Mapei Additives
Mapei Additives
Mapei Additives
INDEX
THE WORLD OF MAPEI LIQUID ADMIXTURE DIVISION CEMENT GRINDING ADDITIVES DIVISION TECHNICAL BACKGROUND OF MAPEI GRINDING AIDS A BRIEF OUTLINE OF AN ANALYSIS OF THE SEPARATION PROCESS
2 6 8 10
22
PRODUCTS MA.G.A./C Technical Data Sheet Industrial Trial with MA.G.A./C1 Industrial Trial with MA.G.A./C2
37 39 41 51
MA.G.A./M
61
MA.P.E./S
63 65
MA.P.E./W
77 79
MA.P.E./A
89
MA.P.E./Cr 05 Technical Data Sheet Scientific Background Industrial Trial with MA.P.E./Cr 05
91 94 100
Founded in Milan in 1937, Mapei is todays world leader in the production of adhesives and chemical products for building. Starting in the 1960s Mapei put its strategy of internationalization into action in order to have maximum proximity to the needs of local markets and reduction of shipping costs to a minimum. The Group now counts 57 subsidiaries with 54 production facilities in operation in the 5 continents in 24 different countries. Furthermore, Mapei has developed a sales and technical service network with offices all over the world and offers an efficient Technical Assistance Service that is much appreciated by architects, engineers, contractors and owners.
TO BE OUR CUSTOMERS BEST SUPPLIER We offer our services as a business partner and we are highly committed to provide our customers solutions with a high added value.
TO BUILD A PARTNERSHIP WITH OUR STRATEGIC SUPPLIERS We are committed to ensuring that our strategic suppliers turn meeting our needs into an opportunity to jointly design new products and solutions which can also cater for the latest market requirements.
TO ALWAYS KEEP ONE STEP AHEAD We try to anticipate designers requirements and interpret business and building-site needs.
TO INNOVATE CONSTANTLY Every year we strategically invest more than 5% of our overall turnover in Research & Development.
TO BUILD A WINNING AND COMMITTED TEAM Our most precious resource is the value of our team: we work together passionately and grow professionally thanks to constant training. TO BE DETERMINED TO ACHIEVE EXCELLENCE We strive to achieve ambitious goals so that we are market leaders in our chosen sectors.
THE 10 PILLARS
OF OUR SUCCESS
TO ALWAYS TELL THE TRUTH A high-profile and transparent communication strategy allows us to convey and share our values with as many people as possible.
TO MAINTAIN SOLID FINANCIAL FOUNDATIONS So that we can invest in the technology and products of the future.
TO IMPROVE ALL OUR PROCEDURES BY MEANS OF QUALITY CONTROLA All our products and services conform to the highest ISO 9001 certified standards.
TO BE AT THE CUTTING-EDGE IN TERMS OF ENVIRONMENTAL SAFETY AND HEALTH We attach great importance to the environmental sustainability of our products, the eco-friendly nature of our procedures and the safety of our customers, workmates and entire community.
Mapei has always devoted a lot of effort to research. 5% of turnover are allocated to investments in this field of activity. 12% of Mapei employees work in research.
Our commitment for the environment More than 150 MAPEI products, featuring the Green innovation mark, help to contribute valuable points toward LEED-certified projects.
2008. ROBBIANO DI MEDIGLIA (MILAN) In the picture, the main manufacturing plant of the 54 facilities of the Mapei Group. In 2008 the expansion project of Robbiano di Mediglia plant is still ongoing with the new wall finishing production line.
Integrated solutions for the cement-concrete sector, for lower consumption of non-renewable raw materials, to reduce CO2 emissions and increase the service life of structures.
CONCRETE ADMIXTURES
more less
energy efciency
more less
durability
clinker and CO
HPSS* SYSTEM
more less
more less
* HPSS System High Performance Solidification System for treating contaminated ground and sediments
CEMENT GRINDING ADDITIVES DIVISION Founded in 2000, D.A.M. (Divisione Additivi di Macinazione) has grown an astonishing 30% every year in terms of turnover and volume, thanks to innovative and highquality products combined with technical support and dedicated Research and Development. Today, supported by the groups structure and expertise, D.A.M. is supplying all major cement groups worldwide, offering new technologies and local technical assistance. By combining high quality raw materials, fully computer-based production facilities and specific expertise in terms of product chemistry, industrial employment and grinding plant technology, D.A.M. is able to guarantee high levels of customer assistance and product quality.
R&D By investing over 5% of its turnover and 12% of its Human Resources in Research and Development, the Mapei Group has become market leader in terms of innovation. The dedicated D.A.M. scientists at Mapeis Research Centres not only develop new raw materials and grinding aid components, but are also active in customer support. In fact, Mapeis state of the art laboratories allow D.A.M. to perform specific and in-depth clinker and cement analysis in order to optimise the use of Grinding Aids and to offer customized solutions for cement performance enhancement and production improvement.
ECO-SUSTAINABILITY Mapei grinding admixtures form a system of innovative solutions for cement works; they allow a reduction in clinker while offering the same mechanical performance of cement, thus guaranteeing a reduction of 5-10% in CO 2 emissions and a saving in nonrenewable raw materials. TAG TEAM (Technical Assistance Group) A team of experienced process engineers from the cement industry joined D.A.M. in order to provide specific technical assistance to D.A.M. customers. By performing complete plant audits and by analysing the grinding circuits performance, they are able to assist D.A.M. customers with the implementation of Grinding Aids and to optimise the grinding process in all its aspects.
Our Products
Product Group
Description
Typical Dosage
Production Strength Workability* Air Cr(VI) Typical CO2 Increase* Increase* Entrainment* reduction* Application Reduction
MA.G.A./C
Highly concentrated, high performance grinding aids, suitable for grinding of all cements.
All Cements
MA.G.A./M
Highly concentrated, high performance grinding aids, particularly suitable for grinding of minerals. Grinding aids, strength improvers, specically formulated for grinding of blended cements (pozzolanic, blast-furnace slag and y- ash cements).
MA.P.E./S
Blended Cements
Grinding aids, strengths and workability (ow) improvers, specically MA.P.E./W formulated for grinding 1000 - 2000 g/t of blended cements (pozzolanic, blast-furnace slag and y- ash cements).
Blended Cements
MA.P.E./A
Masonry Cements
MA.P.E./Cr
50 g/t ppm
All Cements
Please contact us dircetly for specific product selection, assistance and technical documentation.
1. THE AGGLOMERATION PHENOMENA During the grinding process, the increase rate in the specific surface proportionally decreases with the fineness increase. Rittingers law demonstrated that there is a direct proportionality within the grinding time and specific surface till a precise fineness (depending on the material and the grinding system). Beyond this fineness the real curve diverges from the theoric one, and there is no more direct proportionality between grinding time (energy) and produced specific surface. In practice, it is not possible to exceed some fineness values, not even by extending the grinding time. This is principally caused by the particles agglomeration that drastically reduces the process performance. The cement particles agglomeration acts on the grinding and on the mill lining as an abrasion resistant film, but also as fine particles, already grinded, agglomerated by electrostatic forces and local conditions of pressure and temperature. It is easy to understand how the film and particles agglomerates can reduce the mill balls effect, by absorbing bumps and dispersing the energy needed for the particles comminution. The agglomeration phenomena entity depends on: material type (chemical composition, crystalline structure); Grinding fineness; mill type (ball mill, vertical mill etc.); grinding system: open or closed circuit; balls and lining conditions; temperature, humidity, ventilation etc. inside the mill. 2. MECHANISM OF ACTION OF THE CEMENT ADDITIVES Grinding aids have been widely used for more than 50 years. It is also well known that their main aim is to prevent cement particle agglomeration during the milling process. As a consequence they reduce mill retention time and improve separation efficiency, which decrease energy consumption of the plant while maintaining constant the quality and quantity of the cement produced. Cement additives improve mechanical strengths by producing a narrower cement particle size distribution, which at the same time is shifted toward smaller diameters (Figure 1).
Figure 1 Particle Size Analysis
(blank) = 31,50 m
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While all that we have said up to now is evidence of cement additive use which has allowed their diffusion, their real action mechanism in the hydration of cement is not completely understood yet. What is not yet clear are the actual chemical-physical interactions they have with cement, which give it all the properties and advantages already mentioned above. The more accepted thesis is that the grinding aids act to reduce the surface energy forces generated on cement grains during comminution. They are composed of polar organic compounds, which arrange their dipoles so that they saturate the charges on the newly formed particle surfaces of the clinker, reducing agglomeration (Figure 2).
Figure 2
This theory stems from the fact that water, itself a polar molecule, has been considered to be a grinding aid, but deemed less efficient due to its low screening effect. However, this theory does not fully explain the fact that an additive is effective even at very low dosages (< 500 ppm) considered insufficient for a complete covering of the cement particle surface which would be necessary for the free charges screening theory to be the only explanation. Since no exhaustive evidence has been found that this is the unique mechanism, research in this field is still going on, making use of the most sophisticated and modern technologies, trying to find an appropriate answer to this problem. Various research groups have followed distinct approaches, such as analysis of the sample additive extracted from cement after grinding, morphological analysis of the cement paste after addition, evaluation of the relationship between additive effects on mechanical strengths and cement mineralogical composition. Since 2000 MAPEI R&D laboratories have also concentrated their efforts on this subject, with the objective of formulating high performance cement additives, which can satisfy client expectations. Our approach has been as much multidisciplinary as possible with the aim of look at all aspects of this complex subject. To do this, we have used some of the most updated analytical techniques such as:
Figure 3
a (0 mins)
b (5 mins)
c (60 mins)
d (420 mins)
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Since the first gel forms within a few seconds and covers completely the cement grain, it actually represents the grain surface. Then water and any substances added to the cement, working as an admixture, must interact with this gel. This means that during the milling process of the cement, which is usually carried out in presence of water and grinding aids, conditions exist for the electrostatic charges dispersion discussed before, but most of all for a preliminary hydration of the clinker. Once the clinker powder produced is then mixed with water, we observe the formation of a gel, whose structure is drastically different when grinding aids, such as MA.G.A. / C, are used during the milling process (Figure 4).
Figure 4
These preliminary investigations suggest that the cement maintains a memory of the kind of manufacturing process. 3. BENEFITS OF GRINDING AIDS Grinding aids (GA) are principally employed for mill output increase at the same specific surface (specific energy saving). The main benefits of GA are the following: Increase in output at the same fineness. Output increase reduces specific energy costs. The increase in production could be used to cover market demand (increased sales), to reduce production costs (grinding during lower energy cost periods) and to reduce maintenance costs. Fineness increase at equal output, or both effects. In some cases very high fineness may only be obtained by using GA. Fineness increase at equivalent specific consumption allows improvement of the final product performances (e.g. cement strengths). Improved granulometric particle distribution curve at equal fineness. In case of two cements grinded at the same Blaine specific surface, the one grinded with GA has higher mechanical strengths thanks to a more compact granulometric particle distribution curve obtained through the elimination of the finest and coarse particles.
Lower grinding media consumption. Higher separator efficiency. When agglomeration occurs a particle agglomerate would be seen as a coarse particle and swept out by the separator. With the addition of MA.G.A./C the particles are separated and passed as fine particles suitable for the final product. Improved flow characteristic of the cement during transport, silo storage and during loading/unloading operations. Reduction of silo clogging, that usually results in reduced silos volume and extraordinary repairs costs. 4. QUALITY IMPROVERS/PERFORMANCE ENHANCERS Even if the pure grinding aids could be considered as grinding products which somehow improve the quality of the finished material (ex. calcium carbonate with better granulometry and/or with better flow) it is necessary to distinguish them from the pure quality improvers, that are tailor-made formulations, and for which it is advisable to consult with the Cement Additives Division technicians. 4.1 Cement additives Cement performances are principally characterized by mechanical strengths, water demand and setting times. MAPEI has formulated additives focused on improving each single characteristic, while at the same time maintaining a strong grinding effect. Mechanical strengths. The UNI ENV 197-1 sets out the mechanical strengths required for each cement class. The reasons why mechanical strengths (at early and ultimate ages) could be improved are the following: - technical (insufficient strengths) - commercial (competition on the market) - economical (decrease in clinker additions, changing the cement composition etc.) Water demand. For certain types of cement (usually pozzolanic and fly-ashes cements) it is important to control the flow values and modify them on end-users requests. There are specific additives especially formulated to solve this problem, and that do not interfere with concrete admixtures. Initial/final setting time. Special additives work on initial and final setting time, offering a cement adapted to local temperature or to the season. Usually the capacity of the additive to modify the setting times is an additional option, and its principal aim is as a grinding aid or strengths improvement. 4.2 Air entrainers for hydraulic masonry cements Artificial hydraulic masonry cement is obtained with the addition of 15-40% of clinker, and is characterized by good mechanical strengths, but lower workability than the natural one. The MA.P.E./A give to artificial hydraulic masonry cements characteristics similar to the natural ones (workability and durability). They also improve entrapped air and water retention. Air is entrained in micro-bubbles, homogeneously distributed, that improve cement workability, yield per surface unit and resistance to freeze-thaw cycles. Water retention improves adhesiveness by avoiding cracking.
