Germany - 100607 Patent For Manufacturing White Rice Husk Ash

Title:
Method of producing low-carbon, white husk ash

Document Type and Number:
United States Patent 4049464
Link to this page:
http://www.freepatentsonline.com/4049464.html
Abstract:
Low carbon, white husk ash suitable for use in manufacturing building materials,
more particularly refractory building materials are prepared by first removing volatile
constituents by heating the husks, normally rice husks but alternatively, for
example, wheat, oats or barley husks, to a first relatively low temperature below the
ignition point of the husks. Fixed carbon is then oxidized in the presence of a reagent
by heating the husks to a second temperature above the separation temperature but
below the crystallization temperature of the SiO.sub.2 in the husks, following by a
heat treatment at a third temperature above the crystallization temperature of the
SiO.sub.2, to produce a uniform SiO.sub.2 crystal structure.
Inventors:
Tutsek, Alexander (Gottingen, DT)
Bartha, Peter (Bovenden, DT)
Application Number:
720089
Filing Date:
09/02/1976
Publication Date:
09/20/1977
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Referenced by:
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Export Citation:
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Assignee:
Refratechnik GmbH (Gottingen, DT)
Primary Class:
106/406
Other Classes:
423/335
Field of Search:
106/288 B, 288 Q, 309 423/335
US Patent References:
1528371 Mar, 1925 Gambel 423/335.
3125043 Mar, 1964 Gravel 110/28.
Foreign References:
2,070,383 Sep, 1971 FR
697,474 Sep, 1953 UK
Primary Examiner:
Garvin, Patrick P.
Assistant Examiner:
1
Sheehan, John P.
Parent Case Data:
This is a continuation, of application Ser. No. 562,098, filed Mar. 26, 1975 now
abandoned.
Claims:
We claim:
1. In a method of producing low-carbon, white rice husk ash suitable for the
production of building materials, and more particularly refractory building materials,
in which method, for purposes of removing volatile constituents and for purposes of
transforming the fixed carbon into a gaseous compound, the rice husks are heated to
a temperature below the crystallization temperature of the SiO.sub.2 of the rice
husks, whereupon the resultant husk ash is heat-treated at a temperature above the
crystallization temperature of the SiO.sub.2 for the purposes of obtaining a uniform
SiO.sub.2 crystal structure, the improvement comprising: the first step of heating
the rice husks to a first relatively low separation temperature within the range of
from 200.degree. to 450.degree. C. in the absence of air, exclusively for separating
the volatile constituents that are capable of after-burning; subsequently the second
step of heating the rice husks free of volatile constituents to a gasification
temperature in the range of from 450.degree. to 550.degree. C. while feeding an
oxidizing agent thereto for transforming the fixed carbon into a gaseous phase prior
to heat treatment; and the third step of subsequently heating the thus obtained rice
husk ash to a heat treatment temperature in the range of from 700.degree. to
800.degree. C.
2. The method of claim 1, in which the husks are first brought to a separation
temperature of from 200.degree. to 350.degree. C. at a heating rate of from
10.degree. to 40.degree. C./min, from a feed temperature of less than 100.degree.
C., and are subsequently heated at the same rate and in the presence of the
oxidizing agent to the gasification temperature in the range of from 450.degree. to
550.degree.C., after which the resulting husk ash is heated at the same rate to the
treatment temperature between 700 to 800.degree. C.
3. The method of claim 2, in which the rate of heating is 25.degree. C./min.
4. The method of claim 1, in which the oxidizing agent supplied for oxidising the
fixed carbon in the second process step is combustion-supporting air having an air
coefficient of n = 4.0 to 6.0.
5. The method of claim 4, in which the oxidizing agent supplied is water-vapour.
6. The method of claim 1, in which HCl is added so as to inhibit the crystallization of

SiO.sub.2 in the gasification step.
7. The method of claim 1, in which husks are comminuted in order to increase the
bulk weight thereof before heat-treatment.
Description:
The invention relates to a method of producing low-carbon, white husks suitable for
use in the manufacture of building materials, more particularly refractory building
materials.
Rice is a basic food in Asia, more particularly India and Japan, and substantial
amounts are also cultivated in various countries in America and Europe. The present
2
world rice production of about 400 million tons per year will probably increase in the
future, owing to the great increase in population, paticularly in Asian countries. When
rice grains are husked, the husks make up about 14 to 35%, depending on the
variety of rice; since the husks have a low bulk weight of about 100 kg/m.sup.3,
they take up 560 to 1400 million m.sup.3.
Chemical analysis of rice husks shows the following typical composition (referred to
substance free from loss on ignition):
______________________________________
Water 9%
Protein 3.5%
Fats 0.5%
Cellulose 30 to 42%
Pentosan 14 to 18%
Mineral ash 14 to 30%
______________________________________
The composition of the mineral ash is normally within the following limits:
______________________________________
SiO.sub.2 92 to 97%
Al.sub.2 O.sub.3 0.75 to 3%
Fe.sub.2 O.sub.3 0.17 to 2%
CaO 0.36 to 3%
MgO 0.32 to 1.5%
______________________________________
In addition, up to 30% carbon is found, depending on the degree and nature of

combustion of the organic constituents before analysis.
In view of the composition of rice husks, a number of suggestions have been made
for large-scale use thereof in agriculture or industry. These suggestions relate to
direct use, with or without comminution; chemical decomposition of rice husks on an
industrial scale to obtain organic chemical basic materials; combustion for obtaining
heat, and use of the mineral ash residues. The possible applications include; the use
of rice husks as fodder, for loosening up the earth, for pressing fruit or the like, for
producing building materials such as slabs or the like, or use as fillers, packing
materials or oil-absorbing substances. In industrial technology, rice husks are a basic
material for obtaining furfurol for hydrolysis of wood, and for obtaining acetic acid
and other organic basis materials. Rice husks are also used as abrasives, heat-
transfer media for steam and electricity generation, and for producing ferrosilicon,
silicon carbide, silicon nitride, lignin and nitrogen-lignin compounds, sodium silicate,
silicon tetrachloride and the like.
More particularly, rice husk ash is used in the glass industry, the ceramics industry,
the cement industry and especially in the refractory-materials industry, since it has
the properties of a porous silicic-acid raw material. As already mentioned, about 92
to 97% of rice husk ash consists of SiO.sub.2 and, therefore, has a melting-point
above 1600.degree. C. It is, therefore, particularly suitable, as a silicic-acid carrier,
for use as a raw material for manufacturing heat-insulating, refractory and heat-
3
resistant building materials such as refractory, chemically bonded or burnt bricks and
materials, and for manufacturing light building materials bonded with hydrated
calcium silicate (tobermorite synthesis). The aforementioned materials have to be
produced from ashes which have a defined carbon content and also have a given
structure. In the case, for example, of rice husk ash suitable for tobermorite
synthesis, the silicic acid content must be in an "amorphous", vitreous, and therefore
very reactive, form. For refractory purposes, on the other hand, the silicic acid
should occur in crystalline form, for example as quartz, cristobalite or tridymite, so
as to have the required dimensional stability at high temperatures.
It has been found that refractory building materials or the like can be prepared only
from white rice-husk ash, that is ash which is substantially free from carbon or
contains only a small amount of carbon, since black rice-husk ash (that is ash
containing a high proportion of carbon) is water-repellent owing to the carbon
residue, so that the ash particles are insufficiently wetted with aqueous binder
solutions and it is more difficult to bond the bricks and obtain a mechanically strong
structure. The presence of carbon likewise interferes with tobermorite synthesis,
since it prevents, of at least adversely affects, the formation of tobermite. When
ceramic products are produced, an undefined carbon content may result in
undesirable reduction phenomena in the pots. A controlled carbon content and a
definite structure are also required in other applications of rice husk ash, for example
when used as fillers, filter materials or the like, since the colour of the ash is then
uniform.
It has been found that white, low-carbon rice husk ash is obtained when the husks
are charred or "roasted" in open piles. In countries where rice is grown, this process
is usually performed in the open air. The husks are ignited at a certain point and
then heat up, and smoulder from the centre outwards. This process, which produces
hardly any flames, lasts about 3 to 6 months. Aromatic vapours and gases are
produced, and give off a very unpleasant smell over a wide area. Furthermore,
particulars of ash having a high silicic-acid content are blown round the
neighbourhood and are liable to produce silicosis in men and animals. The burnt-out
heap of rice husks, consisting of ash, does not have any uniform colour, chemical
composition, crystal structure or degree of crystallisation, since "roasting" occurs
under uncontrolled conditions, so that the colour of a pile of ash varies between pink,
white, grey and black. It is difficult to separate the individual constituents, which
differ in chemical, mineralogical and physical respects, consequently ash of the
aforementioned kind does not satisfy the conditions which are particularly necessary
for use as a constituent of refractory building materials. Another point is that the
specific weight of "amorphic" and crystalline ash is non-uniform -- for example 2.12
for amorphous rice husk ash and 2.28 for crystalline ash containing cristobalite. The
quality of the finished building material, however, depends on a uniform crystal
structure, on both the crystal modification and the degree of crystallinity of the
SiO.sub.2 in the ash, since these factors have an effect particularly on the coefficient
of thermal expansion.
Owing to the high calorific value of rice husks (3430 to 3995 kcal/kg), the "roasting"
of rice husks in open piles occurs automatically, but the process is inefficient and
also, as already mentioned, takes about 3 to 6 months and can, therefore, not be
used on a large industrial scale for producing white rice husk ash (more particularly
because of the aforementioned pollution problem). It is particularly noteworthy that
the aforementioned process cannot yield ash having a uniform crystal structure and
a uniform low carbon content.
4
On the other hand, when the rice husks are burnt in industrial plants for obtaining
heat (for example to produce steam), the ash occurs in the form of black residues
having a high carbon content, usually between 10 and 25%. For the reasons given,
however, ash having a carbon content as high as this is unsuitable for many
applications, more particularly for the manufacture of refractory materials. In the
present case, the slowness of carbon to react is probably due to the fact that, after
the silicic acid has crystallised, the carbon is not sufficiently accessible for
combination with oxygen.
No success has to date been obtained in attempts to control the combustion of rice
husks so as to produce a low-carbon or carbon-free ash. On the other hand, it has
been shown that subsequent roasting of black-rice husk ash is uneconomic, since the
carbon is in very inert form. Table 4 hereinafter shows that no white ash is obtained
even at high temperatures such as 1000.degree. C. and even after 11/2 hours
treatment.
There is no known process, therefore, which operates under conditions at which the
organic constituents are converted into energy or separable decomposition products
and in which a low-carbon white ash is obtained for the manufacture of building
materials.
An object of the invention, therefore, is to provide a large-scale industrial method of

