Abstract:
Disclosed is a process for the manufacturing of synthetic pozzolan with desirable color properties. Feed material is dried, crushed, and preheated in a drier crusher. The dry, crushed material is collected and fed to a calciner where it is heated to become a synthetic pozzolan. The synthetic pozzolan is then fed to a cooler where it is maintained for a least a portion of the cooling step in a reducing atmosphere.

Description:
[0001]    This application is a continuation-in-part of, and claims priority from, pending non-provisional application Ser. No. 12/966345, filed Dec. 13, 2010. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    There is currently a large amount of attention being paid to the use of additive materials in cement in order to maintain or increase the strength of the cement while reducing the overall energy required to produce the material. In practice, a number of natural and manufactured materials are added to clinker in order to reduce the need for clinker minerals in the cement. These materials include limestone, waste slag from the manufacture of steel and iron, and naturally occurring pozzolan. Disadvantages exist to the use of these materials in practice. Quality concerns limit the introduction of limestone, as limestone naturally provides little to the strength of the finished product. Certain types of slag can be utilized positively for the introduction of strength to cement, but as a waste product of the manufacture of other compounds, the slag often does not have a consistent chemistry. Slags can also contain large amounts of free iron, which can cause premature wear of grinding elements used in the manufacture of cement. Pozzolan provides positive strength development in finished cement, but as a naturally occurring material, is not generally available in locations where the primary raw materials used in the manufacture of cement are mined. 
         [0003]    In recent years, a number of processes have gained prominence in the production of artificial pozzolan from the calcining of clay. The manufacture of artificial pozzolan requires lower temperatures and less energy than the production of cement clinker, and is therefore gaining importance among cement manufacturers for its lower cost of production, as well as the positive effects of producing lower emissions (particularly CO 2 ). 
         [0004]    In practice, however, while the chemistry may be consistent with a positive effect on strength development, the production of these artificial pozzolans may create materials which are colored differently than the clinker used in the manufacture of cement. This is problematic where the color of the finished product is an important concern, such as when multiple sources of cement may be used for a single project. These issues with the coloration of the final product serve to limit the introduction of these synthetic pozzolans in the production of cement. 
         [0005]    Therefore, it is an object of the present invention to provide a method for producing synthetic pozzolan having desired color characteristics, and in particular having a light grey color that many cement producers find desirable. 
       BRIEF DESCRIPTION OF THE INVENTION 
       [0006]    The above and other objects are achieved by the process of the present invention according to which the coloration of the artificial pozzolan produced may be controlled as desired. Having a synthetic pozzolan product with desirable color characteristics will enable the end user to introduce higher amounts of pozzolan into the finished cement, thus resulting in a higher quality product produced utilizing lower fuel consumption than other cement producing systems. 
         [0007]    The invention broadly comprises breaking apart a starting raw material, such as an alumina silicate such as a kaolinic clay, a diatomaceous earth, or a diatomaceous amorphous alumina silicate, to a small feed size, heat treating the raw material to a product pozzolan, and then by affecting the oxidation state of the color-producing components of the artificial pozzolan product, particularly iron and aluminum, through the creation of localized reducing conditions as the pozzolan product cools to a temperature below its color-stabilizing temperature, which color-stabilizing temperature is determined by the amount and identity of color-producing components in the raw materials and therefore in the resulting synthetic pozzolan. 
         [0008]    More specifically, wet raw feed materials capable of producing an amorphous alumina silicate when heat treated as described herein, including kaolinic clay, diatomaceous earth and diatomaceous amorphous alumina silicate are fed to a device for sufficient material drying and disagglomeration/crushing of larger material (a “drier crusher”). The product from the drier crusher is collected in a cyclone, and directed to a calciner. Fuel is fed to the calciner to maintain an exit temperature from the calciner that will provide sufficient dehydration and activation of the product. The feed material is heated at least to a temperature (the “activation temperature”) at which the pozzolanic properties, such as the strength of the end material, are optimized and at which, in effect, the raw material is converted to a synthetic pozzolan. This activation temperature will generally range between about 700° C.-900° C., depending upon the properties of the specific raw material being utilized. 
