Note: Descriptions are shown in the official language in which they were submitted.
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Title of the Invention:
AQVEOUS SLURRIES OF CARBONIZED SUBSTANCES ~A~UFACTURI~G ~ETHOD AND
MANUFACTURING ~QUIPMENT THEREFOR.
This invention relates to an aqueous slurry of carbonized material ana to
apparatus and method for the manufacture thereof. Hors particularly, it
relates to an aqueous slurry of carbonized material of small particle size.
Since carbonized substances from plants are solids of indefinite form,
they are inconvenient for handlin~ such as transport, storage and the like
compared with liquid fuels. Interest in techniques to fluidize and transport
these carbonized plan~ materials has been enhanced because of two factors.
One is the advantages of fluidization in handlin~ durin~ transport and the
other is the expectation of an alternative fuel closer to oil from the
economic aspect. Recently, developments in research on mixed slurries of coal
with water have made progress.
The present invention thus relates to an aqueous slurry obtainable by
adding water to carbonized plant material (hereinafter referred as CCWS~.
Although there are various types of pulverizers for the pulverization of
solid matter such as coal etc. as shown in Table 1, it has been considered
difficult to reduce the diameter of the ~ranules to less than 100 microns as
well as there being a lack of economical pulverizers. The situation is the
same also in the case of pulverizing carbonized plant substances on a
laboratory scale even when not carried out on a commercial basis. Since the
pulverizat.ion thereof is eas;er than that of coal, there hss been the
advantage that the power consumption is somewhat lowar. When mixing these
fine powders with water under fixed conditions using a dispersion stabilizer,
an aqueous slurry can be made. Investigations have also started recently on a
method for carrying ou~ the pulverization and the conversion to slurry
simultaneously.
As to conventional techniques to make aqueous slurries from coal, there
are three ways as shown in following diagrams (There are no techniques to make
an aqueous slurry from carbonized plant material.
PAT 6379-1
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Ta` l. Classification of pulverizers and characteristics thereof placing fine pulverizers in center
~ _ ~ __.
i~cation ~e of pulverizer Name of pulverize Structure of pulverizer I Remarks
_ ~ ., .. ~ ~ . ~
Jaw crusher /
Ccmpressive crusher Gyratory crusher /
(Coarse pulverizer) Cone crusher /
Shearlng coarse CUtterl Blade type /
crusher milllCutter type /
9~ Shredder /
(Harmer mill, / I /
shredder) / I /
Impact crusher Harmer crusher /
~ ~ ~ Ro11 mil1 Roll crusher /
_ _ (Roll -revolution __ /
type) Roll n~schine /
h _ _ _ _ _ __ ~ ~
tDisintegrstor) D1sinteg~tor /
~ Screw mill
_. (Coffee mill) /
~ llol1-ro111n~ w- _ ~ID~;~ Used in the field of ceramic industry since
.~ ment type &dger~er ike rollers on circular plate lcng ago and called fret mill. Knaading is
.~ __ ~f ~ included._To several~-m._
Hitting powder lay- ~mpact on particles in vessel by Simple structure, la~ processing quantity.
er with mallet type Stump mill alling of pounder ~stump) To ten and several ~m with special sub-
l __ - ~. .... _ , ., _ . ,
1, Disk mill, Pin mil ldVeirkZatiln biY Piin8 or giVeS Disintegrating action. To ten and several
_ pulverizer (Hanmer mill) ~ At miZeri and ToriseUveralYf~m occa8ionally.
. ..._ ~ .. . _ _
se oP i~t plate revolving at Supermicron mill, turbcmill and various
CentriPugal classi- igh speed. Particles move to types. To micron order.
Pication type mill ial direction riding on air
~rrent..