producing white, low-carbon rice husk ash, the process being efficient and economic
and adapted to produce homogeneous, white rice husk ash having a uniform low
carbon content and a well-defined SiO.sub.2 crystal modification and a homogeneous
degree of SiO.sub.2 crystallisation.
To this end, in the method of the present invention, volatile constituents are first
removed by heating the husks, in the absence of air, to a first, relatively low
temperature below the ignition point of the husks, after which the fixed carbon in the
husks is oxidised in the presence of a reagent by heating the husks to a second
temperature above the separation temperature but below the crystallisation
temperature of the SiO.sub.2 in the husks, after which the resulting husk ash is
heat-treated at a third temperature above the crystallisation temperature of the
SiO.sub.2, to produce a uniform SiO.sub.2 crystal structure. The husks are
preferably rice husks.
In a preferred embodiment of the method, the volatile constituents are separated at

a temperature in the range of from 200 to 450.degree. C., and the fixed carbon is
oxidised at a temperature between 450 and 700.degree. C. According to another
preferred feature, the rice husks are first brought to a separation temperature in the
range of from 200.degree. to 250.degree. C. at a heating rate of from 10.degree. to
40.degree. C./min, starting at a feed temperature of less than 100.degree. C., and
are subsequently heated at the same rate and in the presence of the reagent to an
oxidation temperature in the range of from 450.degree. to 550.degree. C., after
which the resulting rice husk ash is heated at the same rate to a treatment
temperature between 700 and 800.degree. C.
Preferably, the rate of heating up is 25.degree. C./min. According to another

embodiment, the reagent supplied for oxidising the fixed carbon in the second
process step is combustion-supporting air having an excess air coefficient of n = 4.0
to 6.0 that is an amount four to six times that required for a complete combustion or
5
reaction. Alternatively, the reagent supplied is water-vapour.
In other words, the inventive concept of the method of the invention is as follows:
The rice husks are ashed in a three-step process; in a first step, the husks are
separated, in the absence of air, from volatile constituents, after which the fixed
carbon is oxidised at a higher temperature, which is followed by heat-treatment at a
still higher temperature in order to adjust the degree of crystallisation and the
SiO.sub.2 crystal modification. The combustible gases produced during the
separation of volatile constituents and the gasification of the fixed carbon are
subsequently burnt; the resulting energy is sufficient for the entire process and
under particularly efficient conditions, can provide additional energy.
The method according to the invention can be used, under industrial conditions, to
manufacture white rice husk ash having a low carbon content and a defined
composition and structure, the separated organic constituents being volatilised and
used for heating. The heat obtained from the organic constituents of the husks can
be used for the ashing process itself and/or (as already mentioned) for other
purposes. Alternatively, of course, the organic thermal-decomposition products of
the husks can be further processed in known manner and synthesised to furfurol,
wood vinegar, methanol or the like; alternatively, of course, rice husks can be ashed
according to the invention after being treated in a known process step for obtaining
furfurol.
The method according to the invention, therefore, is adapted for efficient, large-scale
manufacture of white rice husk ash having a definite composition and structure, of
the kind which cannot be obtained by subsequent roasting of black ash from
conventional combustion processes, since such processes are insufficiently economic
owing to the additional energy and time required. The invention is based on the
surprising discovery that an optimum low carbon content is not obtained by burning
the rice husks at a high temperature; instead, a number of tests at between
100.degree. to 1000.degree. C. have yielded the unexpected result that optimum
white ash is obtained at temperatures between 450.degree. and 550.degree. C.,
whereas the ash obtained at lower or higher oxidation temperatures is normally
black or grey and unserviceable. This finding applies both to continuous heating and
to temperature shock treatment in a given temperature range.
According to another feature of the present invention, the husks are normally
comminuted before heat treatment, to increase the bulk weight. The resulting
increase in bulk weight (to about 0.5 t/m.sup.3) considerably increases the energy
yield and the throughput of the process according to the invention.
Other features and advantages of the invention will be clear from the claims and the
following description, in which the invention is illustrated by an example and by
experimental results.
EXAMPLE
Rice husks, untreated or pretreated to obtain furfurol, have the composition and
properties given in Table 1.
Table 1
______________________________________
Rice husks from
6
Rice husks Italy used in the
Designation from Italy furfurol process
______________________________________
Ash 14.4% 20.7%
Combustible constituents
85.6% 79.3%
Volatile constituents
69.7% 53.9%
Lower calorific value
3430 kcal/kg
3995 kcal/kg
Ignition point (air)
.about.250.degree. C
.about.250.degree. C
C 39.6% 43.0%
H 5.4% 4.5%
S traces --
N 0.32% 0.44%
O 40.28% 31.36%
______________________________________
Differential thermoanalysis (DTA) and differential thermogravimetry (DTG) in a

nitrogen atmosphere and in the presence of air showed that the decomposition
reactions proceed as shown in Table 2.
Table 2
______________________________________
Rice husks Rice husks
(.degree. C)
N.sub.2 atmosphere
no exclusion of air
______________________________________
100 100.degree. C endothermic reaction: decomposition of
pentosan and formation of volatile
constituents and tar
200 230-500.degree. C exothermic
reaction:
Decomposition of cellulose
and oxidation of
the free carbon
300 270.degree. exothermic reaction:
decomposition of
cellulose and formation of
volatile constituents (CO)
400 360.degree. C exothermic reaction
decomposition of lignin
and formation of volatile
constituents (CO,CH.sub.4)
500
600
700 700-800.degree. C exothermic
700-800.degree. C exothermic
7
reaction: reaction:
crystallisation of SiO.sub.2
crystallisation of SiO.sub.2
and fixed C residue
800 Black rice husk ash
White rice husk ash
______________________________________
The preceding Table 2 shows that the thermal separation of the volatile constituents
reaches a maximum at approximately 360.degree. C. and is substantially complete
at approximately 450.degree. C. In a nitrogen atmosphere, the fixed carbon content
remains in the ash, whereas in the presence of air it can be removed by oxidation
under optimum conditions at 500.degree. to 550.degree. C., that is precisely by the
method according to the invention.
Structural research on the silicic-acid content of the husks has shown that the acid is
mainly in the form of very imperfect cristobalite, apparently with mainly oxidative
bonding in the "amorphous" state. Depending on the temperature used, the
cristobalite either remains amorphous in X-rays or crystallises out. If mineralising
agents are not added, crystallisation begins at 700.degree. C., with marked vibration
of the ash. If mineralising agents are added, crystallisation begins at 300.degree. C.
Experiments have shown that alkali-metal halides (such as NaF, NaCl and KCl) are
particularly effective mineralising agents. It is sufficient, for example, to wet the
husks with 0.2 N aqueous NaCl solution. It has also been found that crystallisation of
the silicic acid can be delayed if the husks are wetted with HCl before thermal
decomposition. Very reactive white rice husk ash can be obtained in this manner at
700.degree. C. It has also been found that the removal of fixed carbon from the ash
can be accelerated by adding mineralising agents such as NaF, NaCl or KCl.
Systemmatic ashing tests on a semi-industrial scale in the presence of stagnant air