         [0009]    The product from the calciner is collected, such as in a collection cyclone, and the material is fed to a cooler where it is cooled from its activation temperature. The gases from the collector may optionally be used for drying and conveying material through the drier crusher. Reducing conditions are maintained in the cooler for at least a portion, and most preferably the initial portion, of the cooling process. When only a portion of the process of cooling the synthetic pozzolan from its activation temperature to its color-stabilizing temperature is performed under reducing conditions, it is preferred that the balance of the cooling process be performed in an oxygen depleted environment. 
         [0010]    Pozzolan material fed to the cooler may be treated with a small amount of fuel (preferably oil) to maintain a reducing atmosphere near the material inlet. Further into the cooler, water may be optionally sprayed to assist in cooling of the pozzolan to below its color-stabilizing temperature while maintaining a low oxygen environment. Alternatively, an oxygen depleted gas can be passed through the cooler along with or in place of the water vapor to cool the pozzolan to below its color-stabilizing temperature while maintaining a low oxygen environment. The product from the cooler may then be introduced into one or more optional additional coolers, such as a cyclone cooling system, for further cooling. If the material entering the any additional downstream coolers is at a temperature below its color-stabilizing temperature, a reducing or oxygen-depleted atmosphere will not have to be maintained in such additional cooler. The finally cooled product is thereafter collected. The preheated gases from any additional cooler may be optionally directed to the calciner as hot tertiary air. 
     
    
     
       DESCRIPTION OF THE DRAWINGS 
         [0011]    The invention is described with reference to the drawings, in which like numerals represent similar elements, and in which: 
           [0012]      FIG. 1  is a diagram of one embodiment of a heat treating system for manufacture of synthetic pozzolan of a suitable coloration, in which a flash calciner is utilized. 
           [0013]      FIG. 2  is a second embodiment of a system for manufacture of synthetic pozzolan. 
           [0014]      FIG. 3  is a third embodiment of a system for manufacture of synthetic pozzolan. 
           [0015]      FIG. 4  is another embodiment of heat exchanger region  100  with three cyclones  25 ,  52 ,  55  being used as a counter current heat exchanger to capture more heat from the synthetic pozzolan  21  to increase the temperature of the combustion air  23  in duct  26  which subsequently enters flash calciner  13 . 
           [0016]      FIG. 5  is another embodiment of heat exchanger region  200  with three cyclones  4 ,  62 ,  65  being used as a counter current heat exchanger to capture more heat from the calciner exhaust gas to increase the temperature of the dried, crushed material in chutes  10   a  or  10   b.    
           [0017]      FIG. 6  is an embodiment of a kiln system for manufacture of synthetic pozzolan of a suitable coloration in which a rotary kiln is used for processing raw material. 
           [0018]      FIG. 7  is another embodiment where the reducing conditions used for cooling the synthetic pozzolan are generated by a separate gasifier or combustor operating under sub-stoichiometric conditions. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0019]    In all the figures, dashed arrows represent the flow of gas, while solid arrows represent the flow of solid material. With reference to  FIG. 1 , raw material  1  is directed to the drier crusher  2  where the material is crushed to less than 5 mm and preheated and dried from a initial moisture content ranging from about 5% (wt) to about 35% to a moisture content of from about 0.025% to about 2.5% by the hot gas in duct  16  from the calciner cyclone  15 . The dried, crushed material is of a size suitable to be suspended and conveyed in a gas stream through duct  3  to the drier crusher cyclone  4  where it is separated from the gas stream. The gas stream  5  is pulled by an optional ID fan  6 . After the ID fan  6 , any remaining fine dust is removed by dust collector  7 . After the dust collector the gas is pulled by ID fan  8  and exits the system via stack  9 . The fine dust from dust collector  7  is directed either (a) to the calciner  13  via chute  12   a;  (b) to duct  16  via  12   b  and thereafter into drier crusher  2 ; or (c) to duct  3  via chute  12   c  and thereafter into drier crusher cyclone  4 . 
