The Institute of Science, Mumbai Inorganic Chemistry Paper IV: APPLIED CHEMISTRY (Unit I)

MANUFACTURE OF PORTLAND CEMENT

Portland (PL) cement is manufactured by mixing calcarious & orgillaceous materials in proper ratio. The mixture is heated to near fusion i.e. about 1400 C to 1630 C. Clinker obtained is then cooled & finely grinded. The product so obtained is called PL cement. Raw Material: 1) Calcareous materials- Most important calcareous is lime stone. It occurs in variety of forms i.e. chalk, sedimentary limestone, metamorphite (substance transformed naturally by heat or pressure, corals & carbonate. 2) Orgillaceous materials- Principle orgillaceous materials available for making PL cement are clay, blast furnace slag, cement rocks etc. Preparation of raw materials: In manufature of PL Cement composition of these materials should be proper & prcised for good results. While fixing proportion of raw materials there are two problems in front of scientists i.e. ideal composition range of PL Cement & whether cement becomes advantageous from economic point of view as well as quality point of view. Old cements were lower in lime content than modern cement. But strength developed by old cement was low. Therefore to increase strength the lime content was increased along with finer grinding. But higher temperatures are required. It may cause expansion and hence it result in cracking of marker or concrete. If high lime content is fixed then percentage of silica becomes too high and percentage of alumina and ferric oxide decreases considerably. Due to this, temperature of burning may be raised. If lime content is too low then obviously percentage of lumina and Fe2O3 becomes high. Because of low lime content the cement may became quick setting cement and quality of cement decreases. Le-Chatelier and other had shown that in actual practice most basic silicate of constant volume contains 2.8 parts by weight of CaO to one part by weight of SiO2 and most basic alumina contains 1:1 parts by weight of CaO to one part of Al2O3. Hence the formula suggested was

CaO

2.8 SiO2

+ 1:1

Al2O3

M.Sc. (II) Inorganic Chemistry notes by Swapnil Prabhulkar

The Institute of Science, Mumbai METHODS FOR MANUFACTURE OF CEMENTS:There are two methods commonly used for the manufacture of cement. (A) Wet process and (B) Dry process Steps involved in both process are same and are as follows: 1) Proportionate raw materials & preparing intimate mixture of raw material. 2) Sintering of mixture at high temperature and 3) To grind clinkers to required degree of fineness and mixing of gypsum. WET PROCESS: It is quite common and is universally employed for manufacture of PL Cement. In this great control is maintained over composition and product is more homogeneous. Process consist of following stages (1) Crushing, (2) Wet grinding, (3) Preparation of slurry, (4) Firing & cement clinker formation, (5) Cooling of Clinker, (6) Grinding of clinker and (7) Mixing in reactor. 1) CRUSHING Crushing of raw materials like limestone, chalk slate or clay etc. is done by means of jaw or roller crusher. Purpose of crushing is to prepare material for grinding in mills. These materials are stored in large lins having height of 18 to 24 meters and diameter 3 to 4.5 meters. WET GRINDING Crushed material comes in grinder mill (ball mills) through a hopper (container tapering downward to an opening for discharging its contents). Thus crushed materials are mixed with required quantity of water and washed clay. Here the mixture ground well and hence raw material is reduced to very fine state.

2)

PREPARATION OF SLURY To finely grounded mixture 30-40 % of water is added. Here raw material is completely in homogeneous state. Such a mixture is called as Slurry. Here composition of slurry is corrected by adding proper quantities of either calecareous or orgillaceous matter. Slurry is kept in state of agitation by setting operation. It is stored in tanks. 4) FIRING AND CEMENT CLINKER FORMATION Firing of slurry is carried out in rotatory kiln. Rotatory kiln is cylindrical in shape. It is 3-5 m in diameter and 70-140 m long. It is made up of steel plates lined with fire bricks. Kilns are set at slight inclination and mounted on heavy friction rollers. Kiln is rotated at speed of one revolution per minute. Upper end of kiln ends in a circular opening into concrete chamber. From this opening combustion gases escape after removal of dust. At lower end there is also fire pipe for blowing powdered coal or fuel oil along with air. With the help of this fuel the kiln is heated. Upper end of the kiln is at temperature of about 700 C and lower is that of about 1200 C. Slurry is stored in tank placed at height, so that it can be fed into kiln due to gravity. It passes through measuring and feed device which is joined to upper end of cement kiln with slopping pipe. Kiln is heated by burning pulverized coal and temperature is maintained at 1400 to 1500 C in clinking zone to kiln.