have shown that a white ash is obtained in the temperature range between
approximately 450.degree. and 550.degree. C., as shown in the following Table 3.
Table 3
______________________________________
Processing
temperature
Weight loss Colour of ash residue
______________________________________
300.degree. C
29.8% Black
400.degree. C
66.8% Grey
500.degree. C
77.1% White
600.degree. C
74.7% Grey
700.degree. C
69.4% Black
800.degree. C
73.5% Black
1000.degree. C
8
75.8% Black
______________________________________
Table 3: Loss of weight during thermal decomposition of rice husks, and
colour of ash during spontaneous heating to the temperature indicated.
Duration: 1 hour. Stagnant air.
Table 3 also shows that the organic constituents of the husks are not decomposed to
an adequate extent if the temperature is below 450.degree. to 550.degree. C. Above
550.degree. C., heating-up is spontaneous and the ash is unsuitable (black, carbon-
containing). If the temperature is increased far above 1000.degree. C. (this was also
tried experimentally), there is no improvement in the rate of decomposition and the
purity of the inorganic end product, compared with decomposition in the
aforementioned region of 450.degree. to 550.degree. C. Table 3 shows that the
greatest loss of weight occurs during spontaneous heating at approximately
500.degree. C. The end product is white, whereas the quality of the ash
progressively decreases above and below 500.degree. C.
With regard to the rate at which husks must be brought to the temperature of 450 to
550.degree. C. the optimum rate was found to be 25.degree. C./min, as shown from
Table 4 hereinafter:
Table 4
______________________________________
Processing temperature
Weight loss
Colour of ash residue
______________________________________
20 - 300.degree. C
37.1% Black
20 - 400.degree. C
72.1% Grey
20 - 500.degree. C
77.5% White
20 - 600.degree. C
76.9% White
20 - 700.degree. C
78.0% White
20 - 800.degree. C
76.1% White
20 - 1000.degree. C
78.6% White
______________________________________
Table 4: Loss of weight during continuous heating of rice husks to the
temperature indicated. 25.degree. C/Min. stagnant air.
Table 4 shows that white ash is obtained at 500.degree. C. onwards, after gradual
heating at 25.degree. C./min from room temperature. It has been shown that
10.degree. C./min and 40.degree. C./min can normally be regarded as the upper and
lower limit for the rate of heating at which ash having adequate "whiteness" (C.
<2%) can be obtained.
9
Table 5 hereinafter shows the progressive loss of weight at the optimum temperature
of 500.degree. C.:
Table 5
______________________________________
Time Weight loss Colour
______________________________________
0 min 0% gold-yellow
1 min 41.7% black
3 min 45.6% black
5 min 49.2% black
10 min 56.0% black
30 min 76.1% grey
60 min 78.8% white
______________________________________
Table 5: Weight loss during thermal decomposition of rice husks after
spontaneous heating to 500.degree. C, in dependence on time. Stagnant air
As Table 5 shows, 41.7% of combustible constituents have been removed from the
husks after 1 minute. After 10 to 30 minutes, all the volatile constituents have been
driven off. At the same time, the fixed carbon constituent begins to vaporise and is
substantially removed within 60 minutes.
Table 6 hereinafter shows the weight loss during subsequent oxidation of black rice
husk ash obtained by high-temperature combustion:
Table 6
______________________________________
Weight loss/min
Temperature
25 60 120 180 Colour
______________________________________
300.degree. C
2.4% 2.61% 2.6% 2.9% Black
400.degree. C
8.93% 8.98% 9.05% 9.06% Black
500.degree. C
24.26% 24.47% 24.68% 24.90% Grey
600.degree. C
24.60% 24.87% 24.95% 24.96% Grey
700.degree. C
24.00% 24.01% 24.05% 24.07% Grey
800.degree. C
24.41% 24.50% 24.55% 24.54% Grey
1000.degree. C
24.45% 24.83% 24.81% 24.90% Grey
______________________________________
Table 6: Weight loss during subsequent oxidation of black rice husk ash
obtained by high-temperature combustion.
Table 6 shows that the carbon in black ash can likewise be removed at 500.degree.
10
C. by oxidation. No advantage is gained by increasing the temperature or the time.
Our discussion of the results illustrated in Tables 3 to 6 shows that white rice husk
ash having the desired low carbon content (C. <2% or, at least, <3%) and a given
structure can be obtained if the volatile constituents are separated according to the
invention at temperatures preferably below 450.degree. C., whereas the fixed carbon
is vaporised, preferably between 450.degree. and 550.degree. C., by oxidation,
reaction with water gas or the like.
If required, additives such as NaCl should be added so as to accelerate the removal

of fixed carbon in gaseous form during the second process step. The distillation
products obtained by the method according to the invention can be synthesised in
known manner to obtain heat or organic raw materials. In order to obtain a white
ash containing silicic acid in a reactive state (tobermorite synthesis), the maximum
process temperature must remain below the crystallisation temperature of the
SiO.sub.2 in the rice husks, that is below 700.degree. C. In this case, crystallisation-
inhibiting admixtures such as HCl can be used if required.
A white ash in which the silicic acid has crystallised, as is particularly advantageous
in the use of rice husk ash for manufacturing refractory building materials, can be
obtained according to the invention by heat-treating the ash in the range preferably
from 700.degree. to 800.degree. C. after the organic constituents have been
separated. Crystallisation occurs at temperatures between 300.degree. and
800.degree. C., depending on whether mineralising agents such as NaCl, NaF or KCl
are added or absent.
The method according to the invention can take place in one or more steps in known
devices such as rotary furnaces, blast furnaces, retort furnaces and sintering plants.
The inventive concept which relates more particularly to the manufacture of rice
husk ash suitable for use in refractory materials, can of course be modified by the
skilled addessee from the form in which it has been described and is defined in the
claims.
Of course, the process according to the invention can also be applied to the
treatment of other suitable husks, for example, wheat, oats or barley.
The features of the invention disclosed in the preceding description and the following
claims can be used either singly or in any combinations for putting into practice the
various embodiments of the invention.
Title:
Method of producing active rice husk ash
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Abstract:
Active rice husk ash is produced by a method which includes placing a hollow
platform having many holes of a size too small for rice husk to enter on an enclosed
floor slab, erecting a chimney on the hollow platform in communication with the
interior of the hollow platform, forming a cone of rice husk around the chimney to
completely cover the hollow platform, igniting the rice husk at the small holes for
11
smolderingly incinerating the rice husk into carbonized rice husk, and allowing the
carbonized rice husk to self-burn into ash.
Inventors:
Sugita, Shuichi
Application Number:
111569
Filing Date:
08/25/1993
Publication Date:
07/19/1994
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Referenced by:
Export Citation:
Primary Class:
110/346
Other Classes:
106/406, 110/246, 110/347
International Classes:
F23G 005/00
Field of Search:
110/346, 347, 246, 226 106/406
3959007 May, 1976 Pitt 106/406.
4049464 Sep, 1977 Tutsek et al. 106/406.
4829107 May, 1989 Kindt et al. 106/406.
5010831 Apr, 1991 Halfhide 110/347.
Other References:
Proceedings Fourth International Conference, Istanbul, Turkey, May 1992: Fly Ash,
Silica Fume, Slag, and Natural Pozzolans in Concrete S. Sugita, et al. pp. 495-512
"Evaluation of Pozzolanic Activity of Rice Husk Ash".
Primary Examiner:
Favors, Edward G.
Attorney, Agent or Firm:
Oblon, Spivak, McClelland, Maier & Neustadt
Claims:
What is claimed is:
1. A method of producing active rice husk ash comprising the steps of placing a
hollow platform having many holes of a size too small for rice husk to enter on an
enclosed floor slab, erecting a chimney on the hollow platform in communication with
the interior of the hollow platform, forming a cone of rice husk around the chimney
to completely cover the hollow platform, igniting the rice husk at the small holes for
smolderingly incinerating the rice husk into carbonized rice husk, and allowing the
carbonized rice husk to self-burn into ash.
2. A method of producing active rice husk ash comprising the steps of connecting
downstream and upstream rotary kilns in tandem, heating the upstream rotary kiln
to a controlled temperature for carbonizing rice husk, heating the downstream rotary
12
kiln to a controlled temperature for burning rice husk into ash, supplying rice husk to
the upstream rotary kiln to be smolderingly incinerated into carbonized rice husk
therein, supplying the carbonized rice husk to the downstream rotary kiln to be
burned into ash therein, and discharging the resulting active rice husk ash from the
downstream rotary kiln.
3. A method of producing active rice husk ash according to claim 2, wherein the
upstream rotary kiln is heated to a temperature of 300.degree.-400.degree. C. and
the downstream rotary kiln is heated to a temperature of about 600.degree. C.
Description:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of producing active rice husk ash exhibiting a high
degree of amorphousness and suitable for use as a concrete aggregate in place of fly
ash, silica fume and the like.
2. Description of the Prior Art
In technology relating to rice husk and rice husk ash, the fundamental thinking has
conventionally been first to consider rice husk as a heat source and second to try to
find practical uses for the resulting rice husk ash. When rice husk is used a heat
source, it is necessary to blow air into the rice husk after it is lit so as to achieve the
highest combustion temperature possible. However, almost all of the rice husk ash
obtained by such high-temperature burning is crystalline, very low in chemical
activity and black in color. It therefore has few practical uses.
When air is blown into to the rice husk for burning it at high temperature, the
resulting rice husk ash progressively crystallizes, a fact that can be readily confirmed
from the X-ray diffraction pattern of the rice husk ash. The electrical conductivity of
a saturated calcium hydroxide solution of the rice husk ash is very low, generally
measuring around 0.3 mS/cm. Such rice husk ash cannot be expected to produce a
significant effect when used as, for example, a pozzolan for concrete.
To be of high practical utility, moreover, a rice husk ash should preferably exhibit
high chemical activity. It should also not be black. Since no method is available for
low-cost industrial production of rice husk ash exhibiting high activity, there is a
need for developing one.
At the Fourth CANMET-ACI International Conference on Fly Ash, Silica Fume, Slag
and Natural Pozzolans in Concrete held in Istanbul, Turkey, between May 3 and May
8, 1992, the inventor on May 8 announced a method of using an ordinary muffle
furnace as an electric furnace, charging 800 g of rice husk directly into the furnace,
raising the temperature of the furnace from normal room temperature to
280.degree. C. and maintaining it at this temperature for 1.5 hr, raising the
temperature of the furnace to 350.degree. C. and maintaining it at this temperature
for 1.5 hr, raising the temperature of the furnace to between 400.degree. C. and
800.degree. C. and maintaining it at this temperature for 2 hr to conduct
incineration, and removing rice husk ash from the furnace 5 hr later. Differently from
rice husk ash obtained by directly igniting rice husk and burning it in a short time,
the rice husk ash obtained by this method exhibited excellent chemical activity and
13
was white in color. Since the method comprises two steps, the first for carbonization
and the second for incineration, it will be referred to as the two-stage incineration
method.
The object of the present invention is to provide a method for efficient production of
white rice husk ash exhibiting chemical activity which is based on this two-stage
incineration method.
SUMMARY OF THE INVENTION
In the batch method for producing active rice husk ash according to one aspect of
this invention, a hollow platform having many holes of a size too small for rice husk
to enter is placed on an enclosed floor slab, a chimney is erected on the hollow
platform in communication with the interior of the hollow platform, a cone of rice
husk is formed around the chimney to completely cover the hollow platform, the rice
husk at the small holes is ignited for smolderingly incinerating the rice husk into
carbonized rice husk, and the carbonized rice husk is allowed to self-burn into ash.
In the continuous method for producing active rice husk ash according to another
aspect of this invention, downstream and upstream rotary kilns are connected in
tandem, heating of the upstream rotary kiln is controlled to a temperature for
carbonizing rice husk, heating of the downstream rotary kiln is controlled to a
temperature for burning rice husk into ash, rice husk is supplied to the upstream
rotary kiln to be smolderingly incinerated into carbonized rice husk therein, the
carbonized rice husk is supplied to the downstream rotary kiln to be burned into ash
therein, and the resulting active rice husk ash is discharged from the downstream
rotary kiln.
As will be understood from the foregoing, since the present invention first carbonizes
rice husk by burning it in an incineration furnace without flaming and then burns the
carbonized rice husk into ash, it enables easy production of white rice husk ash
exhibiting excellent chemical activity.
The above and other objects and features of the invention will be better understood
from the following description made with respect to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is sectional view of an embodiment of an apparatus for conducting the batch