         [0020]    Most of the dried, crushed material collected in the drier crusher cyclone  4  is directed to the calciner  13  via chutes  10   a  or  10   b.  Optionally, a small amount of the dried, crushed material collected in the drier crusher cyclone  4  may be directed to duct  16  for temperature control of the gas in duct  16 . The calciner  13  shown in  FIG. 1  is an updraft calciner where the combustion air enters through duct  26  into the lower portion of the calciner. Water vapor and/or oxygen depleted gas and some vaporized fuel from inlet  18  enter the calciner through the riser  28 . Fuel can be directed into the calciner  13  or the duct  26  leading to the calciner through a single location or multiple locations  19   a ,  19   b ,  19   c  and  19   d . The number of fuel locations and the proportion of the fuel depend upon the properties of the fuel and the need to control the combustion in the calciner  13 . 
         [0021]    Optionally, a stoichiometric excess of fuel may be utilizing in calciner  13  to promote heat treatment under reducing conditions. 
         [0022]    Fuel can also be fired in a separate air heater (not shown) that receives either ambient air and/or heated air from duct  26 ; the exhaust gas from this air heater is directed into the calciner  13 . 
         [0023]    The crushed, dried materials can be directed into the calciner  13  through a single location or multiple locations  10   a  and  10   b . The split of material in chutes  10   a  and  10   b  is determined by the de-hydration and activation properties of the raw materials and the split also can be used to help control the combustion of the fuel in the calciner  13 . In the calciner the hydrated moisture will be dried off and the material will be heat treated to its activation temperature. The desired activation temperature in the calciner  13  will depend on the chemistry of the feedstock and the associated minerals in the raw feed and will be between 500° C. and 900° C. and most prevalently between about 700° C. and 850° C. Most of the synthetic pozzolan will thereafter become entrained in the gas stream in the calciner  13  and exit via duct  14 . 
         [0024]    The entrained pozzolan in duct  14  is captured by the calciner cyclone  15  and is directed to cooler  20 , which as depicted is a rotary cooler, via chute  17   a , with a portion being optionally re-circulated back to the calciner  13  via chute  17   b . The operator may desire to utilize the recirculation feature to increase the retention time in the calciner for reasons such as, for example, system height restrictions, for better temperature control and/or improved fuel burnout. 
         [0025]    A small amount of fuel, between 10 to 40 kcal fuel per kg of synthetic pozzolan, is added to the synthetic pozzolan via inlet  18  and preferably immediately prior to the pozzolan entering cooler  20 . The preferred fuel is fuel oil. The fuel creates local reducing conditions, i.e., an oxygen depleted or low (from about 0% to about 5% by volume) oxygen environment and either CO and/or volatized hydrocarbons, near the synthetic pozzolan during at least the initial part of the cooling process. Downstream from the cooler area in which the small amount of fuel was added, water sprayer  22  is utilized to spray water onto the synthetic pozzolan to contribute to cooling the pozzolan below the color-stabilizing temperature of the color producing metals, particularly iron, which generally between about 150° C. and about 600° C., and more typically between about 180° C. and about 400° C., with the actual color-stabilizing temperature depending on the composition of the pozzolan, and specifically the amount of iron content. Since the synthetic pozzolan is kept well above 100° C. the synthetic pozzolan remains dry. The water vaporizes upon contact with the hot pozzolan. The generated water vapor occupies most of the space inside the cooler  20 , this helps to maintain an oxygen depleted atmosphere (i.e. no more than about 10% oxygen) in that portion of the cooler which retards the oxidation of metals. The water vapor exits the cooler  20  via the riser  28 . A portion of the fuel oil will volatilize and exit the cooler  20  via the riser  28 . In addition some CO produced by burning the fuel and excess water vapor will exit cooler  20  via riser  28 . By preventing the oxidation of iron, in particular, and other metals including aluminum, magnesium, manganese and chromium during the cooling process, the pozzolan is prevented from changing to a reddish or other color and may be fixed as white or light grey. 