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4.3 Pack-set inhibitors for minerals Pack-set inhibitors are added during the dry minerals grinding process to obtain output increase or high fineness. In case of calcium carbonate the additives must improve the flow characteristics of the grinded material. For this reason specific products have been formulated, and are appreciated as much for their dispersing properties as for their grinding aid characteristics. MA.G.A./M GA are available to satisfy various requirements, and tailor-made formulations can be studied by our Division. 5. GRINDING AIDS EVALUATION The evaluation of grinding aids has to include both technical and economical considerations. The technical evaluation follows a reliable industrial trial, performed after preliminary lab tests. The economical evaluation, to be preferably performed after the technical one, has to consider several factors that are not always easily quantified in terms of money. 5.1 Technical evaluation: industrial trials with grinding aids Industrial evaluation of GA is necessary to verify their real obtainable performances. For this reason a reliable industrial trial has to be carried out for a right evaluation of the product. A reliable industrial trial must reduce to the minimum the quality differences of the raw materials used for the cement production. Our suggestion is to grind for 2 weeks 1 month, in order to compare the average results obtained in a similar control period immediately before the industrial trial. We hereby summarize the most important points that the Cement Additives Division suggests to follow during an industrial evaluation of the additives, specifically referring to the cement. Only a reliable industrial trial performed for a long time can assure reliable results; our policy is to carry out a long period test and to render technical assistance during the trial. A reliable industrial trial must be carried out under normal and regular production cycles. A long-period trial allows results to be obtained that are not affected by the normal variations of the clinker, lime or other added materials. Each MAPEI additive has been completely tested in the lab, but the industrial trial is always necessary to define the real additive performance on the cement. At the beginning of each trial, it is necessary to precisely define the plant working conditions with or without the additive to be tested. It is important to define a sampling plan; it is advisable to divide the samples for the planned lab tests to be performed both by the cement plant and Mapei laboratories. To optimize the results, a co-operation between plant technicians and Mapei consultant is advisable. At the end of the trial, we suggest a meeting in order to work on the same results. At the end of the industrial trial, Mapei technicians will write a complete technical report to be sent to the cement plant. 5.2 Economic evaluation The most apparent effects of a grinding aids are output increase and energy saving, that could be easily evaluated in terms of money. The other benefits are not so easily estimated, though sometimes they are more conspicuous than the energy saving.
The following formula quantifies the energy saving in terms of money S[/t]: Where: -P - - Ke - Ka mill output without additive mill output increase total energy costs (absorbed kWh * cost kWh) additive cost (cost per kg * dosage) [/t] [t/h] [%] [] [/t]
This formula calculates the saving per ton of ground material, in the cases where: - Output increase at equivalent energy consumption; - Fixed energy cost, at all times of the day; - Product with similar quality to the previous one (without additive); - Additive dosage calculated on the initial mill output (most common case). When the dosage is calculated on the new mill output, the formula is modified as follows:
In practice, with the above calculation of the economical advantages, other several factors are not considered; they have to be evaluated case by case and are always more difficult to estimate. We hereby summarize the principal elements to be considered for a correct and complete estimation. It has to be noted that, while the energy saving is always considered, other advantages depend on the process conditions and should be evaluated to each specific situation. 5.3 Production benefits Mill output increase: more material available to increase sales. Grinding during low energy cost periods: lower average cost per unit of energy. Better management of peak market demands, due to increased production capacity. The additive could be considered as a flexible production tool, even though not constituting a structural investment. 5.4 Quality benefits Cement performance improvement; greater competitive position on the market; Production of the same cement by decreasing the clinker percentage, with a saving in production costs. 5.5 Maintenance benefits A higher production per hour allows more time for preventive maintenance interventions, avoiding urgent maintenance that is always more expensive. Better flow characteristic of the cement during transport and in silos, with a significant reduction of the plant stops and maintenance costs.
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6. ADDITIVE SELECTION The grinding aid is liquid, and has to be dosed through a metering pump, onto the conveyor belt or directly in the first chamber of the mill. 6.1 Dosage system The simplest system is a manually regulated pump, installed soon after the other material measurers, at the mill entrance. When the mill is operating under standard conditions, the additive is dosed at a fixed flow rate, and does not alter in line with production variations. It is a very efficient system, but has no flexibility and has to be strictly controlled by the operators. In modern plants, the flow rate depends on the real mill output, and the additive is dosed by a flow gauge that controls the pump through a computer. In this way the additive is treated as one of the other components to be added in the mill, by indicating its percentage in the cement composition. 6.2 Metering pumps Plunger or diaphragm metering pumps can be used. Plunger metering pumps (with steel plunger and pump head) are largely used, due to their low cost. Diaphragm pumps are more sophisticated and their benefit is that the plunger is not in direct contact with the additive. They can also suck viscous additives and are not damaged by impurities sucked from the bottom of the tank. In order to optimize the additive dispersion (especially for low dosage additives) our suggestion is to install a double headed pump: the first head for the GA, and the second one for water, with an additive/water ratio of 1:2 or 1:3. It is advisable to install a cartridge filter between the additive tank and the pump, in order to prolong its functional lifetime. 6.3 Additive dosage onto the conveyor belt This is the simplest system and allows a direct visual control of the flow. The additive must not wet the conveyor, to avoid crusts whose thickness may enlarge on the return and support rolls. The most frequent problems are caused by high dosage additives (0.2-0.3%) and on quick conveyor belt (with a low material layer): in this case is necessary to use a rake to better distribute the additive and avoid drops falling onto the bare belt.
Mill output
Regulation
30 m3
30 m3
6.4 Additive dosage into the first chamber of the mill This is the cleanest dosage system, but it has to be carefully controlled to avoid problems. It is advisable to install a metal lance with two coaxial tubes: the additive will flow inside, and the outside support air will be supplied by a fan. The additive tube must extend 1 cm more than the air tube, to allow any possible drops to fall on the material. The fan has to work for a certain period after each mill stop, to avoid the obstruction of the additive nozzle by the powder in suspension. It is also advisable to position a T tap before the mill entrance, in order to manually measure the additive flow.
Mill output
Regulation
30 m3
30 m3
19
ST
6.5 Pump installation Installation 1. Secure the pump to a horizontal support 2. Control that the oil level for the lubrification of the gears is ok 3. Protect the pump from liquids and powder 4. Leave enough free space around the pump for maintenance operations and adjustments.
150 mm
80 mm
100 mm
Fig. 1
100 mm
Typical scheme of installation in the plant 1. Low positive pressure in suction, hsuc 2. Higher positive pressure in discharge, h.>hdisc 3. Short and linear suction circuit 4. Suction and discharge circuits section pump connection section
hdisc
hsuc
Fig. 2
21
In the cement plants the simple scheme below is used to dose the additives, considering that they are dosed at low pressure and room temperature. For a more complete dosage system the following components could be installed:
Suction circuit a. Realise a short and linear circuit, with tube diameter of about 1.5 times the pump nozzles. The max flow rate per single piston pump is 3,14 times more than the average one. b. Install a permanent filter (1) in front of the pump in an easily accessible place, with 150 m meshes. c. In case of long tubing, install a damper (2) beside the nozzle, in order to avoid the phenomena of cavitation. d. Avoid connecting the pump to the tank bottom, to avoid the suction of potential impurities. e. Install a shut-off valve (3) for the disassembly of the pump when the lines are full. Discharge circuit f. Realize the circuit with tubes with diameter wider than or similar to the one of the pump nozzle. g. It is advisable to maintain between suction and discharge a positive difference of pressure (40 100 KPa), as per fig. 2. If this is not possible due to the position of the tank and of the discharge circuit, (ex. tank positioned higher than the suction circuit) it is possible to install a back pressure valve (5). h. Soon after the pump it is advisable to install a calibrated safety valve (4), with a visible and open discharge. i. To regulate the liquid flow it is advisable to install a pulsation damper (with direct contact or with a dry diaphragm), soon after the pump discharge valve. In case of installation of a back pressure valve, it is better to position the damper after the valve. j. In case of installation of a flow regulator (mechanical or inductive) (6), it is advisable to install a filter before the flow regulator. k. A check valve should be installed for the possible disassembly of the pump when the lines are full.
Amongst the large range of installations schemes of closed grinding circuits, which could include one or more separators, we will consider and study the classic disposition represented in Fig. 1 where one mill and one dynamic separator are used.
Fig. 1
In the above scheme the machines operational systems are well defined. The mill has a comminution function that, from a starting particle size distribution, creates new and smaller cement particles and subsequently new specific surface. From the particle size distribution supplied by the mill it is possible to produce a new product with requested specific surface through a separator: the residue is automatically sent back to the mill for further grinding. In a closed circuit the separator increases the working value of the principal system: the mill. 1. EVALUATION OF A CLOSED CIRCUIT GRINDING SYSTEM 1.1 Circulation coefficient In practice there are several systems for the evaluation of a plant working in a closed circuit; the most immediate one seems to be the circulation coefficient, expressed by the ratio F/P (sep. feed material/final product). It is a general opinion that a high circulation rate means a poor function of the separation and vice versa; this could be true but the concept should not be generalised. In fact the final product could only be evaluated from the particle size distribution obtained with the mill; if the final product is big the separator could only extract a fine product by refusing a significant amount of coarse material, resulting then in a higher circulating load. The circulation coefficient could then be considered as a quality index of the functioning of the complete system, and not only of the separator. It is useful to precise that the circulation coefficient A/F (circulating load) is also based on the mill
23
dimensions, and depends on the L/D ratio. It is then logical that with short mills, the circulating charge F/P has to be proportionally higher. In practice the circulating load represents an artificial extension of the mill, that is to say a uniformity of permanence time of the material in the mill, with respect to other L/D ratios. 1.2 Separator precision Several methods have been proposed for the evaluation of the precision or performance of a separation process. In case of separation in two granulometric classes, having decided a separation dimension, and called a, g and f the fractions (% in weight) contained respectively in the feeding material, coarse and final product, the separator performance can be defined as the ratio between the fine material contained in the final product and that contained in the feed material. Tab. 2 summarizes the methods normally used in accordance with the VDZ and MT28 standards. The above assumptions have already been criticized, by highlighting the inadequacy of the evaluation of the functioning of an air separator, due to the influence of the granulometry of the feed material on the results. Furthermore, the choice of a particular separation dimensions, obtained by the above formulas, can be considered as arbitrary, or at least, unjustified. For this reason it is advisable to apply the Tromp curve (or T curve). This function represents the trend of the separations coefficient rates of the feed material on the coarse and on the final product, for the several granulometric intervals as a frequency curve on which the separation process takes place. This should allow for greater precision, irrespective of the feed materials composition and of the choice of the separation dimensions. The quantitative evaluation of the above precision depends on some curve parameters; the separation precision is defined by the rule VDZ as the rate d35/d65 (being d35 e d65 respectively the granulometries in m corresponding to a separation degree of 35 % and 65 %); the same rule defined the separation limit as the particle dimension of 50% between large and fine. In practice these parameters are not always applicable due to the fact that, as the curve T is dependent on the A/F rate, the separation curve of many plants is above these distinctive points, and it is thus quite impossible to make a reliable calculation. Recently other evaluation methods have been studied and proposed by C.E.T.I.C., always derived from the Tromp curve that, though its value is not intrinsic, allows the location of the curve with precise coefficients, hence allowing calculations to be carried out. In practice, following CETIC (that proposes to use the Gaussian coordinates to draw the diagram), the curve T is resolved into two lines: 1. the horizontal line, that is the mean of the separation degrees below the ordinate at the abscissa point 1 m (soutirage or by pass); 2. a regression line related to the succeeding points on the ascending part of the curve.
We can state the following: a. the soutirage or by pass, measured from the minimum ordinate (1), represents the material passed through the separator without being classified. b. The quality of the cutting, defined by the inclination of the ascending part of the T curve; the inclination has also been measured by the imperfection value. TAB. 3 shows in details the drawing system of the T curve following CETIC. 2. COMMENTS We tried to summarise the different methods applied for the evaluation of the separator functioning. We consider it opportune, at this point, to express our considerations on the argument: We already criticized the limits of the so-called performance (arbitrary choice of the particle dimensions, influence of the granulometry of the feeding material, etc.); it is necessary to remember that the above formulas derives from the mineral preparation technique where, generally, it is necessary to separate the components of a granulometric mix into two fractions. These fractions could be different one from the other for particle dimensions or chemical composition; in this case a product can contain a material that has not been treated and that has to be separated or recycled, or a fine component mixed in a inert mass, that has to be extracted for a further treatment. The formulas represent a concept bound to the results (performance) of a classification; they measure the efficiency of the operation in open cycle in relation, for example, to the loss of fine material (final product) in the coarse recycled product. In our case, separation in closed cycle, the coarse material is re-introduced in the mill for a further refining and consequently, from the point of view of the preparation of the granulometric curve for that type of cement, the material to be ground in the mill is already fine, with a consequent energy saving when compared to a bigger granulometry. The Tromp curve and related parameters, even though they precisely represents the separation process, are affected by the ratio between the loading charge (A) and productivity (F) in such a way that is not possible to evaluate the separator, independently from the kind of mill in use. The separation coefficients confirms the theoretical deduction that the preciseness of the separation, appearing from the T curve, is higher when the circulation coefficient A/F is lower. Following this assumption, the performance of the separator is optimal if combined with a long mill, and on the contrary is worse if combined with a short or very-short mill. 3. CALCULATION EXAMPLES Taking into consideration the limits defined by our assumptions concerning the possibility of comparison between two different separators, we hereby report the T curves of some separator plants, useful for a clear understanding of the above mentioned concepts.
