CA1253006A - Process for producing a high concentration coal-water slurry - Google Patents
Process for producing a high concentration coal-water slurryInfo
- Publication number
- CA1253006A CA1253006A CA000457256A CA457256A CA1253006A CA 1253006 A CA1253006 A CA 1253006A CA 000457256 A CA000457256 A CA 000457256A CA 457256 A CA457256 A CA 457256A CA 1253006 A CA1253006 A CA 1253006A
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- CA
- Canada
- Prior art keywords
- weight
- coal
- less
- slurry
- coal particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 105
- 239000003245 coal Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 238000009877 rendering Methods 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- YHGREDQDBYVEOS-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate Chemical compound CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O YHGREDQDBYVEOS-UHFFFAOYSA-N 0.000 claims 1
- 230000035515 penetration Effects 0.000 description 7
- 230000001186 cumulative effect Effects 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 5
- 239000002802 bituminous coal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000003250 coal slurry Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability is provided, which process comprises causing the slurry to have a composition of coal particles so that when the particles are divided into 8 fractions, each having a particle diameter range listed below, then the proportions by weight of the particles contained in the respective fractions, relative to the total weight of the particles contained in the slurry can fall within the following numeral value ranges:
F1: (DL/4 to DL) --- 29.0 to 50.0 % by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0 % by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0 % by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0 % by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0 % by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2 % by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0 % by weight F8: (DL/4 to 0) --- 0.7 to 9.0 % by weight wherein DL represents the maximum particle diameter.
A process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability is provided, which process comprises causing the slurry to have a composition of coal particles so that when the particles are divided into 8 fractions, each having a particle diameter range listed below, then the proportions by weight of the particles contained in the respective fractions, relative to the total weight of the particles contained in the slurry can fall within the following numeral value ranges:
F1: (DL/4 to DL) --- 29.0 to 50.0 % by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0 % by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0 % by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0 % by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0 % by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2 % by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0 % by weight F8: (DL/4 to 0) --- 0.7 to 9.0 % by weight wherein DL represents the maximum particle diameter.
Description
~2530~6 , .
SPECIFICATION
TITLE OF T~E INVENTION
Process for producing a high concentration coal-water slurry BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a coal-water slurry, and more particularly it relates to a process for producing a coal-water slurry of the so-called good stability having a high coal concentration and a low viscosity with minimal settlings.
Recently coal has come to be actively used in place of petroleum mainly at thermal power stations. However, coal in the form of solid fuel is difficult to handle; hence large transport costs arerequired and there is a great influence on the cost of coal itself. Thus techniques by which coal is slurried to make it possible to handle coal in the form of fluid have been energetically developed. One of products thus developed is a mixture of heavy oil with coal (Coal and Oil Mixtures, hereinafter re~erred to as "COM"). In the case of COM, however, the ratio by weight of heavy oil to coal is about 1 : 1; thus COM cannot be regarded as a oil-free fuel and also its merit in respect of cost is small. Further, methacoal in the form of a mixture of methanol with coal also has a high cost; hence it has not yet been practically used.
On the other hand, CWM in the form of--a mixture of coal with water (CWM: abbreviation of Coal-Water Mixtu~es) is - ' . ", gj~;
SPECIFICATION
TITLE OF T~E INVENTION
Process for producing a high concentration coal-water slurry BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a coal-water slurry, and more particularly it relates to a process for producing a coal-water slurry of the so-called good stability having a high coal concentration and a low viscosity with minimal settlings.
Recently coal has come to be actively used in place of petroleum mainly at thermal power stations. However, coal in the form of solid fuel is difficult to handle; hence large transport costs arerequired and there is a great influence on the cost of coal itself. Thus techniques by which coal is slurried to make it possible to handle coal in the form of fluid have been energetically developed. One of products thus developed is a mixture of heavy oil with coal (Coal and Oil Mixtures, hereinafter re~erred to as "COM"). In the case of COM, however, the ratio by weight of heavy oil to coal is about 1 : 1; thus COM cannot be regarded as a oil-free fuel and also its merit in respect of cost is small. Further, methacoal in the form of a mixture of methanol with coal also has a high cost; hence it has not yet been practically used.