         [0026]    As a supplement or alternative to using water as described above an oxygen depleted gas can be passed through the cooler to cool the pozzolan below the color-stabilizing temperature of the color producing metals. Two possible sources of the oxygen depleted can be the exhaust stream  9  or the gas exiting fan  6 ; however, any oxygen depleted gas can be used. 
         [0027]    In an optional embodiment, the objects of the invention can be achieved if the raw material is heat treated to form synthetic pozzolan under reducing conditions by utilizing a sufficient amount of excess fuel during the heat treating process and thereafter continuing to cool to the “color-stabilizing temperature” under reducing and/or oxygen depleted conditions. 
         [0028]    The term “color-stabilizing temperature” as used herein means the temperature at which the pozzolan can continue cooling, such as in ambient air, without significant oxidation of the primary color-producing species in the pozzolan taking place. This temperature will vary according to the relative proportion by weight of color-producing species, which is defined as those compounds which go from a white or light grey shade to a red or other color when oxidized, and which constitute primarily iron, but also to a lesser extent aluminum, chromium, manganese, titanium and magnesium, in the cooling pozzolan material. Typically, this temperature will range from about 180° C. to about 400° C. If oxidation of a substantial (i.e. at least 90 wt percent) amount of the primary color-producing species is inhibited while the material is cooled to its color-stabilizing temperature, the final cooled product will typically have a light grey shade. 
         [0029]    The activation and color stabilization temperatures, as defined herein, for a given sample of material can be determined by one skilled in the art by a number of test procedures. For example, the activation temperature for a given raw material may be determined by running a furnace test or a thermogravimetric analysis on the sample and the color stabilization temperature may be determined by running thermal studies on the cooling synthetic pozzolan material made from said raw material. 
         [0030]    As used herein, the term “reducing conditions” or “reducing atmosphere” means that the overall conditions in the cooler (or the calciner) favor reduction of the color-changing species in the pozzolan. As used herein, the term “oxygen depleted” or “oxygen deprived” atmosphere or conditions means that while overall conditions do not promote reduction of the color-changing species in the pozzolan, there is also not sufficient oxygen to promote their oxidation. 
         [0031]    The synthetic pozzolan exits the cooler  20  via chute  21  and is directed into duct  24  where it is further cooled by air  23 . The entrained synthetic pozzolan is captured by cyclone  25  and leaves the system as the synthetic pozzolan product  27 . The air preheated by the synthetic pozzolan exits cyclone  25  and is directed to the calciner  13  via duct  26 . The temperature of the air in duct  26  will be almost the same as the product  27 . 
         [0032]      FIG. 2  shows another embodiment of this invention. This embodiment is identical to the embodiment shown in  FIG. 1  and described above except that all or most of the water vapor and/or oxygen depleted gas is pulled out of the cooler  20  via duct  40 . This embodiment increases the fuel efficiency of the system since the water vapor and/or oxygen depleted gas is not heated in the calciner  20 . Ambient air  41  is drawn into or injected into duct  40  to lower the dew point temperature and prevent corrosion in the downstream ductwork and dust collector  42 . Any dust captured in the exhaust duct  40  leaves the system as synthetic pozzolan product  45 . The water vapor, oxygen depleted gas, and ambient air is pulled through the dust collector  42  and exits the system via stack  44 . In this embodiment ID fans  43  and  8  are operated in balance with each other so that the gas, primarily water vapor and/or oxygen depleted gas, in a small area in region  29 , (hashed area in  FIG. 2 ), is stagnant. The gas in this small area in region  29  will not consistently move either to the calciner  13  or to the cooler  20 . 
         [0033]      FIG. 3  shows another embodiment of this invention. This embodiment is identical to the embodiment shown in  FIG. 2  and described in the previous paragraph, except that that the riser  28  is replaced by hopper  70  and chute  30 . Any material that may build up in the calciner  13  and is cleaned out is conveyed to the cooler via chute  30 . This allows the ID fans  8  and  43  to be operated independently without upsetting conditions in either calciner  13  or cooler  20  thereby allowing all the water vapor, oxygen depleted gas and volatilized fuel to exit cooler  20  via duct  40 . 