method of producing active rice husk according to the present invention.
FIG. 2 is a perspective view of the apparatus of FIG. 1.
FIG. 3 is an explanatory view of an embodiment of an apparatus for conducting the

continuous method of producing active rice husk according to the present invention.
FIGS. 4(a) and 4(b) are graphs showing how the compression strength of concrete
incorporating rice husk ash produced by the continuous production method of the
present invention varies with the rice husk ash (RHA) content.
FIG. 5 is a graph showing how the compression strength of concrete incorporating

rice husk ash produced by the batch production method of the present invention
varies with the RHA content.
14
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 are explanatory views of a batch production apparatus for carrying out
the method of producing active rice husk according to the present invention and FIG.
3 is an explanatory view of an apparatus for continuously carrying out the method.
In FIG. 1, reference numeral 10 denotes a concrete floor slab on which rice husk is
stacked for burning. The floor slab 10 is enclosed on three sides by a three-walled
enclosure 11 and the remaining side is provided with a vertically sliding shutter 12.
The floor slab 10 is supported on a four-sided lower enclosure 13 that is provided on
the side of the shutter 12 with an entrance 14 for the apparatus operator. The lower
enclosure 13 is for defining a space 13' for setting fire to the rice husk. The space 13'
is about 1 meter high.
An approximately 50-cm opening 15 is formed through the floor slab 10 to reach the
side of the space 13'. A hollow platform 16 measuring 20-30 cm in height and
slightly larger than the opening 15 in diameter is placed on the perimeter of the
opening 15 and made unmovable. The surface of the hollow platform 16 is formed
with many holes 17 measuring a few millimeters in diameter, a size too small for rice
husk to enter.
A hole measuring about 12-15 cm in diameter is formed in the upper wall of the
hollow platform 16 and a chimney 18 of a diameter slightly larger than the diameter
of the hole is erected on the perimeter of the hole. The apparatus is installed at a
step in the ground so that the ground surface GL.sub.1 at the upper level of the step
can be used by a dump truck or the like for dumping rice husk onto the floor slab 10
and the ground surface GL.sub.2 at the lower level of the step can be used by a tank
truck or the like for loading the product rice husk ash after the shutter 12 has been
opened.
When rice husk is to be burned, rice husk is dumped onto the floor slab 10 enclosed
by the enclosure 11 and the shutter 12 in such manner as to completely cover the
hollow platform 16 and form a conical pile 19 around the chimney 18. When the size
of the batch of rice husk to be burned is 500 kg, the angle of repose of the pile 19 is
about 35.degree. and the height of the pile is about 1.5 m, so that the floor slab 10
can measure about 3.5 m square and the enclosure 11 and the shutter 12 can be
about 1.0 m high.
When the pile 19 is to be ignited, the operator enters the space 13' through the
entrance 14 and sets fire to the rice husk at the holes 17 in the hollow platform 16
by inserting burning paper, cloth or the like into the opening 15 at the center of the
floor slab.
Once the rice husk has been ignited, smoke and heat of combustion pass through
the holes 17 in the hollow platform 16 into the interior of the hollow platform 16 and
then rise to the exterior through the chimney 18, while air passes from the exterior
through the pile 19 and into the interior of the hollow platform 16, as indicated by
the arrows, whereafter it rises through the chimney 18 and is dispersed in the
atmosphere together with the smoke. Flaming of the rice husk during the
combustion is prevented by the smoke passing through the chimney. More
specifically, since the rice husk is smolderingly incinerated at a temperature of about
370.degree.-380.degree. C., namely at a temperature lower than its fire point of
15
410.degree. C., it is carbonized, i.e., becomes carbonized rice husk. When left as it
is, the carbonized rice husk then self-burns at a temperature of about 700.degree.-
750.degree. C. to become an ash, namely the white active rice husk ash which is the
product aimed at by the method of this invention. When necessary, the rice husk ash
can be comminuted with a ball mill or the like.
A 500 kg batch of rice husk requires about 24 hr to carbonize and about 48 hours to
burn into ash following carbonization, and yields about 100 kg of active rice husk
ash. These processing times can be regulated to some degree by varying the
diameter and height of the chimney.
The aforesaid production method can be conducted without need for any complicated
equipment and does not require the supply of electricity, gas or any other source of
combustion heat other than that for igniting the rice husk at the start. The
combustion of the rice husk proceeds solely by flameless self-burning and
carbonization is achieved through the process of smoldering incineration.
The method thus enjoys the advantages of not requiring any heat source other than
that for ignition and of enabling high volume production, notwithstanding that the
burning may be somewhat uneven. Moreover, the method enables production of
highly amorphous active rice husk ash exhibiting a difference in electrical
conductivity of 2-3 mS/cm and a SiO.sub.2 content of 90-95%.
FIG. 3 shows an apparatus for continuously producing active rice husk ash which
comprises an upstream rotary kiln 20 and a downstream rotary kiln 30 connected in
tandem via a material supply hopper 31. A burner, electric heater or other heat
source (not shown) is controlled for heating rice husk in the upstream rotary kiln 20
to 300.degree.-400.degree. C. and for heating rice husk in the downstream rotary
kiln 30 to about 600.degree. C. The length of each rotary kiln is, for example, 1.5 m.
The rice husk conveyance speed in the rotary kilns is adjusted so that rice husk
supplied to a material supply hopper 22 of the upstream rotary kiln 20 is discharged
as rice husk ash from a product discharge port 32 of the downstream rotary kiln 30
in about 1 hr. The waste heat from the downstream rotary kiln 30 is preferably used
to preheat the rice husk in the material supply hopper 22 of the upstream rotary kiln
20. If convenient, the material supply hopper 31 can be removed from the product
discharge port 21 of the upstream rotary kiln 20 and the two kilns be connected
directly to each other. When the illustrated arrangement is employed, i.e., when the
upstream product discharge port 21 is connected with the downstream material
supply hopper 31, it is preferable to insulate the product discharge port 21 and the
hopper 31.
During operation of the apparatus, rice husk supplied into the upstream rotary kiln
20 from the material supply hopper 22 is converted into carbonized rice husk as it is
tumbled and conveyed through the upstream rotary kiln 20. The carbonized rice
husk discharged from the upstream rotary kiln 20 through the product discharge port
21 and into the material supply hopper 31 is then supplied to the downstream rotary
kiln 30. It is thereafter incinerated as it is tumbled and conveyed through the
downstream rotary kiln 30 to be discharged from the product discharge port 32 of
the downstream rotary kiln 30 as highly active rice husk ash of very high whiteness,
a SiO.sub.2 content of 92-95% and a difference in electrical conductivity of 6-6.5
mS/cm. When necessary, the rice husk ash can be comminuted with a ball mill or the
like. For every 100 weight units of rice husk supplied to the upstream rotary kiln 20,
45 weight units of carbonized rice husk is obtained at the product discharge port 21.
16
This continuous production method employing two rotary kilns enables the
temperature control for production of carbonized rice husk in the upstream rotary
kiln 20 and the temperature control for burning the carbonized rice husk into ash in
the downstream rotary kiln 30 to be separately controlled for optimum effect. This
makes it possible to continuously produce active rice husk ash free of uneven
burning and having a high degree of amorphousness, in a very short time. Although
the method requires a heat source, it has the advantages of enabling recovery and
effective utilization of the heat of combustion, being capable of continuous 24-hour
operation, being highly efficient, and enabling large volume production of high
quality rice ash.
As will be understood from the foregoing, in either of its aspects the method
according to the present invention enables ready production of highly active rice
husk ash exhibiting a high degree of amorphousness.
Examples of using rice husk ash produced by the method of this invention as an
aggregate in concrete will now be given.
The graphs of FIGS. 4(a) and 4(b) relate to concretes incorporating rice husk ash
produced using rotary kilns and show how the ratio of the compression strength of
concrete containing rice husk ash to the compression strength of plain concrete (not
containing rice husk ash) increases with increasing rice husk ash content. FIG. 4(a)
shows the compressive strengths of concretes aged 7 days (about 1 week), curve a
being for concretes having a water binder ratio of 45%, curve b for concretes having
a water binder ratio of 55%, and curve c for concretes having a water binder ratio of
65%. FIG. 4(b) shows the compressive strengths of concretes aged 91 days (just
over three months), curve d being for concretes having a water binder ratio of 45%,
curve e for concretes having a water binder ratio of 55%, and curve f for concretes
having a water binder ratio of 65%. In each of these graphs, the vertical axis
represents compressive strength increase rate (i.e., 0% on the vertical axis
corresponds to the strength of plain concrete) and the horizontal axis represents rice
husk ash content (weight ratio of rice husk ash to cement).
FIG. 4(a) shows that the rate of increase in compressive strength with increasing rice
husk ash content was approximately the same for all of the 7-day-old concretes
regardless of water binder ratio. Particularly noteworthy is that the concretes having
a 15% rice husk ash content exhibited about a 40% increase in compressive
strength.
FIG. 4(b) shows that while 91-day-old concretes exhibited a pronounced increase in
compressive strength with increasing rice husk ash content, the increase for the
concretes having a water binder ratio of 45% was smaller than that for the concretes
with water binder ratios of 55% and 65%. This tendency is observed not only for rice
husk ash but also for other pozzolan materials. The concretes with water binder
ratios of 55% and 65% exhibited an approximately 30% increase in strength at a
rice husk content of 15%, indicating that the rice husk ash exhibited very high
chemical activity.
The compressive strength continues to rise when the rice husk ash content is
increased even further.
The graph of FIG. 5 shows the compressive strengths of 28-day-old concretes
17
containing rice husk ash produced by the batch method and having a water binder
ratio of 55%. Concretes with rice husk ash contents ranging between 0% and 40%
were tested. The compressive strength of the concretes increased up to a rice husk
ash content of 20%, at which it was 50% higher than that of plain concrete, and
then stayed substantially the same between 20% and 30%. The concrete with a 40%
rice husk ash content achieved only a 25% increase in compressive strength. The
concretes with the highest compressive strength were those with a rice husk ash
content in the vicinity of 25%. They exhibited more than a 55% increase in
compressive strength.
It is clear from the foregoing that when rice husk ash produced according to the
method of the present invention is used as an aggregate in concrete it imparts the
concrete with a pronounced increase in compressive strength.
Title:
Rice hull ash concrete admixture
Link to this page:
Abstract:
A cement admixture and cement composition containing said admixture comprising
finely ground rice hull ash formed by slurry grinding of said ash to a volume medium
particle diameter or up to 4 micrometers.
Inventors:
Kindt, Lawrence J. (Woodbine, MD, US)
Gartner, Ellis M. (Silver Spring, MD, US)
Application Number:
159978
Filing Date:
02/24/1988
Publication Date:
05/09/1989
View Patent Images:
Account (Free!)
Referenced by:
Export Citation:
Assignee:
W. R. Grace & Co.-Conn. (New York, NY)
Primary Class:
524/3
Other Classes:
106/123.11, 106/406, 106/709, 524/15, 524/492
Field of Search:
524/15, 3, 492 106/98, 288 B, 123.1
4105459 Aug, 1978 Mehta 106/98.
4623682 Nov, 1986 Nicholson et al. 524/3.
Other References:
18
Rice: Chemistry and Technology, B. O. Juliano.
Properties of Blended Cements Made from Rice Husk Ash, by P. K. Mehta, J. Am.
Concr. Inst. 74(9):440-442, (1977).
Cement Replacement Materials, Rice Husk Ash, Chapter 6, by D. J. Cook, Surrey
Press (1986).
Use of Rice Husk Ash in Concrete, by M. N. Al-Khalaf and Hana A. Yousif, Int. J.
Cement Comp. and Lightweight Concrete, 6 241-248 (1984).
Primary Examiner:
Jacobs, Lewis T.
Attorney, Agent or Firm:
Troffkin; Howard J.
Claims:
What is claimed:
1. A product comprising rice hull ash having ultra-high fineness particle size of a
volume-median particle diameter measured by laser-light scattering of up to about 4
micrometers, a BET specific surface area of at least 20 m.sup.1 /g, a silica content of
at least 80% by weight, a carbon content of less than 10% by weight and being
substantially amorphous as shown by x-ray diffractometry, said product being in
combination with from about 0.05 to about 10 weight percent of a cement water
reducing agent.
2. The product of claim 1 wherein the rice hull ash is RHA-PF product.
3. The product of claim 1 wherein the rice hull ash is RHA-LT product.
4. The product of claim 1 wherein the rice hull ash product has a silica content of at
least 85% by weight.
5. The product of claim 2 wherein the particle size is up to about 3 micrometers.
6. The product of claim 3 wherein the particle size is less than 3 micrometers.
7. An aqueous suspension wherein the water reducing agent of the product of claim
1, 2, 3, 4, 5 or 6 is present in from about 0.01 to 10 percent by weight of the
suspension and is selected from at least one of naphthalene-sulfonate formaldehyde
condensates, melamine sulfonate formaldehyde condensates, lignin sulfonates, alkali
or alkaline earth metal polyacrylates or copolymers thereof and said rice hull ash is
present in from about 20 to 80 percent by weight of the suspension.
8. The aqueous suspension of claim 7 wherein the water reducing agent is present in
from 0.1 to 5 percent by weight based on the total weight of the suspension.
9. The aqueous suspension of claim 7 wherein the rice hull ash product is present in
from 40 to 60 percent by weight based on the total weight of the suspension.
10. An aqueous suspension comprising from about 0.01 to about 10 percent by