On the other hand, CWM in the form of--a mixture of coal with water (CWM: abbreviation of Coal-Water Mixtu~es) is - ' . ", gj~;
2 ~.253006 sufflciently practical ln respect of cost; hence it has recently been greatly noted. However, a problem raised in the combustion of CWM is the water content in CWM.
As its combustion efficiency is concerned, naturally the lower the water content, the better the efficiency, and in the case of direct combustion, a water content of 30 % or less is preferred. However, the lower the water content, the higher the viscosity of CWM; this raises a problem that when it is transported by way of pipeline or the like, the pressure loss increases.
Further, when CWM is practically used, a problem of storage is also raised. When CWM is stored in a usual tank, it is necessary for it to have a superior stability, but since CWM consists of coal particles and water, it is preferred to reduce their particle diameter, in order to inhibit coal particles from settling as much as possible.
However, there is a tendency that when the particle diameter is reduced, the viscosity increases.
In order to overcome such drawbacks, it has been attempted to adjust the particle diameter distribution of coal particles to thereby prepare a CWM of the so-calIed good stability having a high coal concentration and a low viscosity with minimal settlings. However, coal particles are not completely spherical, and also the mèthod of measuring the 25- particle diameter of coal particles are various as follows:
a method by means of sieves,a settling method represented by Andreasen Pipette, a method of analyzing the paFticle shapes ' , . . - ~ .
1253006 f . .
by way of photographs of SEM (Scanning Electron Microscope) to calculate their representative diameter, etc. Thus, the definition of the particle diameter also varies depending on the measurement methods. This causes errors in adj~sting the particle diameter distribution, and it becomes difficult to produce a CWM having a high coal concentration, a low viscosity and a good stability.
Now, the present inventors have considered that this problem might be solved by adjusting the particle diameter distribution according to a method of measuring the particle diameter distribution regarded as most adequate, and have made extensive research! As a result, we have succeeded in obtaining the objective CWM having a high coal concentration, a 1GW viscosity and a good stability.
The object of the present invention is to provide a process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability.
SUMMARY OF THE INVENTION
The present invention is characterized briefly in that the particle diameter distribution of coal particles is measured relative to all the particle diameter ranges accordlng to a definite method for measurement and then the particle diameter dlstrlbution is adjusted so as to reduce t~e viscosity of a coal-water slurry at high coal concentra~ions and make partlcle settling minimum i.e. improve the so-called stability.
.
The present invention resides in the following process:
''~3 ' ' .
_ 4 - ~25300~
In the process for producing a coal-water slurry having coal particles dispersed in water, a process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability, which process comprises causing the slurry to have a compo~ition of coal particles, so that when the coal particles are divided into 8 fractions (Fl, F2, -----and F8), each having a particle diameter range listed below ((DL/4 ~
DL), (DL/42~ less than DL/4), ----- (DL/47 ~ 0), wherein DL
represents the maximum particle size of the coal particles), then the proportions by weight of the coal particles contained in the respective fractions, relative to the total weight of the coal particles contained in the slurry can fall within the following numeral value ranges:
Fl: ~DL/4 to DL) --- 29.0 to 50.0% by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0% by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0% by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0% by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0% by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2% by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0% by weight F8: (DL/47 to 0) --- 0.7 to 9.0% by weight BRIEF DESCRIPTION OF THE DRAWINGS
Fig. l shows a chart illustrating the particle sizes of low viscosity slurries and cumulative par*icle diameter .
distributions thereof.
.
.~ .
~253006 , -Fig. 2 shows a bar chart illustrating particle ~ ze and proportions by weight of the respective fractions.
Fig. 3 shows a diagram illustrating the relationship between par~icle size distributions and slurry viscosities.
Fig. 4 shows a chart illustrating the relationship between particle size distributions and stability.
Fig. 5 shows a chart illustrating the relationship between the amount of dispersant added and viscosity.
Fig. 6 shows a chart illustrating ~he relationship betweeen pH and viscosity.
Fig. 7 shows a chart illustrating the relationship between the amount of ultrafine particles of 0.05 ~m or less added and stability.
Fig. 8 shows a view of piping system illustrating an embodiment of an apparatus for producing CWM.