         [0034]    Optional region  100  in  FIGS. 1 ,  2  and  3  shows a single stage (one cyclone), counter current heat exchanger that preheats a portion of the hot gas in duct  26 , which is combustion gas for the calciner, and correspondingly pozzolan product  21  from rotary cooler  20 . This single stage cyclone can be replaced by multiple stages which will increase the heat captured from pozzolan product  21  and raise the temperature of the hot gases in duct  26  to the calciner  13 . As the number of stages increases, the temperature of the gas in duct  26  will increase while the temperature of pozzolan product  21  will decrease. As the number of stages is increased, the heat returned to the calciner is increased and the fuel consumption will decrease. Therefore, the preferable number of cyclones, (if any), will depend upon the temperature of the pozzolan exiting the cooler and the tradeoff between the capital cost of the cyclones versus the operational cost savings. 
         [0035]    In the embodiment of  FIG. 4 , region  100  is modified by the addition of two more cooling cyclones  52  and  55  which serves to cool the synthetic pozzolan  21  and correspondingly heat cooling air  23 . The use of multiple stage cyclones will increase the heat captured from the synthetic pozzolan  21  and raise the temperature of the combustion air  23  in duct  26  which is subsequently used in the calciner  13 . With only a single stage, the synthetic pozzolan product  27  and the air in duct  26  have approximately the same temperature. As the number of stages increases, the temperature of the air in duct  26  will increase—while the temperature of synthetic pozzolan product will decrease. In this embodiment, the synthetic pozzolan exits the cooler  20  (as per  FIGS. 1-3 ) via chute  21  and is directed into duct  24  where it is cooled by the air from cyclone  52 . The entrained synthetic pozzolan is captured by cyclone  25  and is directed to duct  51  via chute  50 . The air preheated by the synthetic pozzolan exits cyclone  25  and is directed to the calciner  13  via duct  26 . The synthetic pozzolan in duct  51  is transported to cyclone  52  where it is captured and directed to duct  54  via chute  53 . The synthetic pozzolan in duct  54  is transported to cyclone  55  where it is captured and leaves the system as product  27 . 
         [0036]    Region  200  in  FIGS. 1 ,  2  and  3  shows a single stage (one cyclone), counter current heat exchanger that preheats a portion of the raw material by inserting it in duct  16 , which is off gas from the calciner, and correspondingly cooling the gas in duct  16 . This single stage cyclone can be replaced by multiple stages which will increase the heat captured from the gas in duct  16  and raise the temperature of the dried, crushed material in chutes  10   a  and  10   b . When only a single stage cyclone  4  is utilized, the dried, crushed material in chutes  10   a  and  10   b  and the gas in duct  5  have approximately the same temperature. As the number of stages increase, the temperature of the gas in duct  5  will decrease, while the temperature of the dried, crushed material in chutes  10   a  and  10   b  will increase. 
         [0037]    However, as the number of stages is increased, the drying capacity of the drier crusher will be reduced, while the fuel consumption in the calciner will decrease. Therefore, the preferable number of cyclones will depend upon the moisture content of the raw material and the tradeoff between the capital cost of the cyclones versus the operational cost savings. 
         [0038]    Per  FIG. 5 , raw material  1  is directed to the drier crusher  2  where the material is crushed to its desired sized, preheated and dried by the hot gas in duct  63  coming from cyclone  62 . The dried, crushed material is conveyed in duct  3  to the drier crusher cyclone  4  where it is separated from the gas stream. The gas stream  5  is pulled by an optional ID fan  6  (not shown in  FIG. 5 ). The fine dust  12  from dust collector  7  (not shown in  FIG. 5 ) is to the duct  61  via chute  12   a  or to duct  63  via  12   b  and thereafter into drier crusher  2  or to duct  3  via chute  12   c  and thereafter into drier crusher cyclone  4 . 