A B R I E F O U T L I N E O F A N A N A LY S I S O F T H E S E PA R AT I O N P R O C E S S
25
The table below summarises the representative parameters (rounded off to significant values): Mill L/D ratio 3.6 3.1 3.3 3.0 Loading charge A/F 1.3 1.4 1.5 3.9 Separator type Wedag ZUB36 Polysius TSU Wedag ZUB60 Smidth CV short Soutirage % 12 19 9 66 Line inclination degrees 31 24 46 22 Circuit N 1 2 3 4
Some comments: The separators are of the 1st (Polysius e Smidth) and of the 2nd generation (Wedag): the Polysius TSU has double shafts while the Smidth separator has only one shaft. The mills L/D ratios ranges between 3 e 3.6, and so are not different one from the other The loading charges, except from circuit no. 4, are coherent to the mills L/D ratios, even if they are quite low. As already anticipated, the "soutirage" value quantifies the material passed through the separator, but that has NOT been classified. It could be defined as a separation error. At this point, the performance of the Wedag separator was good. On the contrary, the performance of the Polysius separator of plant [1] was worse. In fact, with a loading charge of 1.4 (that is quite low, and it is already known the direct correlation within loading charge and soutirage), a by-pass error of 19% has been noted. It has to be taken into account that this is a 1 generation separator. Always considering the soutirage, the separation results of plant [4] would appear really negative; the soutirage error was 66%; however knowing the plant and the separator in use, we can define that these poor performances are essentially caused by the high fineness of the product, and by the limits of the fineness regulation system of the separator itself. Concerning the separation quality, represented by the inclination of the second branch of the T curve, a substantial equality between all the separators is revealed. The inclinations range between 20 and 30 degrees. The only exception is the separator of plant [3] which has a higher inclination, and hence precision, with a line angle of 46. In conclusion, the last observation: Taking into account the limits of our assumption, and also the difficulty of comparison, we deem it useful to highlight the good performance of the Wedag separator which may be judged as reliable and competitive even when compared to the latest 3 generation separators.
Separation Analysis (Tromp Curve) Cement Plant Mill Separator Test no. Date dim.m 2 4 8 16 32 64 128 190 1.0 3.0 6.0 12.0 24.0 48.0 96.0 159.0 Cement Type Production t/h Spec.surf. M2/kg blaine laser g 9.6 16.8 21.0 23.8 28.5 50.9 85.6 98.8 df 16.0 11.7 9.7 11.8 21.4 23.3 6.0 0.1 da 15.0 10.0 7.8 9.5 17.7 23.1 14.8 2.1 dg 9.6 7.2 4.2 2.8 4.7 22.4 34.7 13.2 CEM II/A-M 32.5 R 42.5
494.7
335.0 Materials in cycle residue [determ. laser / m] t/h 30 m 40 m 60 m final 42.5 feeding 56.0 coarse 13.5 A/F 1.3 Sep. Line angle Deg. % 11.6 % 56
90 m
200 m
31
T separation curve
T curve
soutirage
regression
ord.sep.diam.
Linear (regression)
A B R I E F O U T L I N E O F A N A N A LY S I S O F T H E S E PA R AT I O N P R O C E S S
27
Separation Analysis (Tromp Curve) Cement Plant Mill Separator Test no. Date dim.m 2 4 8 12 21 30 60 90 128 192 1.0 3.0 6.0 10.0 16.5 25.5 45.0 75.0 109.0 160.0 Cement Type Production t/h Spec.surf. M2/kg blaine laser g 10.3 17.7 26.9 32.8 47.8 56.1 74.8 87.5 96.0 98.9 8.1 13.9 20.9 24.9 33.0 37.5 53.0 71.2 89.9 96.1 df 11.7 7.8 9.9 6.8 18.0 9.9 19.9 10.3 4.1 1.4 da 10.3 7.4 9.2 5.9 15.0 8.3 18.7 12.7 8.5 2.9 dg 8.1 5.8 7.0 4.0 8.1 4.5 15.5 18.2 18.7 6.2 CPC 30 126.0 325 328 df*F/A 8.2 5.5 6.9 4.8 12.6 6.9 13.9 7.2 2.9 1.0 dg*G/F 2.42 1.73 2.09 1.20 2.42 1.35 4.64 5.44 5.59 1.85 A 10.62 7.20 9.03 5.96 15.04 8.28 18.58 12.66 8.47 2.84 G/A 0.23 0.24 0.23 0.20 0.16 0.16 0.25 0.43 0.66 0.65 T (%) 22.81 24.09 23.18 20.06 16.11 16.25 24.95 42.99 66.06 65.40
f 11.7 19.5 29.4 36.2 54.2 64.1 84.0 94.3 98.4 99.8
591.6
448.5 Materials in cycle residue [determ. ALPINE] t/h 30 m 40 m 60 m final 126.0 feeding 179.8 coarse 53.8 A/F 1.4 Sep. Line angle Deg. % 19.0 m 131
90 m
200 m
24
T separation curve
T curve
soutirage
regression
ord.sep.diam.
Linear (regression)
Separation Analysis (Tromp Curve) Cement Plant Mill Separator Test no. Date dim.m 2 4 8 12 21 30 60 90 128 192 1.0 3.0 6.0 10.0 16.5 25.5 45.0 75.0 109.0 160.0 Cement Type Production t/h Spec.surf. M2/kg blaine laser a 6.6 11.9 22.9 31.3 46.9 55.1 74.8 85.9 93.8 96.4 g 3.6 6.3 9.2 10.3 11.4 13.0 35.1 59.8 83.5 91.5 df 9.8 7.0 12.6 10.2 22.5 11.6 20.1 5.6 0.5 0.1 da 6.6 5.3 11.0 8.4 15.6 8.2 19.7 11.1 7.9 2.6 dg 3.6 2.7 2.9 1.1 1.1 1.6 22.1 24.7 23.7 8.0 42.5 PTL 115.0 397 332 df*F/A 6.6 4.7 8.5 6.8 15.1 7.8 13.5 3.8 0.3 0.1 dg*G/F 1.18 0.89 0.95 0.36 0.36 0.53 7.27 8.12 7.79 2.63 A 7.76 5.59 9.41 7.21 15.46 8.31 20.76 11.88 8.13 2.70 G/A 0.15 0.16 0.10 0.05 0.02 0.06 0.35 0.68 0.96 0.98 T (%) 15.25 15.89 10.13 5.02 2.34 6.33 35.01 68.36 95.87 97.51
f 9.8 16.8 29.4 39.6 62.1 73.7 93.8 99.4 99.9 100.0
624.5
323.7 Materials in cycle residue [determ. ALPINE] t/h 30 m 40 m 60 m final 115.0 26.3 11.4 6.2 feeding 171.3 44.9 32.6 25.2 coarse 56.3 87.0 76.9 64.9 A/F 1.5 Sep. Line angle Deg. % 9.2 m 77
T separation curve
T curve
soutirage
regression
ord.sep.diam.
Linear (regression)
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29
Separation Analysis (Tromp Curve) Cement Plant Mill Separator Test no. Date dim.m 2 4 8 12 21 30 60 90 1.0 3.0 6.0 10.0 16.5 25.5 45.0 75.0 Cement Type Production t/h Spec.surf. M2/kg blaine laser g 12.0 22.9 32.9 41.2 52.3 60.6 82.9 94.4 11.8 21.4 30.4 37.0 45.9 53.3 77.5 91.2 df 16.9 13.3 12.3 11.6 15.7 9.7 17.7 2.8 da 12.0 10.9 10.0 8.3 11.1 8.3 22.3 11.5 dg 11.8 9.6 9.0 6.6 8.9 7.4 24.2 13.7 CEM II/A-S 42.5 R 85.0
490.2
368.5 Materials in cycle residue [determ. ALPINE] t/h 30 m 40 m 60 m final 85.0 feeding 337.0 coarse 252.0 A/F 4.0 Sep. Line angle Deg. % 65.9 m 65
90 m
200 m
22
T separation curve
T curve
soutirage
regression
ord.sep.diam.
Linear (regression)
4. CONCLUSIONS On the separator performance problem, it is important to remember the assumption of B. Beke (Principles of comminution, Akademiai Kiado, Budapest, 1964): luckily the separators do not have a 100% performance, otherwise it would not be possible to create the granulometries necessary for the development of the cement characteristics. In our opinion it may be added that all the formulas, results and evaluations obtained with the available methods, are NOT transferable; that means that an objective analysis of the functioning of the separator is not possible if separated from the analysis of the combined mill. Indisputable is the fact that, inside a grinding system, each single variation of the separation parameters can affect the mill output (and vice versa), and this is revealed by the specific energy consumption. The successive separation analysis will only confirm the variation (positive or negative) of the parameters of evaluation. With the above assumptions, and taking into consideration the usefulness of the analysis of a separation process, we would like to emphasise our belief that it is impossible to have objective comparisons of other and different separators when installed on different circuits.
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31
CAPACITY M A F G t/h t/h t/h t/h fresh material feed = F separator feed fine material coarse material with a one reference particle dimension passing of A passing of F passing of G
GRANULOMETRIES a f g % % %
FUNDAMENTAL EQUATION A = F+ G A*a = F*F + G*G LOADING CHARGE u = A/F u = (f-g) / (a-g)
Ratio between the separator feed A and final product F.
FINENESS PERFORMANCE Vf = F/A*100 Vf = 1/u Vf = (a-g)/(f-g) * 100 PERFORMANCE Ew = F/A * f/a Ew = (a-g)/(f-g) * f/a
The performance is referred to a granulomoeric dimension: it indicates the feeding material that passes in the final product after the separation.
SEPARATION EFFICIENCY
1. SYMBOLOGY M = fresh feed (t/h) A = separator feed (t/h) F = separator final product (t/h) G = separator coarse material (t/h) a = passing of A (%) f = passing of F (%) g = passing of G (%) We can define the passing of the material as the fraction (% in weight) of particles which have equal or lower dimensions to the granulometry of reference. Fundamental equations A=F+G A*a = F*f + G*g [i] [ii]
a = part in weight of a specific granulometric class of A (%) f = part in weight of a specific granulometric class of F (%) g = part in weight of a specific granulometric class of G (%) We can define granulometric class the interval between the two granulometric measures. A*a = F*f + G*g [iii]
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33
Being fi ai gi the fine product, feeding material and coarse passing on the mesh i (for the following dimensions: 2,4,8,16,32,64 e 128 m). Example
We calculate: - performance in fine material Vf = 1/Tc - performance on big material Vg = 1-Vf - the feeding fraction between 2 granulometric measures. a = df*Vf + dg*Vg a = df*Vf + dg(1-f) - the separation degree T
Example We calculate the T separation degrees, with the data from the table - point 2. Tc = 2,04 Vf = 1/Tc = 0.4902 Vg = 1-Vf = 0,5098
Granulometric interval m 0-2 2-4 4-8 8-16 16-32 32-64 64-128 > 128
Final product df[%] 13.3 8.9 12.4 17.2 21.4 18.8 7.4
Separation degree T[%] 36.7 34.9 30.3 27.6 31.1 54.3 74.5
Mean diameter m 1 3 6 12 24 48 96
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35
5. T CURVE DRAWING
The curve is resolved in two lines: - Horizontal: the ordinate is the mean of the separation degrees value, represented by the correspondent points. The points to be considered for the calculation of the mean value (Soutirage) are below the ordinate at the abscissa point 1 m; - a regression line related to the succeeding points on the ascending part of the curve; - [in practice it is better to cancel one or more points on the right that curve the line to the bottom. Only the 2 points situated more or less straddling the normalized separation diameter will be often considered. For this reason it is useful to consider the point on the right of the horizontal line.
100
s d
6.2 Separation diameter p This diameter corresponds to a probability of 50% to be distributed within coarse and fine material. This per centage is not applicable to all the feeding material, but only to the one that has really been separated; that means 100% - soutirage s. The ordinate is calculated as follows: s + (0,5*(100-s)) and we calculate, on the pending part of the T curve, the corresponding abscissa.
100
S+(0.5*(100-s))
6.3 Imperfection I Represents the T curve inclination (perfect separation = 0). It is represented by the difference between the diameters correspondent to the separation coefficients 25% e 75% for the material that has really been separated. That means 100%- soutirage s. On the separation chart the following ordinates have been reported: S+(0,25*(100-s)) S+(0,75*(100-s)) On the pending part of the curve are defined the correspondent diameters 25 e 75; The calculation is the following:
I=
25 -75 2 p
S+(0.25*(100-s))
100
S+(0.25*(100-s))
25
75
Products
/C . .A .G A M
MApei Grinding Aid/C Pack set inhibitors for cement
DESCRIPTION APPLICATION PROCEDURE
MA.G.A./C are high performance grinding aids generally used to increase mill production and to improve the cement quality. They are highly concentrated additives formulated with only selected raw materials, to guarantee absolute constancy of quality and superior performance.
TECHNICAL CHARACTERISTICS
MA.G.A./C may therefore be successfully utilized in all cases of pack-set phenomena (not due to humidity) inside the mill, particularly in the grinding of Portland and limestone cements. Productive increases generally may vary between 10% and 30%, depending on the fineness of the cement, on the grinding system available, on clinker mineralogical composition, on the additive dosage etc. When the right conditions are present, specific formulations for limestone cements allow the increase of even the ultimate strengths; it is possible to decrease the percentage of clinker in the cement recipe, with no loss in cement quality.