Figs.9 and 10 each show a chart illustrating the particle size af slurry produced by the apparatus of Fig. 8 and cumulative sieve pass proportion by weight.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described referring to the accompanying drawings.
Coal is ground in the wet or dry manner by means of a mill and a part of the resulting particles is taken to measure their particle size distribution. In measuring the particle size distributioni it was considered that the weight proportion of finely divided particles had a great influence upon the viscosity and the stability relatlve to .: ' ~ 2530~
settlng of slurry; thus ln an example, the partlcles were divlded into the following 8 fractions (each a constituent part as a group), and the respective fractions were each sieved by a sieve most adequate thereto (e.g. sieve according to JIS standards or millipore ~ilter having the particle size well adjusted ) to measure the weight of the fraction.
In the following list, DL represents the maximum particle diameter of particles. Fl ~ F8 represent symbols of the respective fractions.
Particle diameter range Fl: DL~4 ~ DL
F2 DL/42 ~ less than DL/4 F3 DL~43 ~J less than DL/4 F4 DL~4 ~ less than DL/43 F5 DL/45 ~ less than DL/4 F6 DL/46 ~ less than DL/45 F7 DL~4 ~ less than DL~46 F8 l ess than DL/4 20In the present invention, particles were divided into 8 fractions for measurement, but the number of fractions is not always limited to 8, but practically it may be 5 to 15 unless the distribution of the partlcle sizes changes.
"~ More than one kind of coal or coal slurry were mixed so that the constituent proportions by weight of Fl rJ F8 might have a certain value, respectively, and if necessary, . . . .
' water was added for adjusting the water content, to study i' ` . ' ' 1, ' .: ' .
~ ~ .
.
~l253006 .. .
their vlscositles. In thls case, if the maxlmum partlcle size DL is too large, the amount of unburned matter at the time of combution increases, while if it is too small, the slurry viscosity increases; hénce the maximum particle size DL was made 44 to 420 ~m.
Further, a certain kind of coal was chosen and the proportions of fractions were varied to study the influence upon viscosity. Further, when proportions of fractions exhibiting a relatively low viscosity were converted into cumulative distributions, a tendency was found. Fig. 1 shows a chart illustrating the relationship between the particle size and the cumulative sieve pass weight proportion in the case where three kinds of slurries (No.l ^~
No.3) were prepared from coal A (bituminous coal, ash content 9.5 %). There are shown cumulative particle size distributions in the case of a coal concentration of 70 % and 1,000 cP viscosity or less. In thiscase, the particle size DLis 297~m and only distributions of particle sizes of 1 ~m or larger are shown. Further, the slurry viscosity refers to numeral values obtained when an inner cylinder-rotation type viscometer was rotated at a shear rate of 90 sec 1 for 5 minutes. It is seen from Fig. 1 that the proportions in the case of 1 ~um or more each constitute a nearly straight line. Further, when the -cumulative sieve weight proportion U(D)% is 100 % at D = DL Ds ~minlmum partlcle diameter) at which U(D) = 0 % should be present. Thus, we propose the following equations (1) and (2) as those indicatlng a particle slze distribution mode of ~i j. ~, ................ . .
!~
.
- . . .
" ~
coal partlcles contalned ln a slurry exhlbltlng a low viscoslty at a high coal concentration:
U(D) = ( s ) x 100 % ____- (1) - D
5Dq - Dq Dq - Dq _____ (2) wherein q represents an index of particle size distri-bution, and U(D) represents cumulative % by weight of the particles of smaller diameter than a particle diameter D.
In both the equation (1) and (2), when D = DL, U(D) = 100%, and when D = Ds, U(D) = 0 ~. That is, these equations correspond well to practical particle size distributions.
If Ds = in the equation (1) and (2), the equations both give the following equation ~3):
U(D) = ( - ) x 100 % ----- (3) DL
This equation (3) corresponds to Andreasen's equation which has been known as a particle size distribution equatlon giving the closest packing for powder of a continuous particle size system. As to this Andreasen's equation, studies were made in the past, and it was confirmed that when q = 0.35 ^~ 0.40, the percentage packing attains the maximum.