         [0039]    Most of the dried, crushed material collected in drier crusher cyclone  4  is directed to the duct  61  via chutes  60   a , while some the dried, crushed material collected in drier crusher cyclone  4  may be directed to duct  63  via chute  60   b  for temperature control of the gas in duct  63 . The dried, crushed material in duct  61  is transported to cyclone  62  where it is captured and directed to duct  16  via chute  64 . The dried, crushed material in duct  16  is transported to cyclone  65  where it is captured and directed to the calciner  13  via chutes  10   a  and  10   b.    
         [0040]      FIG. 6  depicts an embodiment of the invention in which a rotary kiln is utilized as the calciner rather than the flash calciner depicted in the various embodiments set forth in  FIGS. 1-3  herein. When using a rotary kiln as the calciner, the front end of the process, that is, the drying and crushing steps, is essentially similar to what is utilized with a flash calciner. In this regard, the embodiment set forth in  FIG. 5  may be utilized with a rotary kiln. 
         [0041]    According to  FIG. 6 , crushed and dried feed material is inserted into rotary kiln  80  via conduit  10 . Fuel is added through inlet  79  and combined with combustion air added via inlet  83  to produce a flame  84  at the end of the kiln opposite where the raw material enters to thereby heat the combustion gases. The material travels through the kiln in countercurrent relation to the heated gases in the kiln and is heat treated to at least its activation temperature. Pozzolan exits the kiln via duct  28  and enters rotary cooler  20 . In duct  28  gas from cooler  20  is directed to rotary kiln  80 . As with the flash calciner, the pozzolan is exposed to a low oxygen environment within rotary cooler  20 , due to the introduction of fuel oil, via inlet  18   b , near the material entrance into the cooler  20 . The low oxygen environment within cooler  20  is further promoted by the spraying of water onto the synthetic pozzolan and/or by passing an oxygen depleted gas through the cooler. 
         [0042]    Optionally, fuel oil may also be inserted behind flame  84  in rotary kiln  80 , via inlet  18   a , to begin exposing the synthetic pozzolan to a low oxygen environment in an area of the kiln in which the temperature experienced by the pozzolan begins to decrease from the maximum temperatures experienced within the kiln. The insertion of fuel oil in the rotary kiln will always be done in concert with maintaining at least a portion of cooler  20  under reducing conditions. In addition, cooler  20  may also provide for the removal of water vapor and oxygen depleted gas through a dust collector in the manner depicted in  FIGS. 2 and 3 . 
         [0043]      FIG. 7  shows another embodiment which departs from the embodiment shown in  FIG. 1  in the method by which the cooling of the synthetic pozzolan under reducing conditions is achieved. In the embodiment of  FIG. 7  the entrained synthetic pozzolan in duct  14  is captured by the calciner cyclone  15  and is directed to and injected into reducing duct or vessel  96  via chute  17   a . A portion of the captured synthetic pozzolan may be optionally re-circulated back to the calciner  13  via chute  17   b . The reducing conditions for reducing vessel  96  are created by directing gases from the reducing gas generator  93  which may be a gasifier or combustor operating under sub-stoichiometric conditions, into a reducing vessel  96 , via duct  95 . Ambient air  90  is added to the reducing gas generator  93  via duct  92  from the optional fan  91 . The fuel  94  needed to generate the reducing conditions in reducing gas generator  93  can be added at one or multiple location(s). The entrained synthetic pozzolan and reducing gas exit the reducing vessel  96  via duct  97  and are directed to the reducing cyclone  98 . The captured synthetic pozzolan is directed to the cooling chamber  99  via chute  20 . The reducing gases exit the reducing cyclone  98  via duct  28  and are directed to the calciner  13 . Water is injected into cooling chamber  99  to cool the pozzolan to a temperature below the color-stabilizing temperature and to help maintain reducing conditions in cooling chamber  99  as additional oxygen is not inserted into the chamber. The synthetic pozzolan exits the cooling chamber  99  via chute  21  and is directed into duct  24  where it is further cooled by air  23 .