.. .___ .. . _ _ _
~anpression, shear and frlctlon~
Roll-rolling move- Roller mlll n powders by ravolution of sev- Mainly raw materials for ceTent
ment type ral rollers ~or balls) around i
tha sun and on own axis on a dis I
a~ Spontaneous pulver- AeroPall mill Lndar oP largeUlVcalriibaetionAin cyl- IAimed at cr lda raw materials such as ores
- _~ _, . ~weep system _ _ _ -
P~ ~ lverization by falling of ball !Most widely used in all fields. Many typas
~all mill in narrch t into revolving cylinder as and diverse operating mathods and condi-
Ball mill (in broad sense (Pot mill, lverizing medium. Continuous, tions. Possible also in a region of sub-
sense) hlbe mil1) tch, dry and wet type. micron. _ _
/Rolling Irovement~ ~ibratory ball mill i~m t lmto cylindrical or persion, mixing ortreParc0Ctiednresp5UCh as dis-
~low speed 7 ~ _ ~ Pulverization in a re~ion of submicron
Planet type pulver Revolutions both aroud the sun Pa~arful for the use in a region of sub-
i~er ~=~ micron. _ _ _
Tcwer type pulveri Agitation of medium in vertical iCombined mainly with rock, partly with neu-
zer (Screw type) ylinder by screw. !tralization procedure etc.
~ ~ . .. . _ ............ . _ __ _ _
.~ Agitator mill iolent agi~ation of pebbles and IStarted frc(n the use for pulverization of
Medium agitation beads in vertical cylinder. Ipigment etc. as sand grinder. Currently,
type pulverizer Agitation of pebbles and beads i attracted attention rapidly also as pulver-
Disk-agitation mil cal ves5el byh5revzeornatall hylindri_ in a reglon of submicron.
____________________ ~ Developed in Germany and Switzerland re-
Annular mill peed revolution of cylinder wit~ cently. For pulverization in a region of
beads put into a space of double submicron.
, Air current pulver- Jet pu~verl~er cles ~ ~et aibrYcurag ing partl limited to a rleAgmiOn OfiSpsebmilve action is
~ . ~ ~ -- .
Wet type high-speed * - t fine pulverizer of high-speed Dispersion into fluid after pulverizing to
revolution mill Colloid mill evolution type. Disk revolu- submicron.
ion, Intragap flow, etc.
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* lverization of powders in mo- Torpedo pulverizer. For preparation of an-
Traditional special Mortar ar by hands using pestle. Motor alytical samples. To submicron.
pulverizer type is available
~ Stone mill _ __ __
_ _ ~ Yagen _ _ _ _ _
, __ _~ ~ _ _ ~
Notet Those marked by * are powerful for production of super fine particles.
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Wet proce&s
¦pulverizer¦ ~ roncentratin~ Mlxlng and Cln-
Water Sulfur T
Ash Dispersant
~ Semidry process
¦Wet pulv ffizerl l
_ _ ¦Mixing and con-
_ ....................... _ jversion to slurry
Dry pulverizer _ , _ _
~ Dispersant
W Dry process
¦Dry pulveri~a~ion ~ X ~
I . I version ~ slurry
.
t . T
Water Dlspersant
There are no reports on the manufacture of aqueous slurries through fine
pulverizstion by the use of a super colloid mill type fine pulverization
device (Masscolloider*? listed in Table 1.
As can be seen from the diagrams of the manuacturing p~ocesses for
coal-water slurries, conversion to a slurry is carried out via two or three
stages. It is a characteristic of the present invention to carry out the fine
pulverization and the conversion to slurry simultaneously in one stage.
Wi.th commercial pulverizers as above, two to three stages are necessary
for the conversion to slurry and the particle size of the granules cannot be
made less than 100 microns. Therefore, the super colloid mill was reformed
and improved ~or pulverizin~ the particles to 18ss than 20 microns and
; convertin~ to aqueous slurry in one stage. Reeping an eye on the improvement
in the upper and lower ~rinders which form the heart of the ~asscolloider*
regarded possibly as representative of a super colloid milL, the inventors
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PAT 6379-1
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have succeeded in making vitrified grinders (grind-stones) composite with
polymer so as to alter the quality of the material entirely. By fitting these
polymer-composite vitrified grinders (trade mark: Grindelt a
polymer-composite vitrified grinder containing thermoplastic or thermosetting
polymer partially filling the voids therein in an amount of 30 to 60~ of the
void pores so that 70 to 40~ of the void pores remain and the volume fraction
Vp of polymer lies within a range of 0.09 to 0.21) to a Masscolloider~, it
became possible to finely pulverize the carbonized plant material continuously
to less than 20 microns for a long period of time. As a result, a method has
been developed wherein, by adding water and dispersant, a stable carbonized
material - aqueous slurry is manufactured together with fine pulverization.