3)

M.Sc. (II) Inorganic Chemistry notes by Swapnil Prabhulkar

The Institute of Science, Mumbai

Reactions in Kiln: Initially 1/4th length of kiln is drying zone. In this zone water is driven out of slurry by means of hot gases; the temperature in this zone is about 200-300 C. Second zone is calcinators zone. Here organic matter burn away. CaCO3 decomposes into CaO and CO2 escapes at about 900 C.

CaCO3

CaO

CO2

When reaction is complete material has traveled 3/4th of length of kiln. Decarbonation is an endothermic reaction. After decarbonation material goes into hot zone known as clinking zone. Temperature in this zone is about 1400-1500 C. Here 20-30 % of material is converted into liquid i.e. it fuses. The reactions occur are:
2 CaO

+ +

SiO 2 SiO2

2 CaO.SiO 2 Dicalcium silicate 3 CaO.SiO2 2 Tricalcium silicate

3 CaO

3 CaO.Al2O3 2 Tricalcium aluminate Similarly MgO is changed into magnesium silicate, etc. The reactions are exothermic in nature. The temp. has to be properly controlled in order to avoid excessive vitrification of the mass. Liquid reacts with surrounding particles. Sintering takes place in this zone. Clinker is formed and it falls out from lower end of rotary kiln.

3 CaO

+ Al2O3

5)

COOLING OF CLINKER At lower end of kiln clinker coolers are attached to kiln shell all around the periphery. Clinker is cooled in these coolers. Simple rotary types of coolers are used to cool clinker. Quality of cement produced depends upon rate of cooling. Following are the effects of rate of cooling on properties of cement:

i) Very slow rate of cooling: If rate of cooling is very slow then no gas is formed by super cooling. Because of this, the phenomenon called as Dusting occurs. Dusting means conversion of 3CaSiO3 to powder from and not to crystalline form. This form of 3CaSiO3 has very less binding power and it hydrates very slowly. ii) Slightly fast rate of cooling: Under this condition all melted alumina and iron is solidified into glass. Hence crystalline compounds of alumina and iron are not formed. This is advantageous because crystalline compound 4CaO.Al2O3.Fe2O3 has no hydrolytic property. iii) Medium rate of cooling: In this method, liquid in clinker crystallizes and large quantity of 3CaO.SiO2 is formed which gives great strength to the cement.

M.Sc. (II) Inorganic Chemistry notes by Swapnil Prabhulkar

The Institute of Science, Mumbai iv) Very rapid cooling: In this, clinkers containing Magnesium form glass. Due to this there will no there will not be expansion of cement even after years. Therefore, ultimately it is very necessary and important that cooling of clinker should be controlled to produce definite degree of crystallization of melted clinker. 6) GRINDING OF CLINKER Final product, which is clinker, comes to tube mill from coolers. Clinker consists of granular masses. Clinker is pulverized and then further ground in tube mills.

MIXING IN REACTIOR During grinding, additives such as retarders, dispersing agents etc. are mixed. Retarder consists of gypsum (CaSO4.2H2O) or plaster of paris (CaSO4.1/2H2O). Retarder is necessary to prevent quick stiffening of cement paste. Final clinker product is called Portland Cement. It is so fine that 98 % to 99 % of it pass through 200 mesh sieve. Then finely ground powder of cement is packed into package by automatic machine. Cement thus produced for common purpose contain following constituents CaO = 63%; SiO2 = 22%; Al2O3 = 06%; MgO = 03% and others = 03%.

7)

CHEMISTRY OF SETTING AND HARDENING OF CEMENT PASTES Setting and hardening of cement is result of hydration reaction occurring between cement compound and water. Main principle behind setting and hardening of cement is non-reversible gel formation and coagulation of suspension of finely divided solid dispersed in liquid. When Portland cement is mixed with water, it is converted into plastic mass called Cement paste. Due to this hydration reaction begins. Because of hydration reaction gel and crystalline products are obtained. These are capable of binding inert particles of aggregate. Setting is defined as, Stiffing of originally plastic mass of cement and water. Hardening follows settling. It is result of further hydration processes advancing gradually into interior of particle core. Strength developed by cement depends upon amount of gel formed and degree of crystallization.

M.Sc. (II) Inorganic Chemistry notes by Swapnil Prabhulkar