The percentage packing, however, varies depending on particle shapes, and as to the systematic relatlonship between the q value and the slurry viscosity and stability of coal-water slurry, no study has never been made. Further,-Andreasen's equation i8 a distrlbution equation in the case where particles B
~253006 g having an infinitesimal partlcle diameter were presumed, but the equation cannot be, as it is, applied to practical coal-water slurry. Whereas, the present inventors confirmed that the equation (1) and (2) correspond ~ell to practical distributions.
Fig. 2 shows the weight proportions of the respective fractions in the case where DL = 297 pm, Ds = 0.01 ~m and q = 0.3 in the equations (1) and (2). In this case, in order to compare the particle diameters more strictly, particles were divided into the following 15 fractions (dotted lines in Fig. 2 indicate the case of the equation (2) and solid lines therein indicate the case of the equation (1)):
Particle size range (1) Fl: DL/2 ~ DL
(2) F2: DL/2 ~ less than DL/2
As its combustion efficiency is concerned, naturally the lower the water content, the better the efficiency, and in the case of direct combustion, a water content of 30 % or less is preferred. However, the lower the water content, the higher the viscosity of CWM; this raises a problem that when it is transported by way of pipeline or the like, the pressure loss increases.
Further, when CWM is practically used, a problem of storage is also raised. When CWM is stored in a usual tank, it is necessary for it to have a superior stability, but since CWM consists of coal particles and water, it is preferred to reduce their particle diameter, in order to inhibit coal particles from settling as much as possible.
However, there is a tendency that when the particle diameter is reduced, the viscosity increases.
In order to overcome such drawbacks, it has been attempted to adjust the particle diameter distribution of coal particles to thereby prepare a CWM of the so-calIed good stability having a high coal concentration and a low viscosity with minimal settlings. However, coal particles are not completely spherical, and also the mèthod of measuring the 25- particle diameter of coal particles are various as follows:
a method by means of sieves,a settling method represented by Andreasen Pipette, a method of analyzing the paFticle shapes ' , . . - ~ .
1253006 f . .
by way of photographs of SEM (Scanning Electron Microscope) to calculate their representative diameter, etc. Thus, the definition of the particle diameter also varies depending on the measurement methods. This causes errors in adj~sting the particle diameter distribution, and it becomes difficult to produce a CWM having a high coal concentration, a low viscosity and a good stability.
Now, the present inventors have considered that this problem might be solved by adjusting the particle diameter distribution according to a method of measuring the particle diameter distribution regarded as most adequate, and have made extensive research! As a result, we have succeeded in obtaining the objective CWM having a high coal concentration, a 1GW viscosity and a good stability.
The object of the present invention is to provide a process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability.
SUMMARY OF THE INVENTION
The present invention is characterized briefly in that the particle diameter distribution of coal particles is measured relative to all the particle diameter ranges accordlng to a definite method for measurement and then the particle diameter dlstrlbution is adjusted so as to reduce t~e viscosity of a coal-water slurry at high coal concentra~ions and make partlcle settling minimum i.e. improve the so-called stability.
.
The present invention resides in the following process:
''~3 ' ' .
_ 4 - ~25300~
In the process for producing a coal-water slurry having coal particles dispersed in water, a process for producing a coal-water slurry having a high coal concentration, a low viscosity and a good stability, which process comprises causing the slurry to have a compo~ition of coal particles, so that when the coal particles are divided into 8 fractions (Fl, F2, -----and F8), each having a particle diameter range listed below ((DL/4 ~
DL), (DL/42~ less than DL/4), ----- (DL/47 ~ 0), wherein DL
represents the maximum particle size of the coal particles), then the proportions by weight of the coal particles contained in the respective fractions, relative to the total weight of the coal particles contained in the slurry can fall within the following numeral value ranges:
Fl: ~DL/4 to DL) --- 29.0 to 50.0% by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0% by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0% by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0% by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0% by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2% by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0% by weight F8: (DL/47 to 0) --- 0.7 to 9.0% by weight BRIEF DESCRIPTION OF THE DRAWINGS
Fig. l shows a chart illustrating the particle sizes of low viscosity slurries and cumulative par*icle diameter .
distributions thereof.
.
.~ .
~253006 , -Fig. 2 shows a bar chart illustrating particle ~ ze and proportions by weight of the respective fractions.
Fig. 3 shows a diagram illustrating the relationship between par~icle size distributions and slurry viscosities.