weight of a water-reducing agent selected from at least one of naphthalene-sulfonate
formaldehyde condensates, melamine sulfonate formaldehyde condensates, lignin
sulfonates, alkali or alkaline earth metal polyacrylates or copolymers thereof; from
about 40 to 60 weight percent of rice hull ash product composed of RHA-PF having a
volume-median particle size of up to about 4 micrometers measured by laser-light
scattering, a BET specific surface area of at least 20 m.sup.2 /g, a silica content of at
19
least 80% by weight, a carbon content of less than 10% by weight and being
substantially amorphous as shown by x-ray diffractometry; and up to about 15 wt.
percent of calcium nitrite.
11. The suspension of claim 9 wherein the rice hull ash product has a particle size of
up to about 3 micrometers.
12. The suspension of claim 9 wherein the water-reducing agent is a mixture of

naphthalene sulfonate formaldehyde and a polyacrylate.
13. An hydraulic cement admixture comprising an aqueous suspension of claim 7.
17. An hydraulic cement composition comprising a portland cement, sand, aggregate

and water in proportions to provide a settable product, the improvement comprising
the addition of from about 0.1 to 30 percent by weight solids of the admixture of
claim 13 based on the dry weight of the portland cement.

the addition of from about 0.1 to 30 percent by weight solids of the admixture of
claim 14 based on the dry weight of the portland cement.

the addition of from about 0.1 to 30 percent by weight of the admixture of claim 15
based on the dry weight of the portland cement.

the addition of from about 0.1 to 30 percent by weight of the admixture of claim 16
based on the dry weight of the portland cement.
Description:
BACKGROUND OF THE INVENTION
The present invention relates to a novel rice hull ash of ultra high fineness and other
particular properties, as described fully hereinbelow, aqueous slurries of said ash and
to their use as an admixture for hydraulic cement to enhance the properties of
hydraulic cement compositions and the resultant set products made therewith.
Rice hull materials, such as the shell, hull or husk of the rice grain, are generally a
discarded waste product from rice production. The rice hull materials are viewed as
having little, if any, commercial value in their raw material form. It is known,
however, that rice hull materials typically contain a substantial amount, typically
about 16 to 20 percent, of silica (SiO.sub.2) and when burned yield an ash which is
rich in amorphous silica. This ash, referred to herein and in the appended claims, as
"rice hull ash" or "RHA", has been used as a pozzolanic additive in hydraulic cement
compositions. The RHA is viewed as a filler material capable of replacing or extending
20
the more expensive ingredients of the composition, such as portland cement and the
like. (See U.S. Pat. No. 4,105,459 to P. K. Mehta.) The RHA material has also been
proposed as a filler or extender in other applications, such as in elastomeric and
plastimeric compositions (see U.S. Pat. No. 3,951,907 to P. K. Mehta). Its use in
these general manners have value in countries where rice is a major crop and where
the other components which are replaced or extended are expensive and/or not
readily available.
The rice hull material is commonly converted into RHA by uncontrolled combustion
methods in which the material is used as the fuel source. More recently, U.S. Pat.
No. 3,959,007 disclosed a process in which a higher amount of energy is obtained
when burning rice hull material under controlled combustion while still obtaining a
RHA useful as a cement pozzolan or as an extender in other applications. The ash
obtained from conventional modes of combustion may be further processed by dry
grinding the ash to a powder form. The resultant ground material is a fluffy powder
of low bulk density having a BET surface area of about 10 sq. m./g. or greater and,
typically, a Blaine specific surface area of lower than 1 sq.m./gm. (The higher the
Blaine value the smaller the particle.) Although the BET specific surface area of RHA
preparations increases as the combustion temperature is reduced, and can be in
excess of 200 sq.m./g., the Blaine specific surface areas of RHA's are usually much
lower than this, typically less than 1 sq.m./g. This difference is because most of the
specific surface measured by the BET technique is internal to the particle while the
internal surfaces of a particle are not measured by the Blaine technique. The Blaine
specific surface area measurements are greatly affected by particle size changes and
are more indicative of particle size. Thus, the RHA material presently obtained and
used is a somewhat coarse particle, having a low bulk density which makes the RHA
hard to handle and deliver in desired amounts into a mix.
In the case where RHA is viewed predominantly as an extender-filler, the particle

