreacts wit clay minerals in the sot fom comentske compounds (for example caksum slleate ane calcium aluminate (calcium aluminositeate) Figure 2. (@)cley particles (b) ticles before adding lime t aay = ‘Figur 2) Cay partes are ‘Figure 2) When imei ace, the surrounded by wate, allowing tham 9 amount of water around the cay be allgned and able ares reduce. The clay paren side ei. The reults m3 cay sore no longer ale oad easly and ths ‘the sl strengthened ow seeng ‘The strengthening of soitenabies the constuction of bulsings by ging a more stable foundation. Lime is also used on building st large vehicles to move more wasiy (Fg 3) Figure 3 The wet sl has ‘bean made harder bythe ‘kon of ime. This ert. ‘moving equipments ale ‘move around easly hid emo of gon ich Limestone is also the main constituent of cement and concrete In cement making CComents made by fest mixing Imestone ang substances such as clays (which contain sica, alumina and ron) oxi) toa fine powder. The mixture is crushed and ed into a rotary kb (hitp:tawn.comentkins.co.uKindex hin), which isan gon pipe, 60-90 m lng and approximately 8 m In diameter. The pipe is rotated and heated to about 1700 K by flr inse of. The kin is sigh incined to allow forthe materials to slowly reach the oer end, whore iis quickly cooled by ato 373-473 K,Figur 4 & rotary kn designed to ‘prodice 5000 tonnes per day of linker. About 7500 tone of ground | a0 material own 2 a met) sr requ for that output. The ‘photo was than ata coment works In Mayan, Us. ‘The heated ar rom the coolers i returned othe kilns, a proces that saves fuel and increases buring efeiency. “The resuling sold comes out ofthe kin as grey balls, about the sizeof marbles and is known as cinker. The cinker fs ground toa fne powder ‘and mixed with calcium sufate (gypsum) to make the familar grey fre powder. This is cement, tis essentally a mixture of calcium slcates and calcium sulfate. About 50% of cement (ten known as Porland cement)isr-calcium slate, which hydrates and gives the cement sinal strength and about 25% is d-calcum slicae, which hydrates more slowly and gives added sirenghh ater afew days. When itis mixed wih water, chemical reactions accurte form a hard sold, impervious to water. The ole of he calcium sulla sto prevent te cement rom setting too wick ‘About 6 bilion tonnes of coment are produced anrualy, ofwhich China accounts for 2.0 biflon tonnes and India 280 millon tonnes". Cement powder is usually mixed wit sand and aggregate (gravel, grante) and when needed, hey are mixed with walr to form concrete. 1 US Gea Sane, Marl Cm Samar, 216 Figures & and 6 Bulger and mesons, prior othe se of modem cement used 2 mitre of lime (callum hydride sand and water, known as line ‘morta or simply mortar Ith Been used forever 6000 years, snes the buildings of Ancient Greece and Rome. When these buléings are renovated ime ‘mortars used rater than coment. these Photographs of York Mint,» relativly modern ‘using dating back ony 900 years, time mortar has atways boon used In renovating the stonework that has tobe replaced because of westhering ove the xmas Ssh premio eres Rigo In industry and the environment Many lakes have become to aise because of aerial poluton (act rain), fr example inthe US, Scandinavia and Scotland The lakes ae sprayed wih very Shel powdered cakum carbonate (Figure 7), Another efactve way to Wea his problem to appl the powdered mesione to sams leading othe lakes. tunplanted areas near to the sources of th‘Figure 7 Powdered imestane Is bang sprayed over alae nar Hers} n Souther Sweden. By tnd periin of ik Cir, Limestone and the various forms oflime are used in large quanites fo clean up the environment, by neutralising acids. For example, imestone and quickie are used to remove sulur dioxide produced inthe buming of coal in power stations. Even ‘chan’ coal can contain about 1% su. ‘The gaseous effuen's, ie gases, rom the bumning ofthe coal are passed through a spray of very ely ground limestone or quicklme suspended in wate. The sullur dioxide, Being an ac, ects wih them, for example on caCo,(s) + SOx) “> CaSOy{) + COxG) ‘Tho resuling calcium sult colbcts athe base of the absorber and compressed aris blown into this residu. The caeium sulle reacts wih the plaster board and coment ato form calcium sulfate (gypsum), usec to make, for exampl Very fine and pure calcium carbonate is used as fli plastics and paper. A filer Vpolymersipalymors-an-overviow himfr) sa substance that ‘ives buk but does nat ater the properte ofthe substance to which tis added and is also inert. Calelum carbonate when very finely rushed (loss than 2 microns) used in paints to give a mat fish, Figure 8 Uses of iestone Calcium carbonate is also used + to make sodium carbonate bythe Sohay process (chemieals/sodium-carbonate.heml¥sodium carbonate) + nthe blast furnace dmetaliyivn.ntmiabast furnace) to make Kon + Inthe manufacture of lass ‘Tho uses are futher summarized in Faure 8. In ogriculture Crushed imestone and ime in alts foms ar used