Fig. 4 shows a chart illustrating the relationship between particle size distributions and stability.
Fig. 5 shows a chart illustrating the relationship between the amount of dispersant added and viscosity.
Fig. 6 shows a chart illustrating ~he relationship betweeen pH and viscosity.
Fig. 7 shows a chart illustrating the relationship between the amount of ultrafine particles of 0.05 ~m or less added and stability.
Fig. 8 shows a view of piping system illustrating an embodiment of an apparatus for producing CWM.
Figs.9 and 10 each show a chart illustrating the particle size af slurry produced by the apparatus of Fig. 8 and cumulative sieve pass proportion by weight.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described referring to the accompanying drawings.
Coal is ground in the wet or dry manner by means of a mill and a part of the resulting particles is taken to measure their particle size distribution. In measuring the particle size distributioni it was considered that the weight proportion of finely divided particles had a great influence upon the viscosity and the stability relatlve to .: ' ~ 2530~
settlng of slurry; thus ln an example, the partlcles were divlded into the following 8 fractions (each a constituent part as a group), and the respective fractions were each sieved by a sieve most adequate thereto (e.g. sieve according to JIS standards or millipore ~ilter having the particle size well adjusted ) to measure the weight of the fraction.
In the following list, DL represents the maximum particle diameter of particles. Fl ~ F8 represent symbols of the respective fractions.
Particle diameter range Fl: DL~4 ~ DL
F2 DL/42 ~ less than DL/4 F3 DL~43 ~J less than DL/4 F4 DL~4 ~ less than DL/43 F5 DL/45 ~ less than DL/4 F6 DL/46 ~ less than DL/45 F7 DL~4 ~ less than DL~46 F8 l ess than DL/4 20In the present invention, particles were divided into 8 fractions for measurement, but the number of fractions is not always limited to 8, but practically it may be 5 to 15 unless the distribution of the partlcle sizes changes.
"~ More than one kind of coal or coal slurry were mixed so that the constituent proportions by weight of Fl rJ F8 might have a certain value, respectively, and if necessary, . . . .
' water was added for adjusting the water content, to study i' ` . ' ' 1, ' .: ' .
~ ~ .
.
~l253006 .. .
their vlscositles. In thls case, if the maxlmum partlcle size DL is too large, the amount of unburned matter at the time of combution increases, while if it is too small, the slurry viscosity increases; hénce the maximum particle size DL was made 44 to 420 ~m.
Further, a certain kind of coal was chosen and the proportions of fractions were varied to study the influence upon viscosity. Further, when proportions of fractions exhibiting a relatively low viscosity were converted into cumulative distributions, a tendency was found. Fig. 1 shows a chart illustrating the relationship between the particle size and the cumulative sieve pass weight proportion in the case where three kinds of slurries (No.l ^~
No.3) were prepared from coal A (bituminous coal, ash content 9.5 %). There are shown cumulative particle size distributions in the case of a coal concentration of 70 % and 1,000 cP viscosity or less. In thiscase, the particle size DLis 297~m and only distributions of particle sizes of 1 ~m or larger are shown. Further, the slurry viscosity refers to numeral values obtained when an inner cylinder-rotation type viscometer was rotated at a shear rate of 90 sec 1 for 5 minutes. It is seen from Fig. 1 that the proportions in the case of 1 ~um or more each constitute a nearly straight line. Further, when the -cumulative sieve weight proportion U(D)% is 100 % at D = DL Ds ~minlmum partlcle diameter) at which U(D) = 0 % should be present. Thus, we propose the following equations (1) and (2) as those indicatlng a particle slze distribution mode of ~i j. ~, ................ . .
!~
.
- . . .
" ~
coal partlcles contalned ln a slurry exhlbltlng a low viscoslty at a high coal concentration:
U(D) = ( s ) x 100 % ____- (1) - D
5Dq - Dq Dq - Dq _____ (2) wherein q represents an index of particle size distri-bution, and U(D) represents cumulative % by weight of the particles of smaller diameter than a particle diameter D.
In both the equation (1) and (2), when D = DL, U(D) = 100%, and when D = Ds, U(D) = 0 ~. That is, these equations correspond well to practical particle size distributions.