CHEMICAL-PHYSICAL DATA
MA.G.A./C, thanks to their polar nature, notably reduce the attraction forces of cement particles which are the main cause of agglomeration inside tubular mills (pack-set). They are also able to modify the hydrates structure (see pictures on the back page). The disappearance or the remarkable reduction of pack-set phenomena favourably modify the granulometric curve of the finished product with a consequent beneficial effect on the strengths and efficiency of theseparation. It is therefore possible to obtain important production increases (savings in kWh/t) or, with the same production, improvements of the specific surface of the finished cement. Specific formulations allow the modification of the hydration products of the cement increasing the early and/or ultimate strengths.
0.1-0.5 kg/t. Ordinary Portland cements (2600-3200 cm2/g): 100-200 g/t. Rapid Hardening Portland cements (3200-4600 cm2/g): 200-500 g/t. Limestone cements: 250-500 g/t. We recommend the higher dosage threshold in presence of high percentages of limestone and when
41
INDUSTRIAL TRIAL WITH MA.G.A./C1 Report of an industrial trial performed with MA.G.A./C1 during the production of high fineness CEM I type cements
t t t
1. TRIAL DESCRIPTION a. Plant description b. Trial objectives and additive selection 2. a. b. c. TRIAL RESULTS Immediate results during the Trial Post-trial results Technical analysis
3. CONCLUSIONS
42
1. TRIAL DESCRIPTION
a) Plant Description The cement grinding facility consists of two mills side by side, one dedicated to the grinding of cements while the second is dedicated to the grinding of slag. Our trials were performed on the cement mill which has the following characteristics: Cement Mill UMS Mill 5.0 x 14.0, two chambers; installed power 5750 kW. The cement grinding circuit is closed with a 3 generation Sepax 450M222 Separator. Separator and mill ventilation is realised with sleeve filters. (Fig. 1 Flow sheet diagram).
Fig. 1
1. 2. 3. 4. 5. 6.
Fresh material feed Cement mill Elevator Separator Mill bag filter Bag filter
b) Trial objectives and additive selection An industrial trial to evaluate the performance of the product MA.G.A./C1, a high performance grinding additive formulated as a concentrated grinding aid able to increase early strengths, on the production of CEM I (400 m2/kg Blaine) and CEM I (550 m2/kg Blaine) cements. The plants objectives was to increase the hourly production (t/h) of the mill as the cement plant had significantly increased their quota of the local market and needed to maximise their production output.
2. TRIAL RESULTS
Table N1. Details Cement
43
Units Type
Blank CEM I
(400 m2/kg)
% Difference
Additive g/t Dosage Production t/h Specific S.A. m2/kg Specific S.A. km2/h production Specific Mill kWh/t Consumption Specific consumption kWh/km2 S.A. production R1 MPa R2 MPa R28 MPa
* Average Plant Data
--133.0*
a) Immediate results during the trial Table N1 in paragraph 3.1 shows the average hourly production obtained during the trial. These results confirm the validity of the MA.G.A./C1 product as a powerful grinding aid. CEM I (400 m2/kg) In the case of the CEM I (400) trial the average production obtained with Mapei MA.G.A./C1 was 144.3 t/hr. This corresponds to an increase of +8.5% with respect to the blank, i.e. without an additive, which was 133.0 t/hr. This blank value is an average value for the month previous to the trial. Grinding without the additive was not possible on this cement due to silo space restrictions. The value of Blaine measured on the mixed sample is 411 m2/kg. This is higher than the desired value (+11 m2/kg) and may indeed be translated into a further increase in hourly production.
44
CEM I (550 m2/kg) In the case of the CEM I (550) trial the average production obtained with Mapei MA.G.A./C1 was 83.5 t/hr. This corresponds to an increase of +12.8% with respect to the blank, i.e. without an additive, which was 74.0 t/hr. This is a significant increase for such high Blaine grinding and is a positive result which allows a reduction of the specific mill consumption from 70.7 to 63.0 kWh/t. Another result is a higher surface production: +8.2% (45.0 km2/h versus 41.6 km2/h).
Additives
133. 133. 0
Blank
144. 144. 3
Mill Production CEM I (550)
Blank
85. 85. 0 144. 144. 3
MAGA/C 1
83. 83. 5
145. 145. 0 80. 80. 0 140. 140. 0 133. 133. 0 135. 135. 0 75. 75. 0 74. 74. 0
130. 0 130.
70. 70. 0
Additives
Additives
b) Post-Trial results The results regarding cement strengths are available in Table N1. All testing is carried out in accordance with the European Standard EN 196. The cement without additive where available is compared to that produced with Mapei MA.G.A/C1. CEM I (550 m2/kg) As regards the strengths at 1 day there is an increase of +12.1% with MA.G.A/C1 from 27.2 to 30.5 MPa, while at 2 days the increase is +7.3% from 41.3 to 44.3 MPa. The results at 28 days are practically the same.
MAGA/C 1
MAGA/C 1
41. 41. 3
1 Day
2 Days
These results are positive when one considers the increase in production obtained at the same time. The values of Blaine reported indicates that the cement produced without the additive is slightly finer than that produced with MA.G.A/C1. Hence here one can appreciate the positive influence of the products formulation on the early strengths.
45
c) Technical analysis The following samples were taken from the separation circuit consisting of a FLS SEPAX 450 type separator during the industrial trial: finished product separatore feed return or recycle material returning to the mill
On these samples granulometric particle size analysis was carried out with the Alpine sieve equipment and the complete particle size distribution curve was defined using a Coulter LS laser equipment. Successively the following were determined: Separation performance according to DIN and Tromp. Separation Performance According to DIN: The calculated values according to the DIN are given in Table N2 determined from the Dry residues of the materials tested; when one considers the very high specific surface area of the finished product: > 400 m2/kg, the calculated characteristic parameters: F/A and ETA w, lie within the normal range. The ETAw parameter is interesting, as it expresses the ability of the separator to clean the material being fed; in our case, on the 40 m control mesh, the recovered fraction of less than -40 m amounts to 67 % of the total present in the feed material. This can be defined as a good result.
46
Separation Performance Analysis according to DIN
CEMENT FLS UMS Cement Mill 5.0 x 14.0 FLS SEPAX 450
Separation Performance According to DIN, Calcolated with Alpine TABLE 2 m (D) 20 30 40 50 60 70 90 200 Total [passing values] final p. sep. feed (f) (a) 87.5 93.5 99.5 100.0 380.5 (f) 93.5 44.0 52.5 75.0 86.0 257.5 (a) 52.5 Output calculation from TABLE 2 F= A= G= A= F= G= t/h t/h t/h t/h t/h t/h 144.3 389.1 244.8
return (g) 19.0 28.0 59.5 78.5 185.0 (g) 28.0 mean values 2.70 0.37 0.55
a (D) m
0.0 0.0
0.0 0.0
PERF a(D)
control mesh [D] 40.0 m a (D) m m 2.67 0.37 0.67 0.61 0.65
eta w format
0.67 0.00
40
()
() A/F F/A ETA w ETA k ETA s f-g/a-g (1/U) 1/U*f/a (a-g)/(f-g)*100*(f-a)/a*(100-a) a-g/a*100/100-g
intended as "ability" of the separator to recover the finished product (F) the material (D) present in the feed A.
According to Tromp: From the laser particle size curves of the material in the separator circuit, the corresponding T curve (of Tromp) was calculated which represents for the various granulometric fractions the development of the separation process; Table 3 shows the T curve drawn, on the co-ordinates of a semi-logarithmic graph and the calculation of the characteristic parameters elaborated according to CETIC. Sepax 3.1 23.8 42 47
47
Circulating load Soutirage Diameter of separation Inclination angle of regression line (2^ branch separation curve)
dimensionless % m G
The profiles of the curves and the parameters deducted from them allow the operation of the separator to be judged as discreet. In relation to the not very high circulating load: approx. 3, the error of soutirage (by pass) is NOT very good; this may depend perhaps on an inadequate ventilation. Also as regards the profile of the 2^ branch of the T curve, which represents the type of separation, an inclination > 40G can be considered as acceptable.
48
Cement Plant Mill Separator Test no. Description dim.m 2 4 6 8 10 15 20 30 40 60 90 100 total calc. F/A G/F Loading Charge Soutirage Sep.diam 1.0 2.0 4.0 6.0 8.0 11.5 15.0 22.5 30.0 45.0 65.0 80.0
Separation Analysis (Tromp Curve) Cement Type Production t/h Spec.surf. M2/kg blaine laser df 2.2 3.6 4.6 5.3 5.9 7.1 8.6 11.9 17.4 36.6 60.5 66.5 9.7 7.4 6.4 6.0 5.4 11.9 9.6 14.6 12.7 11.0 2.7 1.2 da 4.5 3.5 2.9 2.5 2.3 4.9 4.1 6.9 7.4 15.9 15.4 4.2 dg 2.2 1.4 1.0 0.7 0.5 1.3 1.4 3.4 5.5 19.2 23.8 6.0 CEM I 400 144.3 410 362 df*F/A 3.1 2.4 2.0 1.9 1.7 3.8 3.1 4.7 4.1 3.5 0.9 0.4 dg*G/F 1.47 0.96 0.69 0.49 0.37 0.86 0.98 2.28 3.76 13.05 16.21 4.09 a () 4.56 3.34 2.73 2.41 2.10 4.67 4.05 6.95 7.82 16.76 17.08 4.47 T (%) 32.2 28.8 25.1 20.5 17.6 18.5 24.2 32.8 48.0 78.8 94.9 91.4
FLS UMS Cement Mill 5.0 x 14.0 FLS SEPAX 450 Grinding with MA.G.A./C 1 f 9.7 17.1 23.5 29.5 34.9 46.8 56.4 71.0 83.7 94.7 97.4 98.6 663.3 a 4.5 8.1 11.0 13.5 15.8 20.7 24.8 31.6 39.1 54.9 70.3 74.5 368.8 0.32 0.68 g
0.32 0.29 0.25 0.20 0.18 0.18 0.24 0.33 0.48 0.79 0.95 0.91
spec. Surface area m2/kg 230.2 Materials in cycle t/h laser blaine 30 m final 144.3 362 410 12.5 feeding 451.0 181 206 56.0 coarse 307.0 94 122 81.0 A/F 3.1 Sep. Line angle % 23.8 Efficiency Evaluation m 42 Imperfection
residue [determ. ALPINE] 40 m 60 m 90 m 200 m 6.5 0.5 0.0 0.0 47.5 25.0 14.0 3.0 72.0 40.5 21.5 4.0 Deg. 47 =(Sep. Line angle) Average ad 0.43
3. CONCLUSIONS
The results obtained can be considered to be very positive both in terms of production (t/hr) and cement quality (MPa at 1 & 2 days). The most important objective of the plant at the time was to increase hourly production and the results obtained are very interesting when one considers the low dosage (300 g/t) of the MA.G.A./C1 product.
49
MA.G.A./C1 guarantees significant production increases and increases early strengths. Hourly cement production capacity has reached the levels desired by plant management, at the same time reducing production energy costs.
51
INDUSTRIAL TRIAL WITH MA.G.A./C2 Report of an industrial trial performed with MA.G.A./C2 during the production of CEM I 42.5 R
t t t
1. TRIAL DESCRIPTION a. Plant description b. Trial objectives and additive selection 2. TRIAL RESULTS a. Immediate results during the Trial b. Post-trial results 3. CONCLUSIONS
52
1. TRIAL DESCRIPTION
a) Plant Description The cement grinding facility has a group of four mills side by side and the trial was performed on mill number 3 which has the following characteristics: FLS Mill of dimensions 4.6 m x 16.0 m, two chambers of which the first chamber is 3.0 m and the second is 13 m long; installed power is 4500 kW. The grinding circuit is closed with a high efficiency SEPOL SVZ separator, with an ESP filter on the mill. (Fig.1 - Flow sheet diagram)
Fig. 1
1. 2. 3. 4. 5.
Fresh material feed Cement mill Elevator Separator - SEPOL SVZ ESP Filter
B) Trial objectives and additive selection An industrial trial to evaluate the performance of the additive MA.G.A./C2, a high performance grinding additive formulated to increase 28 day strengths, on the production of the cement CEM I 42.5 R (95.6% Clinker and 4.4% Gypsum). The plants objective was to increase the 28 day strengths in order to maintain its market leader position without having to alter the quality of their clinker.
MA.G.A./C2 was proposed given its ability to meet the clients objectives of increased 28 days mechanical strengths while at the same improving the cement mills hourly production. The performance of the product in terms of its excellent grinding aid characteristics and strength improvement are directly related to the product formulation and the high quality of the raw materials utilised.
53
2. TRIAL RESULTS
a) Immediate results during the trial The MA.G.A./C2 product was added onto the clinker transported on the conveyor belt just before the entrance to the mill at a dosage of 450 g/t. The diagram in Figure 2, related to the circulating load (elevator cycle absorption), clearly shows the effect of the additive on the grinding cycle. The yellow line represents the elevator consumption while the red line represents the fresh material feed. Subsequently the circulating load has been returned to previous levels by the following operations:
54
Table N1. Details Cement Additive Additive Dosage Production Specific surface area Specific surface area production Specific mill consumption Specific consumption surface area production Flow Initial Setting Time Strengths 1 days 2 days 28 days
Units Type Type g/t t/h m2/kg km2/h kWh/t kWh*t-1/ km2
MA.G.A./C2 CEM I 42.5 R MA.G.A./C2 450 90.2 410 37.9 47.3 112.6
Table N1 in paragraph 1.4 shows the average hourly production obtained during the trial. These results confirm the validity of the MA.G.A./C2 product. The mill output increase t/h: + 9,9%, has been realised with a slightly higher Blaine specific surface: 410 m2/kg versus 408 m2/kg; a further result is a higher surface production: + 13% (37.9 km2/h versus 33.5 km2/h). The results show a reduction of the average specific mill consumption from 51,7 to 47,3 kWh/t.