In consequence, the power consumption power was lowered and the cost price
for the manufacture became about one half to one fifth of that when using the
various pulverizers listed in Table l. Judged as a total system, the fact
that ~he manufacturing method consists of one stage has proved to contribute
greatly to improvement in productivity.
CCWS is a pseudoplastic fluid with a yield value showing thixotropic
behavior. Therefore, in order to manufacture CCWS having a high
concentration, fluidity and stability simultaneously, a variety of actors are
significant, Mainly these are the manufacturing process etc. by the use of a
super colloid mil1 type pulverizer as well as fundamental physical properties
of the carbonized plant material substances, particle size distribution
thereof, dispersant, etc.
First, the fundamental physical properties originate in that the
~ carbonized substances are porous and can adsorb moisture as opposed to coal.
Although the ~undamental physical properties of coal can vary significantly
depending upon the minin8 district, those of carbonized plant material show
almost constant values without being affected greatly by the kind of plant,
conditions of carbonization, etc. Moreover, since the carbonized substances
hardly contain any impuri~ies, for example, sulfur and organic matter, the
quality control thereo is easy.
Secondly, with regard to the particle size and particle size distribution,
`~ ~ when using a Masscolloider* pulverizer ~or the pulverization, the particle
size concentrates mostly within a range between 20 and 10 microns compared
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PAT 6379-1
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with the case of coal, and the yield in this region exceeds 90~. From the
fact that the particle diameter of the carboni~ed material is uniform, aqueous
slurries which are excellent as to stability can be manufactured.
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: ~1 PAT 6379-1
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Thirdly, as ~o the dispersant, there are two methods for allowin~ solid
particles such as carbonized plant substances to disperse in~o a liquid: one
allows electrostatic repulsion to occur by bindin~ the groups Df ionizable
nature on the surface and the other allows steric repulsion to occur by
bindin~ (adsorbin~) the solvent-philic high molecular substances.
Through the adjustment of particle size distribution, it becomes possible
to make the concentrat;on hi8h (referring to the weight ratios of carbonized
substance and water, the case when the ratio of the former is higher), but
CCWS of excelLent fluidity cannot be obtained by leaving as it is. Therefore,
small amounts of dispersant are needed to giV2 the fluidity. As the
dispersants, anionics and nonionics are mainly used. Anionics principally
allow the surface of the particles of carbonized substances to be char~ed
negatively to provide dispersive action ~y repulsion between surface char~es.
Nonionics principally afford the dispersive action by steric hindrance of long
molecular chains. Besides, anionics can provide ~oth actions by making them
of high molecular waight.
As the dispersants to be used in the invention, almost all of th0
dispe~sants suitable for coal-water slurries can be used. Among them,
anionic~ No. F-l-W* and No. F-6-W* made by ~ihon Oil and Fat Industries Co.
are inexpensive and, by addin~ 1% thereof in tarms of pure ingredient to the
weight of carbonized material as an upper limit9 the aqueous slurry can be
stabilized for about 2 weeks. The stability differs somewhst depending upon
the methods o~ addition. The best method for addition is to spray the aqueous
solution of dispersant several times separately in an atomized state. If
added all at once, the time for the manufacture has been confirmed to be
lengthened about twice. Moreover, the fact that it iq unnecessary for the
dispersants to be selected as to type and amount dependin~ upon the type of
carbonized material, manufacturin~ method thereof, etc., can also b~ said to
be a characteristic. However, it is necessary to take pH, temperature
dependence, history of shear resistance, etc. into account to some extent.
Nevertheless, these do not become decisive factors for the manufacturing
method.
In order that particles of the carbonized material do not precipitate
stabilization due to the mutual dispersion of particles and due to the network
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PAT 6379-1
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structure formed mutually by particles (weak ag~re~ates) is necess~ry. Since
the stabilization due to the dispersion and that due to the ~eak a~regates
are opposed to each other, it is an essential point for technical development
to control these s~ ully. However, when manufacturin~ a carbonized
substance-water slurry by the use of a Masscolloider* pulverizer fitted with
Grindel* ~rinders, the aqueous slurry was found to be extremely stable and all
of these problems could be solved.