If Ds = in the equation (1) and (2), the equations both give the following equation ~3):
U(D) = ( - ) x 100 % ----- (3) DL
This equation (3) corresponds to Andreasen's equation which has been known as a particle size distribution equatlon giving the closest packing for powder of a continuous particle size system. As to this Andreasen's equation, studies were made in the past, and it was confirmed that when q = 0.35 ^~ 0.40, the percentage packing attains the maximum.
The percentage packing, however, varies depending on particle shapes, and as to the systematic relatlonship between the q value and the slurry viscosity and stability of coal-water slurry, no study has never been made. Further,-Andreasen's equation i8 a distrlbution equation in the case where particles B
~253006 g having an infinitesimal partlcle diameter were presumed, but the equation cannot be, as it is, applied to practical coal-water slurry. Whereas, the present inventors confirmed that the equation (1) and (2) correspond ~ell to practical distributions.
Fig. 2 shows the weight proportions of the respective fractions in the case where DL = 297 pm, Ds = 0.01 ~m and q = 0.3 in the equations (1) and (2). In this case, in order to compare the particle diameters more strictly, particles were divided into the following 15 fractions (dotted lines in Fig. 2 indicate the case of the equation (2) and solid lines therein indicate the case of the equation (1)):
Particle size range (1) Fl: DL/2 ~ DL
(2) F2: DL/2 ~ less than DL/2
(3) F3: DL/23 ~J less than DL/22
(4) F4: DL/2 ~J less than DL/23
(5) F5: DL/25 ~ less than DL/24
(6) F6: DL/25 ~ less than DL/25
(7) F7: DL/27 ~ less than DL/26
(8) F8: DL/28 ~ less than DL/27
(9) Fg: DL/2 ~ less than DL/28 ~10) Flo: DLj210 ~ less than DL/29 (11) F11: DL/211 ~ less than DL/210 (12) F12: DL/2 2 ~ less than DL/211 - -(13) F13: DL/213 ~ less than DL/212 (14) F14: DLj214 ~ less than DL/213 (15) F15: less than DL/214 .
,~.. ,. - :
` ~ lo - ~253006 It 18 seen that the case of the equatlon (1) is dlfferent from that of the equation (2) ln that the proportlon of finely divided particles is higher and there are minimum points F13 and F14 where the weight proportion becomes minimum.
~hus, the present inventors varied the values of DL, Ds and q in the equations (1) and (2) to study their influences upon the viscosity and stability of slurry, whereby many findings could be obtained.
From these findings, coal-water slurry of the present invention is preferably composed so that diameter distribution of coal particles having particle diameters in the range of 1,000 ~um to 0.005 ~m substantially satisfies the following equation and the following ranges of numeral values:
/ D - D ~q (1) U(D) = s x 100 D - D
(2) DL = 44 ~ 1,000 ~m (3) Ds = 0.005 ~ 0.1 ~um (4) q = 0.25 ~ 0.50 wherein D represents a.particle size of coal particles; DL, the maximum particle size thereof; Ds, the minimum particle size thereof; ana q, an index of particle size distribution~
Further, the slurry is preferably composed so that coal paricles of 1 um or less can be present ~ 25 in an-amount of 5 to 46 % by weight and those of 0.05 ~m or `~ less can be present in an amount of 0.5 % or more, more preferably 1 % or more.
I ' .
!
2s3Qo6 Further, it is preferable that the coal-water has a coal content of 60 to 80 % by weight and a vi~cosity of S,00~
cP or less, in terms of numeral values obtained when an inner cylinder-rotation type viscometer is rotated at a shear rate of 90 sec l for 5 minutes.
Coal-water slurry of the present invention may contain at least one kind of anionic dispersant selected from the group consisting of naphthalenesulfonic acid, orthophosphoric acid, polyphosphoric acids represented by Hn+2PnO2n+l (n~ 2) or HnPnO2n tn >3), tartaric acid, oxalic acid, citric acid, ethylenediamine tetraacetate, ligninsulfonic acid, salts or condensates of the foregoing, tannins including quebracho-tannin and metal salts of carboxymethylcellulose, as a dispersant for coal particles in an amount of 3 % by lS weight, or less, preferably 1.5 % or less, based on the weight of the coal weight.