size of the RHA is not deemed to be critical as long as it is not so large as to disrupt
the matrix to which it is added. In the case of its use as a pozzolan in cement
compositions, it is known that small increases in the strength of the resultant
hardened cement composition can be achieved by the use of smaller particle size
RHA. However, this relationship tends to plateau as the particle size reaches a Blaine
surface area of 1 to 1.5 sq. m/g. Therefore, there has been no incentive to attempt
to develop a means to further reduce the RHA particle size and achieve a resultant
product.
In summary, rice hull ash (RHA) is generally of high silica content (at least about
85% SiO.sub.2), but its usefulness as an additive in hydraulic cement mixes has
heretofore been limited by the difficulty in obtaining it and handling it in a controlled,
convenient and efficient manner. It has been demonstrated that the pozzolanic
reactivity of RHA may be enhanced by burning the rice hulls at relatively low
temperatures in specially-designed furnaces (U.S. Pat. No. 3,959,007). The strength
of hardened hydraulic cements can be enhanced to small extents by using smaller
particle RHA but this relationship plateaus. Because of this as well as the mechanical
restrictions in dry grinding and the required need of specialized combustion
techniques, there has been no desire to produce a RHA of very high Blaine value.
Additional barriers to the need to form and use a high-Blaine RHA are the difficulty
believed associated with handling the ultrafine dry powder, its presumed poor flow
properties and with its dust hazards.
SUMMARY
21
The present invention is directed to RHA of ultra high fineness as more specifically
defined hereinbelow. The present invention is further directed to cement admixture
compositions containing said RHA of this invention which provides for a means of
easily handling and metering the ultra high fineness RHA and to improved cement
compositions containing said admixture.
The present invention has been found to be an effective means of causing the
resultant cement structures to exhibit substantial inhibition to permeation of
materials which adversely affect the durability of the resultant structure, such as
chloride ions and the like and thus form a structure of high strength and low
corrosion potential.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a rice hull ash product of ultra fine particle size, to
stable and easily handle aqueous suspensions containing said rice hull ash and to
hydraulic cement compositions to which the present rice hull ash has been added.
In order to provide a clear description of the present invention, the following terms
are used in this description and in the appended claims with the meaning given
below.
The term "hydraulic cement" refers to a dry powder which sets and hardens to a
solid mass when mixed with water. Among the cements included under this definition
are plaster of paris, high alumina cements, lime-pozzolan cements, blastfurnace slag
cements, portland cements, and blended cements based principally on portland
cement. The term "hydraulic cement composition" is taken to refer to a mixture of an
hydraulic cement with water, and also, if desired, with aggregate and admixtures.
The term "aggregate" refers to an essentially chemically inert filler, such as a sand or
gravel or crushed rock, whereas the term "admixture" refers to materials which when
added to a cement composition in small amounts imparts a large influence on the
physical and/or chemical properties of the uncured composition and/or upon the
cured composition. Hydraulic cement compositions include a cement paste when
there is no aggregate, a mortar when the aggregate is a sand, and a concrete when
the aggregate also contains coarse particles such as gravel or crushed rock.
A "pozzolan" is an inorganic material which consists principally of chemically reactive

compounds of silicon and aluminum in their oxide forms, and which is capable of
reacting with lime (calcium hydroxide, Ca(OH).sub.2), to form a hardened mass of
calcium silicate hydrates and calcium aluminate hydrates. A common application is to
use pozzolans as additives to enhance the economy or modify the properties of
mixed based primarily on portland cements. In such cases, the pozzolans react with
the lime evolved by the normal reaction between cement and water. In some cases
the pozzolan is interground or interblended with the dry solids during the
manufacture of the portland cement, while in other cases, pozzolans are added as an
admixture during the preparation of portland cement compositions, such as
concretes.
The terms "rice hull ash" and "RHA" refer to the ash obtained from the combustion of
rice hull materials, that is from the shell, hull and/or husk of the rice grain. Rice hull
material is generally viewed as a waste product of little or no commercial value
("Rice: Chemistry and Technology" 2nd Ed. Chapter 19, by B. O. Juliano, 1985).
22
The terms "rice hull ash product," "RHA product," "RHA-LT product" and "RHA-PF
product" refer to the product of the present invention, as fully described below,
which is formed from conventional RHA. The present invention is directed to a new
rice hull ash product, aqueous suspensions of this product and to its use as a
hydraulic cement admixture. The rice hull ash used to form the RHA product of the
present invention must be an amorphous silica formed by the combustion of rice
hull. The combustion can be accomplished by various modes, such as by the
controlled slow combustion of rice hulls at low to moderate temperatures, preferably
below 800.degree. C. and more commonly between about 500.degree. and
600.degree. C. Such a combustion process is described in U.S. Pat. No. 3,959,007,
the teaching of which is incorporated herein by reference, or by other known low
temperature processes. The rice hull ash produced by such low temperature modes
of combustion is herein referred to as "RHA-LT." When the combustion period is
maintained for an extended period the RHA-LT may be light gray or off-white in color
while short combustion periods tend to yield a darker gray to black material. Material
formed under such low temperature combustion has high internal porosity as shown
by its high BET specific surface area values which are typically in the range of about
20 to 200, more typically about 100 to 200 sq.m./g. and greater. Higher values are
obtained by the lower combustion temperature. Alternately, the rice hull ash useful
in forming the present RHA product can be formed by combustion of rice hull
material in a conventional pulverized fuel burner. The rice hulls, chopped to an
average particle size of from about 0.1 to about 1 mm, are blown into a flame along
with the combustion air. The combustion, although reaching temperatures well in
excess of 1000.degree. C., occurs over a very short time period. Materials formed in
this manner have BET surface area values of about 20 to 50 sq.m./g. and are
identified herein as "RHA-PF." The use of a pulverized fuel burner as the combustion
means is a simple method of manufacturing the needed and useful RHA, because the
technology for pulverized fuel combustion is well established and is also well suited
to the use of the combustion heat for steam or electricity generation.
The RHA found useful in forming the RHA-product of the present invention must have
a silica (SiO.sub.2) content of at least 80% by weight and preferably at least 85%
and most preferably at least 90% by weight. It should consist primarily of
amorphous silica as determined by x-ray diffractometry. The formation of RHA under
high temperature for extended periods results in crystallization of the silica dto
cristobalite or quartz. Such RHA is not useful. The carbon content should be less than
10% and more preferably less than 6% by weight. Therefore, an amorphous silica
RHA having at least 80% by wt. SiO.sub.2 and less than 10% by wt. carbon is
suitable but the preferred RHA would contain at least 85% by wt. SiO.sub.2 and less
than 6% by wt. carbon. The BET specific surface area should be at least 20 sq.m./g.
and normally will range from 20 sq.m./g. to 200 sq.m./g. Higher values are useful.
The particle size of RHA which is ground by conventional means of dry processes
normally has a Blaine specific surface area of less than 1 sq.m/gm. with the value
rising as high as about 1.5 sq.m./g. By excessive dry grinding a Blaine specific
surface area value of about 2 sq.m./g. may be achievable. Values in excess of about
2 sq. m./g. are not achievable by conventional means of dry grinding. The Blaine
specific surface areas of RHA's are usually much lower than the BET values for the
same material because most of the specific surface measured by the BET technique
is internal to the particle, in the form of fine pores, which are not measured by the
Blaine technique. Thus, the BET specific surface area is not significantly increased by
further grinding RHA preparations, whereas the Blaine specific surface area is very
23
amenable to increase by grinding up to the limitations discussed above.
The RHA-product of the present invention is required to have all of the physical
characteristics described above for RHA, that is the characteristics of morphology,
carbon and silica content, and BET surface area except that its particle size must be
significantly smaller than previously taught. It has been unexpectedly found that by
processing such RHA by the manner described below one can achieve a product of
ultra high fineness, that is the particle diameter is ultra small. The ultra-small
dimensions of the particles of the present RHA-product is of values that can not be
accurately measured by conventional Blaine surface area measurements. An
appropriate means of measuring the present ultra-fine particle size is by a laser-light
scattering analyzer which gives a statistical analysis of the volume-median particle
diameter (D.sub.50). The present RHA-product must have a volume-median particle
diameter (D.sub.50) of up to 4 micrometers, preferably up to about 3 micrometers
and most preferably up to about 2.5 micrometers. Because of the systematic
differences among the various analytical techniques for determining size with the
presently required ultra-high fineness product, the laser-light scattering analysis is
the basis used here. Specifically, a Leeds and Northrup "Microtrac" laser-light
scattering analyzer or its equivalent was used. The Blaine air permeability method of
specific surface area determination, which is commonly used in the measurement of
the fineness of cements and even of microsilicas, is not recommended herein
because it is an imprecise means of analyzing materials of ultra-small particle size
especially if the particles are also very non-spherical and internally porous, as is the
case with RHA. For example, a sample of presently formed RHA, which was
determined to have a D.sub.50 of 3.7 micrometers by a laser-light scattering
analyzer, was also found to have a Blaine air permeability specific surface area of 4.5
sq.m./g. Using this Blaine value and assuming that all of the particles were
uniformly-sized spheres, a calculated diameter of only about 0.6 micrometers would
be obtained. Knowing that the laser technique directly measures particle diameter,
one readily observes that the Blaine technique is inappropriate for the present ultra
fine product.
The process required to achieve the RHA-product of ultra-high fineness is to grind