to neutralize acids ithe sll and so create the optimum slleandion or op growth. They also help to break down clays as describes above, mprovng te sol structure, thus improving drainage and reducing sol erosion. Further, hey provid a source ofealcum fons hat ae an important plant nuttet. Annual production of limestoneData forte annul production of calcu carbonate ae rotreadlyavalable Approximately 1 bilon omnes of Ho pncpaoes,Imesone and dobmie are mined annaly nthe US. Gente lave armours Tine atlases in eeert counties, an estate of wre mining of cakium earponote 818 ilon ones a year, Annual production of lime (calcium oxide and calcium hydroxide) rs [380 mien ones (cha [230 mito tonnes us. | +8 mtn tonnes nga | 16 millon omnes Russia | 1% millon tonnes US Geary Mal Commo Samar, 2016 Manufacture of calcium oxide (quicklime) Calcum carbonate (Imestone) Is heated to form calelum oxie (qulekime) and carbon dixise: cacoys) 0(6)* COn{g) AH = +180 kd mot! Itis an endothermic reaction and the equllorum los far tothe left at ow temperatures, Only at about 1200 K does te partial pressure of carbon Gioxie excoed atmosphere pressure and the decompositon proceeds to completon. Quickie Is produced in retractorytned kins. Many designs aro used, but the most common are based on the Vertical Shat Ki (Figure 8) The kin is made of steel, ned wih retractor bricks. The Imestone fs fed in rom the top and aris either sucked by fans or pushed by roots type blowers, through the kh rom the batom (counter fow). The fuels fed trough the sides of he kin, using about 8-10 lances inserted around the kan. “The me kin consats of three principle zones: + inthe preheating zone, the heat in the combustion products, including earbon dioxide from the dissociation a limestone is used to preheat the Imestone to 1200 K + inthe burning zone he limestone is decomposed to qui at gas temperatures of 1500 K, 2 process known as calcining + inthe cooling zone the heat in the quieKime leaving the burning zone is used to preheat the air required for combustion to 600-750 K “The fuss uses vary, depending on whatis available. Many kins use natural gas but in others ills pumped in. n oters, solids, such as friely powered coal’ pressurized and pumped in so that tacts as a uid It there fs not enough ato complete combustion ofthe fuel, mora is fed in directly tothe burning zane, exten ‘oar Into pening zona mast, i met pret {hod prannt inet osha A ra, A vaiea _| te Vy snk Ine paring iB [] Seeonpined aire, 4 eaaing — |] ine coating ona the nat D, crore J) meme achinn oto 2, worreax /:/| “SoRipaera te room — [4 Sosa Z L ‘cam ‘Figure 9 Manufacture of ime: The verte shat inMany recently invoduced kins have two parallelunts (Figure 10).They are known as two:shaft kis. Inthe simple single kin, described above, the avis pumped up the kin asthe Imestone hws down. This known as a counter flow system. nthe two.shalt ki, known as the Paral Flow Regeneraive (PFR: lime kn, the air and combustion gases travel paallelto the Imestone. The fvells injected just above the buming zone and the Imestone absorbs most ofthe heat released by the fuel and so the temperature of he burning zone can be reduced 1400 K, the temperature of tre decomposition of limestone. ot “ne \, i feo Figure 10 Manufacture of ime: The Paral! Flow ‘Figure 1A Paalel Flow Regenerative (PFR) line Reganernve PER) lie Mn nn Mano, And poms fre Oba A pin poms are Oa A In the diagram, the lef-hand shafts deserbed as in buming mode. The exhaust gases cross over into the right-hand shat, which i said tobe in non-buming mode. “These hot gases travel up in counterfow othe stone, heating itup ready forthe righthand shaftto become the burning shaf and the lefthand aft becomes non-buring, Each shaft cycles trough te buming and non-butning mode about every 10 minutes. ‘Tete i a large reduction inthe fuel used by the to-shaftkih compared tothe single shat kin, ‘Shaft kins have eapacties for producing up to 800 tonnes of ime per day. Quickie is generally sold shor as granules o Manufacture of calcium hydroxide (hydrated lime) “The reacton of quickime wih watoris exothermic. finaly ground powder, Powdered calcm hydroxice is produced by hydrating quicklme witha contolled excess of water to make a dty product. Mik of Ime is prepared by slaking quickime wih an excoss of water. Date last amended: 16th January 2017‘Aninvitation Wi invite you to wie fous fyou have any specific comments about this ste, fr example ‘errors that you have found, suggestions for new topics or for adding ta the existing unis, ‘suggestions for Inks to other sites and addtions or atenatves to cur examples. Please send these comments to: ecl@essentalchemicalindustry.org(malto:eci@essentiachemicalindusty org) “This web she Is produced by the Centre for Industry Education Collaboration a non-profit organization and an integral pat ofthe Department of ‘Chemistry, Univers of York, UK. Copyright © 2016 University af York Centre for Industry Education Collabratin, York UK. Al Ra Reserved