Further, at least one kind of pH-adjustors selected from the group consisting of sodium hydroxide, potassium hydroxide, bari~m hydroxide and sodium carbonate is added to the slurry as a pH-adjustor for rendering the pH value of the slurry 7 or more, in an amount of 3 % or less, preferably 1.5 % or less, based on the coal weight.
The present invention will be described in more detai]
by way of Examples.
Example l .
With coal A (bltuminous coal, ash content 9-.5 %), the proportions of the respective ractions were adjusted 1 . . . .- .
., - , ~.253006 according to the above-mentioned method to prepare 20 kinds of coal samples having particle size distributions corresponding to DL = 297 ~m and 149 ~m, Ds = 0.01 ~m and q = 0.15, 0.20. 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55 and 0.60 in the equation (1), followed by preparing a slurry having a coal concentration of 72 ~ by adjusting water content from the respective samples, thereafter adding a poly-sodium naphthalenesulfonate as dispersant in an amount of 0.5 %
based on the coal weight and sodium hydroxide as pH adjustor in an amount of 0.1 % based thereon and measuring their slurry viscosities. The results are shown in Fig. 3. It was observed that the viscosities became minimum at q = 0.40 ^J 0.45 irrespective of DL.
The same studies were made as to the equation (2) to similarly give the minimum viscosities at q = 0.40 ~ 0.45.
Further, it was observed that the viscosity values, too, accorded nearly with the above in the case of the same values f DL' Ds and q-Further, the same studies were made on other kinds of coals to give the minimum viscosities at q = 0 40 rV 0 50 Example 2 With the same slurries as in Example 1, their stabilities were studied. Each of the slurries was placed in a 500 ml graduated cylinder up to a depth of 170 mm, followed by allowing a glass stick o 5 mm in diameter and 10 g ln weight to penetrate thereinto only by its self weight to observe the change in the penetration time during which the stick reached B
~.253006 the bottom of the cylinder. Fig. 4 shows the relationship between the penetration time at the time when 30 days lapsed after preparation of the slurries (the penetration time just after the preparation being made 1), and the q value.
Namely Fig. 4 shows comparison of stabilities as to the slurries having viscosities shown in Fig. 3 and DL = 297 ,um.
The penetration time became minimum at q = 0.25 ^~ 0.35, and , it is seen that the penetration time is shorter and the stablility is superior in the case of the equation (1) as compared with those in the case of the equation (2).
Other kinds of coals were studied varying ~L~ etc. to obtain similar results.
It was found through Examples 1 and 2 that slurries according to the equation (1) were superior in stability to those according to the equation (2) and they exhibited equal values as to viscosity. Further it was found that in view of viscosity and stability, particle size distrib~ticns at q = 0.25 ^~ 0.50 in the equation (1) were preferable.
Example 3 With coal B (bituminous coal, ash content 13.6 %), Example 1 was repeated to prepare a slurry having a partiçle size distribution corresponding to DL ='297 ~m, Ds = 0.01 ,um and q = 0.40 in the equation (l) and a coal çoncentration , of 70 %. A condensate of sodium'naphthalnne suIfonate as dispersant was added,to the slurry to observe the relation-ship between its amounts add,ed and the slurry viscosities.-The results are shown in Fig. 5. In this casej the addition :,, -, , .
~253006 amounts are values based on the coal weight, and sodium hydroxide was added as pH adjustor in an amount of 0.1 based on the coal weight.
The~viscosities became minimum in an addition amount of 0.5 % of the dispersant, and more amounts resulted in an adverse effect.
Other kinds of coals were similarly studied, and the viscosities became minimum in addition amounts of 0.2 ^~ 1.2 ~.
When other anionic dispersants were added, slurries having a minimum viscosity was similarly obtained in addition amounts of 0.1 ~ 1.5 %.
Example 4 With coal B ~bituminous coal, ash content 13.6 ~), the same slurry as in Example 3 was prepared, followed by varying the amount of sodium hydroxide added, in a fixed amount of a condensate, of sodium naphthalenesulfonate added of 0.5 ~
to adjust the pH of slurry to thereby study the influence of pH upon slurry viscosity. The results are shown in Fig. 6.