RHA by wet grinding technique. The liquid medium should be water. The water
should contain or have introduced therein at least one low or high range water
reducing agent used in cement formulations to achieve a resultant stable slurry. The
wet grinding can be accomplished by various means, such as a ball mill, tube mill,
sand mill, or any type of stirred or vibrated media mill, operated either in batch or
continuous mode. Use of stirred media mills, such as an Attritor Mill has been found
to be particularly effective for ultrafine grinding of RHA to produce slurries of the
subject invention. The wet grinding has been found to achieve the desired ultra fine
particle sizes and also provides low operating costs, reduced dust emissions and
reduced noise levels. Dry grinding does not achieve the present RHA-product of
ultra-high fineness.
Although the resultant RHA-product may be dried and used in its powder form, it is
preferable to maintain and use the RHA-product in aqueous suspension. The
suspension shall contain the RHA-product in from about 20 to 80%, preferably from
about 30 to 70% and most preferably from about 40 to 60% by weight. The RHA-
product suspension must also contain small amounts of conventional water reducing
agent cement admixture material, such as naphthalene sulfonate formaldehyde
condensate, melamine sulfonate formaldehyde condensate, lignin sulfonates,
polyacrylic acid and its alkali and alkaline earth metal salts as well as copolymers of
24
the polyacrylate and the like. The term "polyacrylate" shall include polymers of
acrylic acid, methacrylic acid as well as C.sub.1 -C.sub.3 alkyl esters thereof which
are water soluble by having a sufficient amount of metal salt therein. The copolymer
may be mixtures of the polyacrylate monomeric units indicated above or with other
olefinic monomeric units including ethylene, hydroxyalkyl acrylates and the like. The
water reducing agent must be present in at least 0.01% by weight of solids
contained in the suspension, with normal range of from 0.01 to 10%, preferably from
0.1 to 5%. The most preferred suspension contains a mixture of a naphthalene
sulfonate formaldehyde condensate and a polyacrylate. It has been unexpectedly
found that the present RHA-product provides a stable, non-setting and non-settling
suspension even when used in high concentrations, such as greater than 40% by
weight.
The solid RHA-product of the present invention must contain substantially uniformly
mixed therewith a water reducing agent, as described above, in amounts given
above for the solid, powder RHA-product composition.
In addition, other conventional cement admixture materials may be combined in the

RHA-product suspension without causing detrimental effects such as solidifying,
gelling or settling of the suspension. Other types of admixtures which have been
found to be desirable to be incorporated into the present RHA-product suspension
includes viscosifiers, such as polyhydroxyalkyl celluloses, polyvinyl alcohol,
polyethylene oxide and the like; wetting agents such as vinsol resins, sulfonated
organic compounds, polyethoxylated alkyl phenols and the like; and set retarders
such as sugar derivatives, polycarboxylic acids, hydroxycarboxylic acids, phosphates,
phosphonic acids, borates and the like; accelerators, such as chlorides, sulfates,
formates and nitrates of alkali and alkaline earth metals, especially of calcium,
sodium or potassium. Another class of accelerator which is very suitable for this
application is the hydroxyalkylated amines, such as triethanolamine, and corrosion
inhibitors such as alkali and alkaline earth metal nitrites.
The subject slurry can be used directly as a hydraulic cement admixture. The slurry
of RHA-product is stable and storable and is a means of readily transporting and
metering the desired amount of RHA-product without incurring the handling and
health (breathing) hazards associated with dry powders of rice hull ash and other
conventional pozzolans. In addition, because the present RHA-product is capable of
being contained in the slurry in high concentrations, the water content of the slurry
does not have an adverse effect on the water to cement ratio and on the physical
properties of the resultant cement composition.
Another embodiment of the present invention relates to a particularly useful and

unexpected observation that stable and pourable suspensions can be formed of a
combination of highly desired materials. Specifically, when the subject RHA-product
suspension, as described above, is formed from RHA described above as RHA-PF,
one can include into the suspension high concentrations, such as up to about 10% by
weight, and even up to about 15% by weight of the total suspension, of calcium
nitrite. Calcium nitrite is a known agent which effectively inhibits corrosion of metal
pieces (such as rebars and the like) contained in cement compositions when used in
concentrations ranging from at least 0.5 to 10 percent and preferably of at least
about 2 percent based on the portland cement contained therein. The present
suspension permits the addition of the desired RHA-product and of sufficient calcium
nitrite by a single application. Thus it alleviates on-site multiple application of
admixture materials, and provides for accurate dosage of the desired materials. The
25
ability to combine the present microsilica product with high concentrations of calcium
nitrite to provide a storage stable, pourable suspension is unexpected as suspensions
formed with other microsilicas, such as condensed silica fume, with calcium nitrite
harden after only a few hours to unworkable consistency which can not be poured or
metered. Thus, a particularly novel and useful form of this invention is suspensions
containing from about 20 to 80% (preferably from 40% to 60%) RHA-PF, from about
0.5 to 10% (preferably from 2 to 8%) Ca(NO.sub.2).sub.2, and 0.01 up to 5%
(preferably, 0.1 to 5%) by dry weight of a water reducing agent, as described above,
which is preferably selected from naphthalene sulfonate formaldehyde or melamine
sulfonate formaldehyde condensates. This has exceptionally good properties as an
economical durability enhancing admixture for use in reinforced portland cement
mortars or concretes, since it acts both to reduce the permeability of the hardened
concrete to aggressive species such as chloride or sulfate ions, and also to inhibit the
onset of corrosion of reinforcing steel even if aggressive species, including carbon
dioxide, penetrate through to the steel.
The RHA-product admixture slurry of the present invention can be added to

conventional hydraulic cement compositions in amounts ranging from about 0.1 to
30, preferably to 20 percent solids of the slurry based on the dry cement used in the
cement composition (S/S).
The following examples are set forth to further illustrate and describe the present
invention, and are not meant to limit its scope in any way except as defined in the
claims appended hereto. All parts and percentages are by weight unless otherwise
indicated.
EXAMPLE 1
This example illustrates the production of RHA slurries by the wet-milling process.
Rice hull ash of the RHA-PF class was purchased from Agrilectric Power Partners,
Inc., of Lake Charles, La. They were waste byproducts of an electricity generation
process. The samples had bulk densities of between 17 and 22 lb/cu.ft., silica
contents of 92 to 93 wt.%, carbon contents of 2.5 to 5.5 wt.% and a moisture
content of less than 2 wt. %, the remainder of the mass being principally in the form
of calcium, potassium and magnesium oxide compounds. The median particle
diameter was 65 um, as measured by laser-light scattering technique using a
Microtrac (TM). The RHA was milled in a 3.4 gallon ceramic jar mill, with a grinding
medium consisting of 23.3 kg of steel balls (1/4 and 3/8 inch). The mill was of 12-
inch internal diameter, and was rotated on rollers at 38 rpm. It was first charged
with the steel balls plus 2250 g of an aqueous solution containing 110 g of sodium
naphthalene sulfonate formaldehyde condensate (Daxad-19) sold by W. R. Grace &
Co. Then 2750 g of RHA was added in three increments over a period of 3 hours,
after which the mill was allowed to continue running for a further 16.5 hours. At the
end of this period, the resulting RHA product slurry was withdrawn from the mill, and
analyzed for particle size distribution using a Microtrac laser-light scattering
analyzer. The mass median particle diameter was found to be 2.6 um. The slurry was
a stable liquid with a total RHA solids content of 55% by weight. It has a viscosity of
about 1400 centipoise as measured by a Brookfield viscometer at 60 rpm, and was
pourable.
EXAMPLE 2
This example illustrates the production of a slurry RHA-LT. The RHA-LT was produced
26
by burning raw rice hulls in a current of air at a temperature well below 700.degree.
C., using a 2-foot diameter by 24 foot long externally-heated steel-shelled rotary
calciner. The resulting product was off-white in color, and had a BET specific surfact
area of about 150 sq.m./g, and a carbon content of less that 0.5%. This RHA-LT
sample was ground in a 5-gallon steel ball mill, with a charge of 23.3 kg of steel balls
(1/4 and 3/8 inch), operating at 54 rpm. The mill was first charged with the steel
balls plus 3200 grams of a 2% aqueous solution of sodium naphthalene sulfonate
formaldehyde (Daxad-19), and then 3200 grams of the RHA-LT was added in small
increments over a period of 1.3 hours. The mill was then operated for a further 29.5
hours, with samples being taken at intermediate times. These samples were
subjected to particle size analysis using the laser-light scattering analyzer
(Microtrac). Results are summarized in Table 1. The resulting slurries contained 50%
RHA and 1% Daxad-19 by weight, and were all pourable liquids. The samples were
stored and later observed as being a readily pourable liquid after brief agitation.
TABLE 1
______________________________________
WET GRINDING OF RHA-LT SLURRIES
Sample Grinding Time, hrs.
Vol. median diameter, um
______________________________________
E2-1 7.0 4.0
E2-2 8.0 3.8
E2-3 13.5 3.3
E2-4 29.5 3.3
______________________________________
EXAMPLE 3
This example illustrates the formation of RHA product slurries using a stirred-media
mill. Samples of RHA-PF and RHA-LT as described in Examples 1 and 2 above,
respectively, were milled in a 30-gallon "Attritor" stirred media mill, as supplied by
Union Process, Inc. The milling process was started by adding an aqueous solution of
the indicated water reducing agent to the mill charge in the mill chamber, the mill
charge consisting either of 1/4 inch ceramic balls or 1/8 inch stainless steel balls.
The mill stirrer motor was then started, and unground, dry RHA was fed in slowly at
the top of the mill until the desired quantity had been added. The mill was allowed to
run until the median particle diameter of the RHA in samples taken from the mill had
reached the desired value, as determined by laser-light scattering (Microtrac)
analysis, after which the slurry was discharged by pumping it out of the bottom of
the mill chamber. Results of six such experiments are shown in Table 2. It is clear
that both types of RHA can be ground to the desired particle size range of 4 um or
less by this technique, and that median diameters as low as 1.1 um are achievable.
TABLE 2
______________________________________
RHA Slurry Production with a Stirred Media Mill
Code Ingredients, (% by mass)
Media Median
No. RHA Type* Diam um
______________________________________
E3-1 RHA-PF (52%); DX-19 (1%)
27
C 4.0
E3-2 RHA-PF (52%); DX-19 (1%)
C 2.9
E3-3 RHA-LT (50%); DX-19 (0.3%);
C 3.0
DX-36 (0.3%)
E3-4 RHA-PF (48%); DX-19 (2%)
C 2.4
E3-5 RHA-LT (46%); DX-36 (0.3%)
S 2.1
E3-6 RHA-PF (49%); DX-19 (2%)
S 1.6
E3-7 RHA-PF (49%); DX-19 (1%)
S 1.1
______________________________________
Notes:
*C = 1/4 inch diameter ceramic balls
S = 1/8 inch diameter stainless steel balls
DX-19 = Daxad19, (calcium neutralized NSFC, W. R. Grace & Co.)
DX-36 = Daxad36, (sodium neutralized polyacrylic acid, W. R. Grace & Co.)
EXAMPLE 4
This example illustrates the manufacture of a hydraulic cement composition using