55
b) Post-Trial analysis The results are available in Table N1. All testing was carried out in accordance with the European Standard EN 196. Table N1 shows information regarding cement strengths, Blaine, setting times and cement flow. The cement produced without any additive, i.e. Blank, is compared to that produced with MA.G.A/C2. As regards the strengths there are increases at all ages with MA.G.A/C2. At 1 and 2 days the increases are respectively +29,4% and 13,0%. There is also a reduction in the setting time from 95 minutes to 80 minutes, particularly appreciated by the cement plant as this cement is for the most part employed by precast clients. Meanwhile at 28 days the strengths have increased from 49,8 MPa to 55,6 MPa corresponding to an increase of +11,7%.
Compressive Strengths
60.0 60. 0 60. 50.0 50. 0 50. 40.0 40. 0 40. 30.0 30. 0 30. 20.0 20. 0 20. 10.0 10. 10. 0
20.1 15.6 28.4 25.2
Blank
MAGA/C 2
55.6 49.8
1 day
2 days Days
28 days
This increase at 28 days fully meets the clients objectives while at the same time obtaining a significant production increase.
56
The comparison between the energy consumption indexes, with reference to the strength characteristics of the cement produced (kWh*t-1/MPa), clearly demonstrates the improvements which may be obtained using a high performance product such as MA.G.A/C2.
Description 28 days
Laser particle size analysis of the cements are available in Fig. 3 (Blank cement) and Fig. 4 (MA.G.A./C2). The laser distribution curves demonstrate the superior fineness (higher laser specific surface) of the cement with the additive even though at the same time significant increases in production are achieved. The increases in strengths at all ages can be principally accredited to the positive effect of the MA.G.A./C2 additive. In Fig. 5 and Fig. 6 the granulometric curves for the two cements produced have been drawn on the RRB grid using data from the laser analysis, based on the correspondent regression equation, calculating also the characteristic distribution parameters. The two distribution lines are quite similar, having the same uniformity coefficient(n) of 0,66 which also is not particularly high. This could possibly be interpreted as being related to a low or perhaps insufficient level of air for separation.
3. CONCLUSIONS
The principal objective of the client to increase 28 day strengths on the CEM I 42.5 R has been fully achieved through the use of the MA.G.A./C2 product , increasing strengths from 49.8 MPa to 55.5 MPa equivalent to an increase of +11.7%. At the same time a production increase of +9.9% has been obtained further improving the clients grinding performance while reducing energy costs. The MA.G.A./C2 product is an effective solution where ultimate strength increases are specifically required on Portland and on blended cements where there is a significant limestone addition.
Fig. 3
Blank cement
57
58
Fig. 4
MA.G.A./C2
Fig. 5
Equation of the Regression Curve (RRB Curve) according to Laser analysis Cement Plant Mill Separator Test no. Description dim.m 1 2 4 6 8 10 15 20 30 40 60 90 pass. (%) 3.4 7.7 14.8 21.4 27.4 32.8 44.1 52.8 65.5 75.4 88.9 94.3 Cement Type Production t/h Spec.surf. M2/kg blaine laser CEM I 42.5 R
59
408 305
Residue
(%)
30 m 34.5
40 m 24.6 Y=a+nx
60 m 11.1
90 m 5.7
200 m 0.0
Linear Regression Uniformity Coe Cross Line Angle Charact. Diam. Corrsp. Diam. (n) (a) (Gr) (Xo) P80
Res. 36,8%
Notes
60
Fig. 6
Equation of the Regression Curve (RRB Curve) according to Laser analysis Cement Plant Mill Separator Test no. Description dim.m 1 2 4 6 8 10 15 20 30 40 60 90 pass. (%) 4.1 9.1 17.3 24.4 30.6 36.1 47.3 56.2 69.8 80.0 91.7 95.9 Cement Type Production t/h Spec.surf. M2/kg blaine laser CEM I 42.5 R
410 344
Residue
(%)
30 m 30.2
40 m 20.0 Y=a+nx
60 m 8.3
90 m 4.1
200 m 0.0
Linear Regression Uniformity Coe Cross Line Angle Charact. Diam. Corrsp. Diam. (n) (a) (Gr) (Xo) P80
Res. 36,8%
Notes
/M . .A .G A M
MApei Grinding Aid/M Pack set inhibitors for minerals
DESCRIPTION MA.G.A./M are high performance grinding aids for minerals (limestone, quartz, feldspar, zirconium, sands) and raw materials and are suitable for obtaining a higher level of fineness. They increase mill output, and modify the particle size distribution, improving the dry flow characteristics of the grinded materials. They are used in dry grinding processes, preferably in tubular mills, but are also effective in vertical mills, hammers mills, etc. TECHNICAL CHARACTERISTICS MA.G.A./M, thanks to their polar nature, notably reduce the attraction forces of cement particles which are the main cause of agglomeration inside the mill. MA.G.A./M act by coating the particles which normally cause agglomeration, with a mono-molecular film which neutralizes the surface electrical charges, improving dry flow characteristics during transport, storage and handling. APPLICATION PROCEDURE MA.G.A./M has been conceived taking into account the characteristics of the different minerals and their final use. A first distinction can be made between additives for the grinding of limestone and additives for the grinding of other minerals.
Limestone Grinding limestone is always difficult due to the pack-set phenomena inside the mill. For this reason a highly effective grinding aid is recommended. MA.G.A./M offers specific additives for: limestone for the food industry; limestone for applications with controlled dielectric constant (power line fillers, etc.). Other minerals Other minerals such as quartz, feldspar, sands etc. are usually used in the ceramic industry (tiles, sanitary ware), glass and refractory products industry. For these minerals with a low agglomeration tendency, specific formulations of MA.G.A./M are available. CHEMICAL-PHYSICAL DATA Please refer to the appropriate safety data sheets. DOSAGE 0.3-0.8 kg/t. The optimum dosage depends on the grinding system and material type and fineness. In any case it has to be found through a reliable industrial trial, preferably with the help of MAPEI Cement Additives Division technicians, that are also available to select the most suitable additive for each specific need.
/S . .E .P A M
MApei Performance Enhancer/S Pack set inhibitors and strength enhancers
DESCRIPTION MA.P.E./S are highly concentrated grinding aids formulated with only selected raw materials, to guarantee absolute constancy of quality and superior performance. They are additives formulated to improve cement quality (early and/or ultimate strengths) and to aid cement grinding by increasing mill production. TECHNICAL CHARACTERISTICS MA.P.E./S also guarantee, in addition to all the advantages which come from the usage of the grinding aids (refer to MA.G.A./C), remarkable increases to early and ultimate strengths. At equal cement fineness, MA.P.E./S are able to increase mechanical strengths thanks to a better granulometric redistribution of the finished cement, to a higher fineness and to a higher rate of the calcium silicates hydration, which can be significantly modified. APPLICATION PROCEDURE MA.P.E./S may be successfully utilized in the grinding of blended cements (i.e. pozzolanic, blast furnace slag and fly ash cements) and in all cases where a significant increase in early strengths is needed. MA.P.E./S are generally formulated to reach the goals placed by the cement factory. The obtainable strength increases may be used to improve the binder quality, reaching early strengths quite similar to those of Portland cements. Alternatively, keeping the cement quality unaltered, it is possible to substitute in the mixture up to 4-6% of clinker with blended material. In normal conditions the strength increases are in the range of 20-50% after one day and 5-15% after 28 days. MA.P.E./S can also be used successfully when grinding Portland and limestone cements to increase significantly early strengths. CHEMICAL-PHYSICAL DATA Please refer to the appropriate safety data sheets. DOSAGE 1.0-3.0 kg/t. We suggest the higher dosage threshold, if the aim is the substitution of clinker points with blended material (i.e. blast-furnace slag, fly ash, pozzolan). The optimum dosage, in any case, has to be found through a reliable industrial trial, preferably with the help of MAPEI Cement Additives Division technicians. MA.P.E./S should be added to the clinker on the mill feed conveyor belt or sprayed in the first mill
65
INDUSTRIAL TRIAL WITH MA.P.E./S Report of an industrial trial performed with MA.P.E./S during the preparation of CEM I 52.5
t t t
1. TRIAL DESCRIPTION a. Plant description b. Trial objectives and additive selection 2. a. b. c. TRIAL RESULTS Immediate results during the Trial Post-trial results Technical analysis
3. CONCLUSIONS
66
1. TRIAL DESCRIPTION
a) Plant Description In the cement plant of reference, the clinker is produced in a rotary kiln with cyclone preheaters produced by PSP Eng., with a potentiality of 2500 t/d. The cements produced in the plant are: CEM I 52.5 R, CEM II/AL 42.5 R, CEM IV/B 32.5 ARS. The industrial trial has been performed on a grinding system Wyss 3.2 x 14 (see Fig. 1) during the production of the CEM I 52.5 R.
Fig. 1
MILL CHAMBER DIMENSIONS Drying chamber 1^chamber 2^chamber 3^chamber Total values BALL CHARGE 100 90 80 70 60 50 40 30 25 20 25 x 25 Lg 22 x 22 Lg 20 x 20 Lg 16 x 16 Lg Total Filling Level Mill Total LININGS type blocking system material DIAPHRAGM type slots material central hole regulable position GRINDING PLANT CHARACTERISTICS INSTALLED POWER lg ut (m) Vut (m3) REDUCTION GEAR 4.20 30.40 9.10 65.30 Installed power rpm (n1/n2) 13.3 95.7 rotation speed 2^cham 3^cham Critical speed Loading device diameters [in/out] CYCLE ELEVATOR capacity STATIC SEPARATOR 10 diametre 20 SEPARATOR 50 diametre Q air FILTERS 1850 Kw brand type kW n/1' n/1' % type m type t/h type m brand type m Em /h type model no. m Em /h mbar C No. type FLS Symetro 1850 990/16.3 16.3 67.1 channel
15 10 10 5
150
3^cham
chambers filtering surface FILTER FAN capacity pressure temperature FEEDING MEASURES
mill 37,600 36 80
3^cham
mm tipo mm
double 8
discharge 10
REGULATION SYSTEM cycle elevator kW measuring contr.gravim.sep.refusal electronic ear CEMENT TRANSPORT capacity type t/h
no
Fig. 1 bis
67
fly ash
dosing system
cement sampling
b) Trial Objectives and additive selection A strength enhancer has been added to the CEM I 52.5 R type cement, at a dosage of about 2.5-3.0 kg/t. When formulating our offer, we also proposed an enhancer, the MA.P.E./S, that offers, in addition, good grinding aid characteristics. We added our MA.P.E./S in the plant during a normal production cycle with the addition of the competitors product, without intervals, at the same dosage. The diagram in Figure 2, related to the circulating charge (cycle elevator absorption), clearly shows the effect of the additive on the grinding cycle. Subsequently the circulating charge has been re-settled by the following operations: Cement fineness improvement Mill output increase
Fig. 2
Loading charge
Introduction of MA.P.E./S
68
2. TRIAL RESULTS
Additive Dosage Production Specific surface Spec. Surf. Produc. Mill consumption Specific mill cons. Specif. surface production cons. Flow Mixing water Start hardening Strengths 1d 2d 28 d Type Kg/t t/h m2/kg km2/h kW kWh/t kWh/km2 COMPETITOR 3.0 20.0 490 9.8 1346 67.3 137.3 MA.P.E./S 2.8 22.2 504 11.1 1350 60.8 120.6 DIFFERENCE 0.93 1.11 1.03 1.13 1.00 0.90 0.87
mm % min MPa
a) Immediate results during the trial The above results confirm the validity of our MA.P.E./S in comparison to the competitor additive. The mill output increase t/h: + 11%, has been realised with a higher Blaine specific surface: 504 m2/kg versus 490 m2/kg; a further result is a higher surface production: + 13% (11.8 km2/h versus 9.8 km2/h); in practice this means that, at the same specific surface of the competitors additive: 490 m2/kg, a production of 24 t/h could have been realised, with a final increase of 20%. b) Post-Trial Analysis The physical-mechanical characteristics of the cement improved thanks to Mapei additive. At higher strengths value at 1 and 2 days (+7 e + 6%) respectively, corresponds also better hardening times if compared to the competitors product: 250/1 vs. 270/1. It is also to be noted that the problem of the cement hardening is, in this case, particularly perceived, and the competitor's additive has been previously modified due to its tendency to excessively protract the hardening times. c) Technical Analysis During the trial with the MAPEI additive, some samples of the materials in the system have been collected: separator final product; mill exit (separator feeding); separator coarse. On the above samples we performed the granulometric analysis with the Alpine Siever, and the complete distribution curve has been determined by the laser Coulter LS.
Wedag separator The separator working, in the plant closed circuit, has been evaluated with the usual analysis methods: Performance based on the DIN rule; Tromp separation curve. Tables 7 e 8 report the performance calculation based on DIN, related to the granulometric determinations with the Alpine siever; Table 8, in particular, analyses the cleaning function of the separator: quantity of fine material extracted from the feeding, referred to a 40 m separation diameter. From the granulometric laser analysis of the loading charge, the T separation curve (foll. Tromp) has been traced on a scheme with linear coordinates: table 9. Then, the characteristic parameters of the curve following CETIC have been calculated: soutirage and curve inclination.