In the D~awings,
Fig. 1 is a schematic dia~ra~ showing manufacturin~ process for carbonized
material-water slurries according to the invention. Fig. 2 ~A) ~nd (B) are
elevational and sectional elevational views, respectively, showing the parts
of manufacturin~ equipment for makin~ carbonized material-water slurries
accordin~ to the invention.
The correspondence of She numbers in ~he drawin~s to the abbreviated
titles is as follows:
_
Number Abbreviated Cltle
A Body of ~o. l.. pulverizer
A - 1 Adjusting plate
A - 2 Rotor
A - 3 Impaet pawl
A - 4 Stator
A - 5 Sereen
B Body of ribbon type mixer
B - 1 Damper-switehing handle
B - 2 Dustproof eover
B - 3 Ribbon type agitation arm
C sody of serew fesd deviee
C - 1 Screw wing
D Body of Masseolloider MKZA 10-10
D - 1 Hopper
D - 2 Body of eop cover
D - 3 Lever handle
D - 4 Adjusting handle
D - 5 Stator ~asscolloider~
D - 6 Rotor Masscolloider~
D - 7 Exit chute
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PAT 6379-1
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In Fig. 1, a schematic diagram of the manufscturing process for carbonized
substance-water slurries is shown. The following is an explanation.
To 30kg of bark charcoal containin~ 7% of moisture (weight of moisture
amounts to 2.1kg) used as the carbonized material was added a well agitated
aqueous solution containing 27.~kg of water and 0.558kg of dispersion
stabilizer w;th a purity of 50~. At this sta~e, the weight of water amounts
to 1 per 1 unit of weight of carboniæed material 9 and the concentration of
dispersant in ter~s of pure ingredient corresponds to 1% by ~eight of
carbonized material. By kneading for several minutes in a ribbon t~pe mixer
after adding the water incorporating dispersant to the carbonized substance,
about 113kg of kneaded material was obtained. This kneaded material was
pushed into No. 1 Masscolloider* with built-in polymer-composite Grindel*
grinders using a scr~w feed device and the clearance was adjusted to 0.06mm.
As the kneaded material was subjected to super colloidal millin~, the
carbonized substance and water were unified by the action of the dispersant
into slurry form. This slurry was transferred through a pipe, injected into a
No. 2 Masscolloider* pulverizer and the clearance was adjusted to O.Olmm. The
fact that the clearance can be adjusted to O.Olmm is an important basis of the
invention. From the outlet of the No. 2 machine, CCWS was ejected
continuouslr. The particle size distribution of carbonized suhstance in this
slurry is shown below. The viscosity was S,S00 cp.
We~t (Z) O _ O 4.7 3.4 19.0 9.9 11.6 6.3 10.3 10.8 8.3 10.3 2.6 2.8 100
Partic1e~) 60 50 ~ 30 20 10 8.0 6.0 5.0 4.0 3.0 2.0 10 0.8 0.6 0.5 _
The weight of carbonized material~water slurry obtained was about 56.4kg.
This corresponds to 43 litres in volume. The specific gravity was about 1.3.
In the following, a concrete example will be described in detail based on
Fig. 2.
Illustration is made with regard to the manufacturing method for CCWS
using industrial waste carbonized material (mainly waste papar) as the raw
material, and the equipment therefor. The carbonized materlal was first
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PAT 6379-1
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subjected to coarse pulverization. For this, 30kg each of carbonized raw
material were pulverized coarsely with two pulverizers A (having a
pulverization capacity of 30kg/hr at O.llmm screening). The carbonized
material was fed to ~he body of A by A-l in appropriate amounts at a time,
pulverized by the mesh of A-3 provided on A-2 revolving at 4,500 rpm with A-4
fixed to A, and ejected through A-5 with O.lmm. At this time, the consumption
voltage was 200V (three-phase) and the consumption current was about 7 AH per
pulverizer. On the other hand, 25.8Xg of water and 0.558k~ of disper~ion
stabilizer, nonionic ~o. F-6-W (50~ solution of pure in~redient) made by Nihon
Oil and Fat Industries Co. were weighed, mixed thoroughly in a simplified
mixer and stored (It is necessary to prepare twice the amounts).