RHA product prescribed by the present invention. A standard high-strength concrete
mix was formulated, using a water/cement ratio of 0.35, and tested as-is or with a
RHA product slurry, the actual slurry used being slurry E3-6, as described under
Example 3. Full details of the cement compositions are given in Table 3. As indicated
additional amount of water reducing agent was introduced one minute after mixing
commenced to cause the slump of the samples to be approximately equal. D.C.
resistivities were measured on 4 inch diameter by 8 inch long concrete cylinders, by
applying 60 volts end to end, using a 3.0N sodium hydroxide solution as the
contacting medium. The method is a modification of the Federal Highway
Administration's Rapid Chloride Permeability Test (FHWA-Report No. RD-81/119
[1981]), and gives results which can be correlated with chloride impermeability,
(i.e., a higher resistivity indicates less permeability to chloride ions). The formed
hydraulic cement compositions having the subject RHA-product (E4-2 and E4-3)
therein exhibited multifold resistance to allowing adverse chloride ions to permeate
therein in comparison to the untreated comparative sample (E4-1).
TABLE 3
___________________________________________________________________
_______
HIGH STRENGTH CONCRETES MADE WITH MICROSILICA SLURRIES
Fresh concrete Properties
Compressive Strength
D.C. Resistivity
Fresh Concrete Mix Proportions. lb/cu.yd.
Final after moist curing
after moist curing
Mix RHA Air
28
Slump
Set,
Density,
1 day,
28 days,
for 28 days,
Code
Cement
Sand
Gravel
Water
Prod.
DX-19
% in. hr lb/cu.ft.
kpsi kpsi ohm-m
___________________________________________________________________
_______
E4-1
744 1421
1707
260 0 10.2
2.2
6.5 8.8
153 3.6 8.2 81
E4-2
730 1395
1675
256 55 8.2 2.6
5.0 5.7
152 4.7 10.5 280
E4-3
740 1289
1696
259 111 12.0
2.5
4.5 7.5
152 4.8 12.0 530
___________________________________________________________________
_______
EXAMPLE 5
This example illustrates the effect of RHA type and particle size on the resultant
permeability properties of cement compositions made using the methods of the
present invention. Mortar cement compositions were mixed in a Hobart mixer, using
a Type 1 portland cement, a concrete sand at a sand/cement ratio of 2.5, and a
water/cement ratio of 0.45, including water added with any admixtures. Rice hull ash
product was added, in slurry form, as a direct volume for volume replacement for
sand, at a total dosage rate of 10% by weight of cement. A total of 1% (solids basis,
relative to cement,) of water reducing agent (Daxed 19) was included in each mix,
29
some of it coming from the RHA product slurries and the rest added directly with the
mix water. Mortar cubes and cylinders were cast and moist cured following ASTM
C109 procedures, and tested for permeability by measuring D.C. resistivity of the
cylinders after 28 days. Results are summarized in Table 4. All samples containing
the RHA product slurries exhibited low permeability as measured by electrical
resistivity, compared to the blank. Compressive strength (cubes) of the blank was
8.4 kpsi while those containing RHA-product were within the range of about 10-12
kpsi after 28 days of cure.
For comparative purposes, a class F fly ash pozzolan was used in the same manner
as above to produce a sample. The sample was formed to have about the same air
and flow properties but the D.C. resistivity exhibited very little increase. Further, two
samples were made in the same manner using RHA-PF material having vol. median
diameters of 65 and 6 micrometers, respectively. These samples also showed very
little benefit to the composition.
TABLE 4
___________________________________________________________________
_______
EFFECT OF MICROSILICAS AND OTHER
ADDITIVES ON MORTAR PROPERTIES
Vol. median
Fresh Mortar
28-day Cured Mortar
Additive type
Diameter, um
Air, %
Flow, %
Resistivity, ohm-m
___________________________________________________________________
_______
None (Avg. 3)
-- 7.3 92 36
RHA-PF 4.0 2.2 116 145
RHA-PF 2.7 4.0 120 188
RHA-PF 1.8 1.7 102 219
RHA-PF 1.1 1.3 89 272
RHA-LT 3.3 4.2 64 301
RHA-LT 2.1 3.1 60 368
Class F Fly Ash*
3.0 126 41
RHA-PF* 65 4.3 50 49
RHA-PF* 6 2.4 107 78
___________________________________________________________________
_______
*Comparative Examples.
EXAMPLE 6
30
This example illustrates the ability to form aqueous slurries of RHA-product and
calcium nitrite which are useful as cement admixtures. Samples of the formed slurry
E3-4 described hereinabove were mixed with calcium nitrite in the amounts indicated
in Table 5 below. The particle size of the RHA-product used was not altered by the
required additional mixing to provide a substantially homogeneous composition. The
pH of the samples was measured with a glass electrode immersed directly into the
suspension. The samples were shaken and their ability to flow was observed. This
visual observation is indicated in the Table 5.
TABLE 5
______________________________________
RHA-PRODUCT/CALCIUM NITRITE SLURRIES
Ca(NO.sub.2).sub.2
Storage Condition Stability
Sample
% of Slurry
Days .degree.C.
pH Fluidity
______________________________________
1 0 84 23 -- Stable; Fluid
2 5 0 23 8.1 Stable; Sl.
Thicker than
Sample 1
3 5 4 50 7.4 Stable; Fluid
5 8 4 23 8.0 Stable; Thick
liquid
6 8 7 50 7.7 Stable; Thick
liquid
31

Germany - 100607 Patent For Manufacturing White Rice Husk Ash

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Germany - 100607 Patent For Manufacturing White Rice Husk Ash

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Title:

Method of producing low-carbon, white husk ash

3. The method of claim 2, in which the rate of heating is 25.degree. C./min.

5. The method of claim 4, in which the oxidizing agent supplied is water-vapour.

6. The method of claim 1, in which HCl is added so as to inhibit the crystallization of

In addition, up to 30% carbon is found, depending on the degree and nature of

An object of the invention, therefore, is to provide a large-scale industrial method of

In a preferred embodiment of the method, the volatile constituents are separated at

Preferably, the rate of heating up is 25.degree. C./min. According to another

Differential thermoanalysis (DTA) and differential thermogravimetry (DTG) in a

Systemmatic ashing tests on a semi-industrial scale in the presence of stagnant air

If required, additives such as NaCl should be added so as to accelerate the removal

1. Field of the Invention

2. Description of the Prior Art

SUMMARY OF THE INVENTION

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is sectional view of an embodiment of an apparatus for conducting the batch

FIG. 2 is a perspective view of the apparatus of FIG. 1.

FIG. 3 is an explanatory view of an embodiment of an apparatus for conducting the

FIG. 5 is a graph showing how the compression strength of concrete incorporating

The graph of FIG. 5 shows the compressive strengths of 28-day-old concretes

5. The product of claim 2 wherein the particle size is up to about 3 micrometers.

10. An aqueous suspension comprising from about 0.01 to about 10 percent by

12. The suspension of claim 9 wherein the water-reducing agent is a mixture of

13. An hydraulic cement admixture comprising an aqueous suspension of claim 7.

14. An hydraulic cement admixture comprising an aqueous suspension of claim 9.

15. An hydraulic cement admixture comprising an aqueous suspension of claim 10.

16. An hydraulic cement admixture comprising an aqueous suspension of claim 11.

17. An hydraulic cement composition comprising a portland cement, sand, aggregate

18. An hydraulic cement composition comprising a portland cement, sand, aggregate

19. An hydraulic cement composition comprising a portland cement, sand, aggregate

20. An hydraulic cement composition comprising a portland cement, sand, aggregate

In the case where RHA is viewed predominantly as an extender-filler, the particle

DETAILED DESCRIPTION OF THE INVENTION

A "pozzolan" is an inorganic material which consists principally of chemically reactive

The process required to achieve the RHA-product of ultra-high fineness is to grind

In addition, other conventional cement admixture materials may be combined in the

Another embodiment of the present invention relates to a particularly useful and

The RHA-product admixture slurry of the present invention can be added to

This example illustrates the manufacture of a hydraulic cement composition using

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