69
3. CONCLUSIONS
The strengths improvements obtained with the MA.P.E./S, if compared to the competitors product, did not change at different aging (1-28 days). Obviously also the comparison between the energy consumption indexes, referred to the strengths characteristic of the cement produced (kWh/Mpa), demonstrates the better performance of MAPEI additive: COMPETITOR (kWh/MPa) 2.28 0.54 MA.P.E./S (kWh/MPa) 1.91 0.46
1 day 1, 3, 28 days
The results of the Separator Performance Analysis have been summarised in TAB. 3. The granulometric curves of the 3 samples have been drawn on the RRB reticule (Fig. 4,5,6) based on the correspondent regression equation, calculating also the characteristic distribution parameters: uniformity coefficient n (curve inclination) characteristic diameter Xo (diameter correspondent to R 36.8). For the final product the uniformity coefficient was 0.96 (line pending of 44 degrees); this is a mean/high value, that is characteristic of the 2nd generation separators, when producing cements that need water additions on normal values.
70
Tab. 4
Cement Plant Mill Separator Test no. Description dim.m 2 4 6 8 10 15 20 30 40 60 90 pass. (%) 15.1 23.3 29.7 35.4 40.9 53.9 65.4 82.3 91.2 97.7 99.7
Residue
(%)
30 m 17.7
40 m 8.8 Y=a+nx
60 m 2.3
90 m 0.3
200 m 0.0
Linear Regression Uniformity Coe Cross Line Angle Charact. Diam. Corrsp. Diam. (n) (a) (Gr) (Xo) P80
Res. 36,8%
Notes
Tab. 5
71
Cement Plant Mill Separator Test no. Description dim.m 2 4 6 8 10 15 20 30 40 60 90 pass. (%) 7.1 10.9 13.8 16.3 18.7 24.5 30.6 42.9 53.9 70.0 83.8
Residue
(%)
30 m 57.7
40 m 46.1 Y=a+nx
60 m 30.0
90 m 16.2
200 m
Linear Regression Uniformity Coe Cross Line Angle Charact. Diam. Corrsp. Diam. (n) (a) (Gr) (Xo) P80
Res. 36,8%
Notes
72
Tab. 6
Cement Plant Mill Separator Test no. Description dim.m 2 4 6 8 10 15 20 30 40 60 90 pass. (%) 10.3 16.1 20.5 24.6 28.4 37.3 45.4 59.1 69.1 80.5 90.3
Residue
(%)
30 m 40.9
40 m 30.9 Y=a+nx
60 m 19.5
90 m 9.7
200 m
Linear Regression Uniformity Coe Cross Line Angle Charact. Diam. Corrsp. Diam. (n) (a) (Gr) (Xo) P80
Res. 36,8%
Notes
Tab. 5
73
Separation Performance According to DIN TABLE 2 m (D) 20 30 40 50 60 70 90 200 Total [passing values] final p. sep. feed (f) (a) Output calculation from TABLE 2 F= A= G= A= F= G= t/h t/h t/h t/h t/h t/h 22.2 70.4 48.2
return (g)
a (D) m
80.4 82.8 93.1 99.6 355.9 (g) 80.4 mean values 3.17 0.32 0.34
0.0 0.0
0.0 0.0
0.0 0.0
PERF a(D)
control mesh [D] 40.0 m a (D) m m 3.23 0.31 0.36 0.33 0.34
eta w format
0.36 0.00
40
()
() A/F F/A ETA w ETA k ETA s f-g/a-g (1/U) 1/U*f/a (a-g)/(f-g)*100*(f-a)/a*(100-a) a-g/a*100/100-g
intended as "ability" of the separator to recover the finished product (F) the material (D) present in the feed A.
74
Tab. 8
Separation Performance According to DIN Calculation of the values related to [D] (f) 98.8 (a) 86.1 passing t/h 61.70 21.93 39.77 (g) 80.4 residue t/h 9.96 0.27 9.69 % 35.5 64.5 Dm 40.0 40m Output calculation F= A= G= A= F= G= t/h t/h t/h t/h t/h t/h 22.2 71.7 49.5
A F G
0.0 0.0
presence in final prod. (F) of [-D], [3] in the feeding A. material of [-D], present in A, that remains in the separator coarse Dm 3.23 0.31 0.36 0.33 0.34 40
Separation characteristic parameters CIRCULATING LOAD A/F EFFICIENCY F/A PERF.ACC. DIN ETA w CLASS.EFFICIENCY ETA k DIVISION PERFORM. ETA s
Tab. 9
Separation analysis
Separation Analysis (Tromp Curve)
75
Cement Plant Mill Separator Test no. Date dim.m 2 4 6 8 10 15 20 30 40 60 90 100 total calc. F/A G/F 1.0 3.0 5.0 7.0 9.0 12.5 17.5 25.0 35.0 50.0 75.0 95.0
Cement Type Production t/h Spec.surf. M2/kg blaine laser g 10.3 16.1 20.5 24.6 28.4 37.3 45.4 59.1 69.1 80.5 90.3 92.1 7.1 10.9 13.8 16.3 18.7 24.5 30.6 42.9 53.9 70.0 83.8 86.8 df 15.1 8.2 6.4 5.7 5.5 13.0 11.5 16.9 8.9 6.5 2.0 0.1 da 10.3 5.8 4.4 4.1 3.8 8.9 8.1 13.7 10.0 11.4 9.8 1.8 dg 7.1 3.8 2.9 2.5 2.4 5.8 6.1 12.3 11.0 16.1 13.8 3.0
492 df*F/A 6.3 3.4 2.7 2.4 2.3 5.4 4.8 7.0 3.7 2.7 0.8 0.0 dg*G/F 4.14 2.23 1.69 1.46 1.40 3.39 3.56 7.18 6.43 9.40 8.06 1.75 A 10.42 5.64 4.36 3.83 3.69 8.79 8.35 14.21 10.13 12.11 8.89 1.79 G/A 0.40 0.40 0.39 0.38 0.38 0.39 0.43 0.51 0.63 0.78 0.91 0.98 T (%) 39.71 39.55 38.89 38.12 38.00 38.52 42.69 50.55 63.45 77.67 90.65 97.68
f 15.1 23.3 29.7 35.4 40.9 53.9 65.4 82.3 91.2 97.7 99.7 99.8 734.4
459.3 Materials in cycle residue [determ. ALPINE] t/h 30 m 40 m 60 m final 22.2 1.2 0.3 feeding 53.4 13.9 11.8 coarse 31.2 19.6 17.2 A/F 2.4 Sep. Line angle Deg. % 38.8 % 48
T separation curve
T curve
soutirage
regression
ord.sep.diam.
Linear (regression)
/W . .E .P A M
MApei Performance Enhancer/W Pack set inhibitors, strengths and flow enhancers
DESCRIPTION MA.P.E./W are highly concentrated grinding aids formulated with only selected raw materials, to guarantee absolute constancy of quality and superior performance. They are additives formulated to improve cement quality (early and/or ultimate strengths, flow) and to aid cement grinding, increasing mill production. TECHNICAL CHARACTERISTICS MA.P.E./W also guarantee, besides all the advantages which come from the usage of the grinding aids (refer to MA.G.A./C), remarkable increments in early and ultimate strengths and an improvement of the workability (flow) of the cement paste. At equal fineness MA.P.E./W are able to increase mechanical strengths thank to a better granulometric redistribution of the finished cement and to a higher rate of calcium silicates hydration, which can be significantly modified. APPLICATION PROCEDURE MA.P.E./W may be successfully utilized in the grinding of blended cements, (i.e. pozzolanic, blast furnace slag and fly ash cements) and in all cases where it is necessary to improve the cement flow. MA.P.E./W are generally formulated to reach the goals placed by the cement factory. The achievable strength increment may be used to improve the quality of the binder or, keeping cement quality unaltered, it is possible to substitute in the mixture up to 4-6% of clinker with blended material. In normal conditions the strength increases are in the range of 20-50% after one day and 5-15% after 28 days. The formulations, which are specifically oriented towards improving the water demand of the cement, especially used in the production of pozzolanic cements, allow increases to the flow of up to even 20 points (UNI standard 7044-72). CHEMICAL-PHYSICAL DATA Please refer to the appropriate safety data sheets. DOSAGE 1.0-3.0 kg/t. We suggest the higher dosage threshold, if the aim is the substitution of clinker points with blended material (i.e. blast-furnace slag, fly ash, pozzolan) or the reduction of the water demand of the cement. The optimum dosage has, in any case, to be found through a reliable industrial trial, preferably with the help of MAPEI Cement Additives Division technicians.
79
INDUSTRIAL TRIAL WITH MA.P.E./W1 Industrial Trial Report on the production of CEM IV/B-P 32.5 R using the Mapei grinding additive MA.P.E./W1
t t t
1. TRIAL DESCRIPTION a. Plant description b. Trial objectives and additive selection 2. a. b. c. TRIAL RESULTS Immediate results during the Trial Post-trial results Technical analysis
3. CONCLUSIONS
80
1. TRIAL DESCRIPTION
a) Plant Description The grinding circuit is particularly interesting in that it consists of two mills and a mixer. Pozzolana is dried and ground in a Lesche LM24 vertical mill and is then stored in an intermediate silo. Clinker and gypsum are ground in a Fema tubular ball mill, 3.8 x 13.75m in a closed circuit consisting of a 3 generation Humboldt separator, 3.5 m with 4 cyclones. The gases exiting from the mill are filtered by means of a bag filter. The grinding additive is added to the first chamber of the ball mill. A mixer receives and homogenises the cement (clinker & gypsum) coming from the ball mill and the pozzolana coming from the intermediate silo, thus producing the finished CEM IV/B-P 32.5 R cement. The power absorption of the principle machines are as follows: Lesche vertical mill: 465 kW Fema tubular ball mill: 1.990 kW Humboldt separator: 98 kW
b) Trial Description and Additive Selection An industrial evaluation of the grinding additive MA.P.E./W1, a liquid product for the production of Pozzolanic cements specifically formulated with raw materials of the highest quality. MA.P.E./W1 is an additive with a triple action, developed to increase the workability and mechanical strengths of the ground cement as well as ensuring high mill productivity. The trial consisted of grinding a CEM IV/B-P 32.5 R cement at the same level of fineness, with and without the addition of MA.P.E./W1, verifying immediately the effects on mill productivity and successively on workability, mechanical strengths and separation performance.
2. TRIAL RESULTS
Table A
81
Details Cement Additive dosage Production Passing material at 40 m. Passing material at 63 m. Specific Mill & Separator Consumption Workability Strengths at 24 hours Strengths at 2 days Strengths at 28 days
Units Blank Type CEM IV/B-P 32.5 R g/t --t/h 83.9 % 80 % 94 kWh/t 30.4 Flow 36 MPa 8.0 MPa 16.3 MPa 34.9
MA.P.E./W1 CEM IV/B-P 32. 5 R 2.700 93.8 81.5 95 27.2 48 10.6 18.5 40.3
a) Immediate results during the trial On examination of Table A, it is possible to see that the addition of MA.P.E./W1 has produced an increase in productivity of 11.8% with relevant energy savings. This confirms the products valid grinding aid characteristics.
100. 0 100.
83.9
93.8
27.2
82
b) Post Trial Analysis Strengths Strength testing was conducted in accordance with the European standard EN 196-1. The utilisation of the additive increases the strengths of the cement as follows: + 32.5% at 24 hours, + 13.5% at 2 days and + 15.5% at 28 days.
Compressive Strengths
Blank MAPE/W 1
40.3 34.9
45. 0 45. 40. 40. 0 35. 0 35. 30. 0 30. 25. 0 25. 20. 0 20. 15. 0 15. 10. 0 10. 5. 0 5. 0. 0. 0
1 day
2 days
28 days
Workability The utilisation of the additive increases the workability by 12 points equivalent to 33.3%.
Cement Flow
Blank MAPE/W 1
60. 0 60. 50. 0 50. 40. 0 40. 30. 0 30. 20. 20. 0
Flow
48.0
36.0
c) Technical Analysis During the industrial trial samples of the following materials were taken: Separator feed Separator finished product Recycle from separator Finished cement The samples were subjected to laser and Alpine granulometric particle distribution analysis. In Table B the results of the separator yield, the Tromp curve and the R.R.B. regression line equation are reported.
83
Table B
Details Units Cement Type Additive dosage g/t Circulating load A/F Soutirage (by-pass) % Diameter of separation m Inclination of the 2 branch of the curve Efficiency evaluation Angle R.R.B line Characteristic diameter (res. 36,8%) m
MA.P.E./W1 CEM IV/A 32. 5 R 2,700 3.0 18.8 37 56 Good 45.7 28.4
The results indicate the separators (3 generation) good level of separation efficiency in both conditions of operation. It is interesting to observe how the utilisation of the additive leads to a significant reduction of the circulating load from 4.1 to 3.0. Mill grinding has improved and the cement particles are less agglomerated. In addition there is a substantial reduction in the quantity of the material which bypass the separator without being classified, passing from 41.5% without an additive (blank) to 18.8% with the additive. As regards the investigations conducted on the cement, tracing the R.R.B. regression line we do not find substantial differences except a minimal increase in the slope of the line and a minimal reduction of the particle distribution curve when the additive is utilised.