Followin~ this, 30k~ each of carbonized material powder pul~erized with A
separately were thrown into two ribbon mixers B, the opening portion thereof
bein~ closed by B-l, and, after the addition of an aqueous solution of
dispersion stabilizer uniformly in amount, the mixer was covered and mixing
was carried out for about 8 minutes by B-3 revolving at 55 rpm to manufacture
43 litres for each run, total 86 litres (about 113kg) of primary CCWS. The
consumption voltage was 200V (three-phase) and the consumption current was 5
AH per mixer.
The slurry manufactured with mixer B was ejected completely by opening the
opening portion by B-l and switching on.
~ext, the slurry was fed into ~asscolloider* pulverizer D by means of
screw feeder C ~capacity of lOOkg~hr) fitted to hopper D-l. The consumption
volta~e was 200V ~three-phase) and the consumption current was O.7 AH at C.
With D, the clearance had been adjusted beforehand. While off, D-2 was closed
and D-3 was locked firmly. Putting the point where rotor D-6 was contacted
with stator D-5 by turning D-4 as far as possible as ~he zero point, the
clearance was adjusted to 0.06mm (co~rresponding to 3 divisions) which was
required for the pretreatmant pulYerization, and locked. With D switched on,
D-6 revolved at 1,450 rpm and 113k~ of CCWS were manufactured over about 52
minutes, and was ejected from D-7. At thls time~ the consump~ion voltage was
200V (three-phase) and the consumption current was 4.0 to 4.4 AH. The product
CCWS was transferred further to D, the clearance thereof being set up to O to
O.Olmm for finishing, and the particle size of carboni~ed material was brought
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PAT 6379-1
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to less than 20 microns to obtain stabilized CCWS. The consumption current of
this step was 3.6 to 3.9 AH. The viscosity of CCWS obtained finally was 6,500
cp. ~oreover, the running cost calculated from the consumption of power was
0.2 yen/k~. The particle size distribution of this CCWS is shown below.
ht (Z) lo lo lo lo 116-3117-~LO-4111-518-4~8-318-417-912-4~ oozl
¦Pa~ ~le~ ~¦30¦20 ¦10 ¦ 8-0¦6-0¦5-0¦4-0¦3-0¦2-0¦1-0¦0 8¦0-6¦0-5¦
When carbonized substances are pulverixed by the dry process, the
consumption of power is hi~h and dangers such as explosions are sometimes
pre~ent. Horeover, the pulverization is also involved in health problems for
the human body such as dirt in surroundinss etc. For these reasons, fine
pulverization by the wet process was investigated. However, it is extremely
diffi.cult to reduce the particle size of carbonized substances to less than 20
microns, and expensive treatment i5 needed to obtain such fine particles.
Recently, CCS conception (Coal Cartridge System) has been proposed and
CCCS conception ~Charcoal Cartrid~e System) is now in the course of
investigstion. In particular, carboni7ation of inflammables in urban refuse
and industrial wastes and the manufacture of CCWS using these as raw materials
is re8arde~ as the important technique of the 21st century.
The fulfillme~t of this conception depends upon systemization and
equipment capable of integrating the manufacturing processes, which make the
particles fine and convert them to an aqueous slurry, into one process.
As a result of the invention, by utilizing this system, arbitrary
production systems ranging from small scale to large scale can be built up
inexpensively on the site where the carbonized substances are produced. This
can be a lar~e saving in economy of resources and ener~y conservation.
It was confirmed by the present invention that not only aqueous slurries,
but also alcohol slurrias of carbonized material can be manufactured usin~
alcohols (ethyl, methyl, etc.~ in place of water.
This means that the transport of alcohols and that of fine powders of
carbonized material can be made efficiently at the same time. Tharefore, when
PAT 6379-l
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importing carbonized substances and alcohols from overseas, they can be
transported at a high concentration and economical savings are expected.
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