84
Cement Plant Mill Separator Test no. Description dim.m 2 4 8 10 15 20 30 40 60 90 1.0 2.0 5.0 7.0 11.5 15.0 22.5 30.0 45.0 65.0 FEMA 3.8 x 13.75 Humboldt Blank Grinding f 6.9 13.8 27.1 33.4 47.9 59.4 74.1 85.7 93.0 96.8 a 3.1 6.2 11.6 14.1 20.0 25.2 33.0 41.6 55.9 69.0 g
Separation Analysis (Tromp Curve) Cement Type Production t/h Spec.surf. M2/kg blaine laser df 2.0 3.8 6.7 7.9 10.6 13.5 19.1 26.6 43.6 62.0 6.9 6.9 13.3 6.3 14.5 11.5 14.7 11.6 7.3 3.8 da 3.1 3.1 5.4 2.5 5.9 5.2 7.8 8.6 14.3 13.1 dg 2.0 1.8 2.9 1.2 2.7 2.9 5.6 7.5 17.0 18.4 Intermediate 93.8 411 342 df*F/A 1.69 1.69 3.26 1.54 3.55 2.82 3.60 2.84 1.79 0.93 dg*G/F 1.51 1.36 2.19 0.91 2.04 2.19 4.23 5.66 12.83 13.89 a () 3.20 3.05 5.45 2.45 5.59 5.01 7.83 8.50 14.62 14.82 T (%) 47.2 44.6 40.2 37.0 36.4 43.7 54.0 66.6 87.8 93.7 T (%) corr 16.9 12.8 5.9 0.8 0.0 11.4 27.6 47.4 80.7 90.1
538.1
195.8 Materials in cycle spec. Surface area m2/kg t/h laser blaine 30 m final 94.0 300 14.5 383.0 157 58.3 feeding coarse 289.0 104 78.4 A/F 4.1 Sep. Line angle % 36.4 Efficiency Evaluation % 41.5 Imperfection m 45
residue [determ. ALPINE] 40 m 60 m 90 m 200 m 7.5 1.5 0.0 0.0 49.2 21.3 10.1 1.0 66.7 31.0 14.2 1.0 Deg. 56 Good =(Sep. Line angle) ad 0.24
Separation Analysis (Tromp Curve) Cement Plant Mill Separator Test no. Description dim.m 2 4 8 10 15 20 30 40 60 90 1.0 2.0 5.0 7.0 11.5 15.0 22.5 30.0 45.0 65.0 Cement Type Production t/h Spec.surf. M2/kg blaine laser df 1.1 1.9 2.9 3.3 4.5 5.9 10.7 19.9 43.7 68.5 6.8 6.5 11.4 5.0 11.6 10.5 16.3 14.3 10.7 4.1 da 2.9 2.8 4.4 1.8 4.5 4.6 8.8 10.6 20.3 16.5 dg 1.1 0.8 1.0 0.4 1.2 1.4 4.8 9.2 23.8 24.8 Intermediate 93.8 411 342 df*F/A 2.23 2.14 3.75 1.64 3.81 3.45 5.36 4.70 3.52 1.35 dg*G/F 0.74 0.54 0.67 0.27 0.81 0.94 3.22 6.18 15.98 16.65 a () 2.97 2.67 4.42 1.91 4.62 4.39 8.58 10.88 19.50 18.00 T (%) 24.8 20.1 15.2 14.0 17.4 21.4 37.6 56.8 82.0 92.5 T (%) corr 12.6 7.0 1.3 0.0 4.0 8.6 27.4 49.7 79.0 91.3
85
FEMA 3.8 x 13.75 Humboldt Grinding with MA.P.E./W 1 (0.27%) f 6.8 13.3 24.7 29.7 41.3 51.8 68.1 82.4 93.1 97.2 a 2.9 5.7 10.1 11.9 16.4 21.0 29.8 40.4 60.7 77.2 g
508.4
162.4 Materials in cycle spec. Surface area m2/kg t/h laser blaine 30 m final 94.0 300 14.5 285.0 157 58.3 feeding coarse 192.0 104 78.4 A/F 3.0 Sep. Line angle % 14.0 Efficiency Evaluation % 18.8 Imperfection m 37
residue [determ. ALPINE] 40 m 60 m 90 m 200 m 7.5 1.5 0.0 0.0 49.2 21.3 10.1 1.0 66.7 31.0 14.2 1.0 Deg. 56 Good =(Sep. Line angle) ad 0.39
86
Cement Plant Mill Separator Test no. Description dim.m 1 2 4 6 8 10 15 20 30 40 60 90 100 pass. (%) 2.8 6.6 13.0 18.9 24.3 29.2 40.6 50.2 62.3 73.1 84.0 94.4 97.3
Equation of the Regression Curve (RRB Curve) according to Laser analysis Cement Type Sample Spec.surf. M2/kg blaine laser Pozzolanic CEM IV/B-P 32.5 R
FEMA 3.8x13.75m; Loesche 2.4m Humboldt 3.5m Blank Grinding res. (%) 97.2 93.4 87.0 81.1 75.7 70.8 59.4 49.8 37.7 26.9 16.0 5.6 2.7
419.7 296.7
Residue
(%)
30 m 26.5
40 m 20.0 Y=a+nx
60 m 6.0
90 m 1.0
200 m 0.0
Notes
Equation of the Regression Curve (RRB Curve) according to Laser analysis Cement Plant Mill Separator Test no. Description dim.m 1 2 4 6 8 10 15 20 30 40 60 90 100 pass. (%) 2.8 6.7 13.0 18.9 24.5 29.6 41.5 51.5 64.7 76.0 86.5 95.4 97.5 Cement Type Sample Spec.surf. M2/kg blaine laser Pozzolanic CEM IV/B-P 32.5 R
87
FEMA 3.8x13.75m; Loesche 2.4m Humboldt 3.5m Grinding with MA.P.E./W 1 (0.27%) res. (%) 97.2 93.3 87.0 81.1 75.5 70.4 58.5 48.5 35.3 24.0 13.5 4.6 2.5
419.7 296.7
Residue
(%)
30 m 25.0
40 m 18.5 Y=a+nx
60 m 5.0
90 m 1.0
200 m 0.0
Notes
88
3. CONCLUSIONS
The results obtained from the industrial trial have confirmed the triple action of the additive MA.P.E./W1 and continuous utilisation of this product gives the following benefits: Increases in productivity, especially in the periods when energy costs are lower ensuring significant energy savings. Cement mechanical strength increases. An increase in the workability of the cement. The inferior water demand reduces the consumption of cement and helps the synergy with plasticizer additives employed in the production of concrete.
/A . .E .P A M
MApei Performance Enhancer/A Grinding aids for masonry cement
DESCRIPTION MA.P.E./A are air-entraining agents formulated for grinding of artificial and natural hydraulic masonry cements. Artificial hydraulic masonry cements are obtained by the grinding of clinker (15/40%) together with one or more inert materials (limestone or siliceous). Natural hydraulic masonry cements are obtained by firing natural marls at +900C, and are characterized by low mechanical strengths, but have a pasty consistency, high workability and adhesiveness. MA.P.E./A confer to artificial hydraulic masonry cements characteristics similar to those of the natural ones (workability, adhesiveness, resistance to frost-thaw cycles, etc). MA.P.E./A can also further improve the performance of natural hydraulic masonry cements. Specific formulations of MA.P.E./A also allow mill output increases. Masonry cement evaluation is principally based on air entrapment (>10%) and water retention (> 85%) potential. These characteristics guarantee better workability, yield and durability of the cement. TECHNICAL CHARACTERISTICS MA.P.E./A have both air entraining and water retention actions. Air entraining can reach 15 to 18% improving the workability of the product. Water retention can easily exceed 95% (based on ASTM standards). Air is entrained in micro-bubbles, homogeneously distributed, improving workability, yield per surface unit and resistance to freeze-thaw cycles. Microbubbles, with controlled diameter and high stability, act as a lubricant between mortar layers, improving flow and workability. Water retention prevents the mortar mixing water from migrating towards the external substrate, improve adhesiveness and helps avoid crack formation. Regular water content in the mortar allows a homogeneous and controlled hardening. APPLICATION PROCEDURE MA.P.E./A are formulated to improve the characteristics of natural and artificial hydraulic masonry cements. They are to be added to the mill during the grinding phase for a correct dispersion and to maximize the performance. CHEMICAL-PHYSICAL DATA Please refer to the appropriate safety data sheets. DOSAGE 0.6-1.0 kg/t. The optimum dosage depends on the type and fineness of the masonry cement.
5 0 r /C . .E .P A M
MApei Performance Enhancer/Cr 05 Cr(VI) Reducing Additive
DESCRIPTION MA.P.E./Cr 05 is a chromate reducing agent, formulated with selected raw materials, ensuring an elevated and constant quality. MA.P.E./Cr 05 is a liquid additive which has to be added to the mill during the cement grinding process. It ensures the production of cements without Cr(VI), according to European obligation 2003/53/EC. TECHNICAL CHARACTERISTICS MA.P.E./Cr 05 guarantees, besides advantages coming from the usage of a liquid product, an efficient and stable reduction of soluble chromates in cement and hydraulic binders. It is an absolutely innovative liquid product, based on antimony*, dispersed on to clinker and other raw materials during the grinding of cement. During cement hydration the reducing agent acts on soluble chromates, transforming Cr(VI) into Cr(III). In comparison with traditional Cr(VI) reducing additives, MA.P.E./Cr 05 has an alkaline pH. APPLICATIONS MA.P.E./Cr 05 can be successfully employed in cement or hydraulic binders and in general wherever it is necessary to reduce Cr(VI).
The additive must be used only during grinding, added on to the clinker conveyor belt or directly in first chamber. In any case it should be added as close as possible to the mill entrance, avoiding long and complicated distances which could cause a loss of additive before mill entrance. It is recommended to avoid mixing MA.P.E./Cr 05 with grinding aids normally employed in cement factories. Under normal cement storage conditions and applying a dosage based on grinding plant conditions, the reducing action shall remain unchanged for at least six months. CHEMICAL-PHYSICAL DATA Please refer to the appropriate safety data sheets. The dosage depends on Cr(VI) cement content and plant type. Generally speaking we suggest a dosage between 50 and 55 g/t for each ppm of Cr(VI) existing in cement. The optimum dosage, in any case, has to be found through a reliable industrial trial, preferably with the help of MAPEI Cement Additives Division technicians. DOSAGE MA.P.E./Cr 05 can be dosed by means of peristaltic or membrane pumps.
93
t t
SCIENTIFIC BACKGROUND (Previously published in ZKGMagazine) MA.P.E./Cr 05: Industrial case studies and economical considerations
94
Thanks to intensive Research, D.A.M. developed a new, liquid and now patented technology for the reduction of Cr(VI) in cement, with numerous advantages in terms of technical functionality, practical application and economic impact. In fact, MA.P.E./Cr 05 allows cement manufacturers to guarantee their customers extremely long lasting Cr(VI) reduction (up to 12 months), even in extreme conditions (like cement transport by sea) and without any negative effects in concrete applications. The advantages for the cement manufacturers themselves, however, are confirmed in terms of material handling (the product has a neutral pH), application (dosing a liquid product is much easier than powder compounds) and costs (the product is to be dosed stoichiometrically which allows it to be competitive in certain cases, even with Ferrous Sulfate).
increases, their red-ox potential drop faster than the red-ox potential of Cr6+) and the Fe(OH)2 and Sn(OH)2 become strong reducing agents; soluble chromates are reduced to Cr(OH)3. In Table 1 the red-ox potential of Cr(VI)/Cr(III), Fe(III)/Fe(II) and Sn(IV)/Sn(II) in alkaline solution are reported [2]: the lower is the red-ox potential, the higher is the reducing power of the couple. Both ferrous and stannous salts present advantages and disadvantages. Ferrous sulphate (available in different hydrated forms) is very cheap, but presents serious problems related to the durability of the reducing properties: it is very sensitive to moisture and temperature and tends to loose efficacy after grinding and during cement storage. This requires the use of very high dosages of ferrous sulphate, with costs higher than expected and undesired effects (spots on the concrete surfaces, due to the red colour of Fe3+ compounds, are reported). In our opinion, the poor durability of iron(II) reducing agents can be explained considering the acid character of iron and the presence of water of crystallisation. We can suppose that ferrous sulphate may react during cement grinding (or storage) with very alkaline free lime, being partially converted to ferrous hydroxide according to the following acid-base reaction: 3) FeSO47H2O + CaO = Fe(OH)2 + CaSO4 + 6H2O If ferrous sulphate is converted before having soluble chromates available for reduction, due to the strong reducing properties, ferrous hydroxide is readily oxidised by oxygen and looses its reduction ability.
95
Half-reaction CrO42- + 3e- + 4H2O = Cr(OH)3 + 5OHFe(OH)3 + e- = Fe(OH)2 + OHSn(OH)62- + 2e- = Sn(OH)2 + 4OH-
Stannous sulphate has a superior reduction capacity (allowing very low dosages) and no undesired effects, but is very expensive. Recently it has been reported [3] that in presence of high amounts of free lime and moisture, stannous compounds partially loose their reduction ability. This is more evident with liquid additives based on tin(II) compounds (stannous chloride or sulphate), in particular with stannous sulphate aqueous solutions, as reported elsewhere [4]. The reason, as explained for iron(II), can lie in the fact that tin(II) has strong acid properties, and during cement grinding it can react with free lime and water being partially converted to stannous hydroxide: 1) SnSO4 + CaO + H2O = Sn(OH)2 + CaSO4 2) SnCl2 + CaO + H2O = Sn(OH)2 + CaCl2 The stannous hydroxide, due to its very low red-ox potential, is unstable and, if no soluble chromates are present, is immediately oxidised by oxygen or water or spontaneously converts to
96
tin(IV) and metallic tin. This behaviour is summarized in the Pourbaix diagram of tin [5], that reports the stability range of several tin compounds in function of pH and red-ox potential (Figure 1). It is possible to see that, as the pH increases, the stability area of Sn(OH)2 is reduced and, above pH=12, only Sn4+ and metallic tin are stable. As a result, in some cases higher tin dosages are required, with negative effects on costs and durability of reducing properties. The reactions 4 and 5, in order to proceed, require the presence of water. This may be the reason why stannous sulphate in powder is more efficient than water-based liquid formulations containing tin salts.
E (volt)
2.0
1.0
0.0
-1.0
-2.0
Figure 1: Pourbaix diagram of tin. The red area represents the pH range of cement mixing water. The variation of red-ox potential of oxygen and hydrogen are pointed out
A brand new technology: antimony(III) compounds A very promising and innovative class of reducing agents (at the moment object of an international patent application by Mapei SpA) has recently been studied and developed in Mapei R&D lab. The efficacy and the superior performances of this novel class is based on the red-ox properties of antimony(III). The couple Sb(V)/Sb(III), has a red-ox potential in alkaline solution E=-0,59 volt [2]. From a thermodynamic point of view, this means that Sb(III) is a strong reducing agent at high pH and can reduce Cr(VI) present in the cement mixing water, according to the following equation: 6) 2CrO42- + 3H2SbO3- + 2H2O = 2Cr(OH)3 + 3SbO3- + 4OHThe Pourbaix diagram of antimony [5], reported in Figure 2, shows that the Sb(III) is stable at alkaline pH. In comparison to ferrous and stannous salts, Sb(III) compounds have weaker acid properties. This is an interesting advantage, because the reaction with free lime does not proceed,
avoiding any efficacy loss during cement grinding or storage, even in case of high free lime content and high level of humidity. As a result, the reduction performance of antimony(III) is unaffected by moisture and high grinding or storing temperatures. The reducing properties of antimony(III) remain unchanged even after more than one year.
97
E (volt)
1.0
0.5
0.0
-0.5
-1.0
Figure 2: Pourbaix diagram of antimony. The red area represents the pH range of cement mixing water. The variation of red-ox potential of oxygen and hydrogen are pointed out Antimony(III) in a liquid additive: MA.P.E./Cr 05 The formulation of a liquid additive based on antimony(III) for the reduction of hexavalent chromium requires the selection of the most appropriate Sb(III) compound. This should be: easy to incorporate in a water-based formulation; with an economical impact inferior to tin-based liquid additives; no effect on the properties and quality of the cement. Most of all, in order to maintain its reduction ability safe for as long as possible, the reducing agent should remain unaltered during the storage of the additive and, after being added in the mill, during the storage of cement. Strong reducing agents (like ferrous or stannous salts) are readily oxidised by oxygen (or directly by water, as described for stannous hydroxide), and high temperatures and high levels of humidity (e.g. presence of coordination water, as in the case of fer-
98
rous sulphate) speed up the reaction. If it was possible to activate the reducing agent only when cement is mixed with water (when soluble chromates are available for reduction), we would obtain an excellent improvement of shelf life and durability after prolonged storage. We have found that it is possible to reach all the targets using a liquid additive based on antimony trioxide. This compound is amphoteric: it is soluble only at very low or very high pH and is completely insoluble at medium pH. A liquid additive with high load of insoluble particles of antimony trioxide can be easily prepared by using the well-known technology of solid liquid dispersion, widely used in several industrial sectors (ceramic, polymers, textile, paints, paper, cosmetics and pharmaceutical, detergents) [6]. The principle of action is now clear: the antimony trioxide is dispersed in to the cement by simply dosing the liquid additive on to the clinker conveyor belt and ground in the mill. Thanks to its insolubility and low acidity, it is not modified by water or free lime and it remains unaltered until cement is mixed with water: at pH higher than 12 the antimony trioxide is dissolved in water and is fully available to reduce the Cr(VI) released in water. The advantages of MA.P.E./Cr 05 are the following: neutral (or alkaline) pH, while other liquid additives based on tin have strong acid pH and are highly corrosive. No recrystallisation of partially solubilised salts (the active component is completely insoluble) and consequently no formation of precipitate and difficulties in pumping. No reducing agent lost, in any mill conditions (high amount of cooling water, high temperature). This allows the cement plant to avoid any extra dosage, as usually happens with ferrous sulphate and sometimes with tin-based liquid reducing agents. No reducing agent lost during storage: this allows to maintain constant the Cr(VI) content for a very long time, without requiring an over dosage. Case study In order to check the reduction performance of MA.P.E./Cr 05, the following laboratory test has been performed. The performances of ferrous sulphate, stannous sulphate and MA.P.E./Cr05 (a liquid suspension of antimony trioxide, with 20% active matter), have been compared. A cement has been reproduced in a laboratory mill by grinding clinker and gypsum. A clinker with a very high level of free lime has been chosen (free CaO = 1.78%). The amount of soluble Cr(VI) released in water (without reducing agent) is 10 ppm. The same cement has been reproduced by grinding with the reducing agents reported in the table 2.
Reducing agent Ferrous sulphate (FeSO47H2O) Stannous sulphate (SnSO4) MA.P.E./Cr 05 (20% water suspension of Sb2O3)
0.045 %
45 g/tppm
The samples of cement have been stored in the same conditions and the soluble Cr(VI) content has been evaluated for a period of six months, using the following method: 100 g of cement are
added to 100 g of water. After magnetic stirring for 15 minutes, the water is filtered off and analyzed by ionic chromatography (see [7] for details). The results are summarized in the graph 1. It can be clearly seen that with this cement (characterised by a high content of free lime) the stannous sulphate is effective only for a limited period of time: after two months the soluble Cr(VI) content exceeds the limit of 2 ppm. The ferrous sulphate at a dosage commonly used (0,2%) is unable to eliminate Cr(VI). The performances of antimony trioxide (MA.P.E./Cr 05) are clearly superior: the Cr(VI) level is close to zero even after several months. On an industrial scale, the results are similar. In addition it is possible to see that the economical incidence of such an additive is lower than the incidence of stannous sulphate and sometimes can be similar to that of ferrous sulphate. Graph 1: results of lab test about reducing agents
99
day
days
days
days
days
month
months
months
months
Conclusions The use of antimony(III) compounds for the reduction of hexavalent chromium in cement and cement based materials presents interesting advantages: 1. Due to the high stability and low acidity of antimony(III), these reducing agents are insensitive to temperature and humidity and are not affected by the presence of high levels of free lime. This allows superior performances to be obtained in comparison to the usual reducing agents based on ferrous or stannous salts. 2. Antimony(III) compounds can also be used for the formulation of liquid additives. If antimony trioxide is dispersed in water (using well known technologies), it is possible to obtain a stable suspension that can be dosed during cement grinding as a liquid additive. Thanks to its amphoteric properties, the antimony trioxide remains unchanged on the surface of cement and is activated only when the cement is mixed with water and the pH rises above 12. This theoretically allows to maintain the efficacy of the reducing agent for an infinite time. 3. The MA.P.E./Cr 05, a liquid additive formulated according to this new technology, shows superior performances in comparison to iron and tin based reducing agents.
100
How to use MA.P.E./Cr 05 It is important to point out that, thanks to the long term stability, it is not necessary to reduce completely the hexavalent chromium present in cement. MA.P.E./Cr 05 can be dosed in order to reach a Cr(VI) level of about 1 ppm. This value will usually be maintained even after several months, which allows interesting cost savings. MA.P.E./Cr 05 has a great Cr(VI) reducing effect on any type of cement, as shown in Table 2.
Table 2: efficacy of MA.P.E./Cr 05 on different cements Cement type Cr(VI) Dosage Cr(VI) Cr(VI) after 6 months CEM I 52.5 R 22.3 ppm 1.02 kg/t 1.1 1.1 CEM II/A-LL 42.5 R 10.3 ppm 0.45 kg/t 1.0 1.0 CEM II/B-S 32.5 R 7.6 ppm 0.29 kg/t 0.9 0.9 CEM II/B-M (LL-P) 32.5 R 6.0 ppm 0.23 kg/t 0.8 0.8 CEM III/A 32.5 N 4.4 ppm 0.17 kg/t 1.0 1.0 CEM IV/B-P 32.5 R 5.7 ppm 0.22 kg/t 1.2 1.2
Comparison with stannous sulphate Stannous sulphate is a widespread Cr(VI) reducing agent, available in both powder and liquid form. Usually, the powder is more difficult to handle and to dose accurately than the liquid product. The average dosage of stannous sulphate is 15 g/t for each ppm of Cr(VI) and guarantees a Cr(VI) reduction for several months. Stannous sulphate prices have increased very much in the last few months. At the moment we can consider a price of around 8 - 9 /kg. Industrial case n1 A CEM I 52.5 R is produced with 5000 cm2/g Blaine fineness, with a mill productivity of 48 t/h. The hexavalent chromium content of this cement is about 13 ppm. The reducing agent used is stannous sulphate (powder form) at a dosage of 15 g/tppm. MA.P.E./Cr 05 was tested in comparison to stannous sulphate. As summarized in Table 3, it has been possible to dose MA.P.E./Cr 05 at 48 g/t*ppm, allowing a 17% cost saving. Compared to stannous sulphate MA.P.E./Cr 05 presents the following advantages: Technical advantages: easy dosing and pumping Economical advantage: cost savings in the cement production process (-17,3%) Considering the use of stannous sulphate-based liquid additives, it is possible to overcome the difficulties in handling a powder, but the economical impact is obviously higher, sometimes even 40 50% higher than MA.P.E./Cr 05.
101
Table 3: industrial case - comparison with stannous sulphate Stannous sulphate MA.P.E./Cr 05 Price (/kg) 8.5 2.2 Dosage (g/t*ppm of Cr(VI) 15 48 Dosage (g/t) 195 624 Economical impact (/t) 1.66 1.37 Differences (%) // -17.3%
Comparison with iron sulphate Iron sulphate is available only in powder form. It is commonly employed in cement plants in spite of the following technical problems: Unstable product: over dosage is necessary in order to guarantee Cr(VI) reduction for at least 3 months. Dosing system: difficult and expensive handling. Side effects: possible red/dark spots on concrete surface. The very low price is the only advantage of iron sulphate, even if this is not always true: sometimes the economical impact of MA.P.E./Cr 05 has been found lower (or comparable) than iron sulphate. The following example describes one of our practical experiences. Industrial case n2 An Italian cement plant produces a CEM II/A-LL 42,5 R (80% clinker, 15% limestone, 5% gypsum) with Cr(VI) content of 5 ppm. To reduce and maintain the level of Cr(VI) constant for three
102
months, iron sulphate is used at a dosage of 1.5 kg/t (0.15%) of cement produced. The price of iron sulphate is 0.14 /kg (including delivery costs) so its economical impact is 0.21 /t of cement. Several dosages of MA.P.E./Cr 05 were tested in order to clarify the economical impact. Considering that no overdosing is needed, it is not necessary to reduce Cr(VI) completely: the industrial trial was performed in order to have a final Cr(VI) content of 1 ppm. Graph 1 shows that MA.P.E./Cr 05 dosed at about 100 g/t has the same economical impact as iron sulphate. Any dosage below this value means lower economical impact and allows to maintain the level of Cr(VI) below 2 ppm even for several months.
Graph 1: industrial case - economical impact of MA.P.E./Cr 05 in comparison to iron sulphate. Pink line: ppm of Cr(VI) residual. Blue line: economical impact of MA.P.E./Cr 05 (/t) Red line: economical impact of iron sulphate
Conclusions 1. MA.P.E./Cr 05 is a new liquid additive for Cr(VI) reduction in cement and cement based materials. 2. Thanks to the properties of its active ingredient (antimony trioxide), MA.P.E./Cr 05 shows superior performances in comparison to iron and tin based products. 3. In most cases, the use of MA.P.E./Cr 05 allows lower economical impact (in terms of euro for each ton of cement produced), with technical performances comparable (or superior) to other reducing agents.
NOTES
103
104
Since 2008 DAM is part of Mapeis Liquid Admixtures Division. This division has been formed in order to optimise the synergy between the various stages of the building process of any type of structure: Cement Manufacturing - Concrete Application Terrain Decontamination - Underground Technology. Through joint projects in terms of Research & Development, Technical Customer Assistance and Product Development, knowledge is shared and products and services are improved. Within the Liquid Admixture Division special attention is paid to the reduction of CO2 emissions and the limitation of the use of non-renewable resources. In this specic eld of interest, DAM is offering various specic solutions to the cement industry for the reduction of both clinker content and the specic energy consumption during the production of cement.
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In the year 2000 the Robbiano di Mediglia plant obtained the certication of its occupational health and safety management system in accordane with the OHSAS 18001 standard, as well as the certicate of excellence that attests to its compliance with the requirements of the ISO 9001, ISO 14001, OHSAS 18001 standards and of CE 761/01 (EMAS) Regulation
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