Up to pH 8, the higher the pH, the lower the slurry viscosity, and at higher pHs, the viscosity is almost unchanged. Taking into consideration the amount of sodium hydroxide consumed and corrosion of material, a pH of 7 ~ 9 is preferred. In the case of coal, although the pH of slurry prepared therefrom varies depending on the kind of coal and the oxidation degree of its surface, the amount of sodium hydroxide added, necessary for adjusting the pH to 7 ~v 9, is about 0 to 1.0 based on the weight of coal.
~253006 Example 5 Ultrafine paricles having passed through a millipore filter of 0.05 ,um were further added to a slurry of coal B
having a particle size distribution expressed ~y the equation (1) and corresponding to DL = 297 ~m, Ds = 0.01 ~m and q = 0.40, to study the influence of the ultrafine particles upon the stability of the slurry. The results are shown in Fig. 7. In this figure, the penetration time of the oridinate axis refers to a ratio of the penetration time in 30 days after preparation of slurry to that just after the preparation, and the amount of ultrafine particles added refers to a proportion thereof based on the total weight of coal after the addition.
The stability is best in an amount of the ultrafine particles added of 3 %, and it is seen that particles of 0.05 ~m or less contributed to the slurry stability. Studies were carried out varying the particle diameter distribution and the kind of coal. As a`result it was found that the viscosity was unchanged when the weight of particles of 0.05 ~um or less effective for improving the slurry stability fell within the range of about 0.5 to 6.5 % (preferably 1.0 to 4.0 %).
Further, it was found that this tendency was unchanged even when the kind of coal, its concentration and DL were varied.
Example 6 With coal A (bituminous coal, ash content 9.5 %), a process for preparing a slurry having a particle size distribution coresponding to the equations (1) and (2~, by ~3 , ~253006 means of a tube ball mlll (650 mm in diameter x 250 mm in length) was studled. The apparatus and flow in this case are shown in Fig. 8. Coal stored in a bunker l was fed into a mill 3 through a feeder 2, and at the same time, water and additives were fed into the mill through a feed pipe 4. At that time, conditions were established so as to give a coal concentration of 70 % and average retention times of coal in the mill, of 90 minutes and 120 minutes, and when a stationary state was attained, the resulting slurries were taken to observe their particle size distributions. The results are shown in Fig. 9. It is seen that the slurries had particle size distributions corresponding to DL = 420 ,um, Ds = 0.04 ~um and q = 0.40, and DL = 300 ~m, Ds = 0.01 ~um and q = 0.40 in the equation (2).
Next, 10 % of the slurry of the average retention time of 120 minutes discharged from the exit of the mill was returned to the inlet of the mill and again ground. When a stationary state was attained, particle sizes were measured to give a particle size distribution correspond-ing to DL = 300~um, Ds = 0.01~um and q = 0.40 in the equation ~l). See Fig. 10.
Other kinds of coals were similarly studied. As a result, it was found that in order to prepare a-slurry having a particle size distribution according to the equation (l) and a good stability, it was impossible to achieve the object merely by adjusting the retention time in the mill, but a process fo recycling 10 ~ 50 % of the product slurry (i.e.
:.
,.~ ,~ .
~2~;300~;
recycling feed) was effective.
In view of the above-mentioned Examples, it has been found that in order to obtain a CWM having a high coal concentration, a low viscosity and a good stability, if a S strict and systematic control of the particle size distribution is conducted by means of sieves and the particle size distribution is caused to comply with the following equation, then the viscosity and stability of the resulting slurry becomes optimum:
( D - D ~q ~ D - D J
wherein q = 0.25 to 0.50 D~ = 44 to 420 ~m Ds = 0.005 to O.l~um Further it has been found that when finely divided particles of 0.05 ~m or less are present in an amount of 0.5 to 6.5 % (preferably 1.0 to 4.0 %), the slurry stability becomes optimun.
Furthermore it has been found that the amount of the dispersant added is optimum in 0.1 to 1.5 % and it i5 preferred to add a pH adjustor so as to give a pH of 7 to 9.
When this invention is conducted, there is exhibited an effectiveness of rendering a mixture of water with powdered coal, a water-coal slurry having-a high coal concentratlon, a low viscosity and a good stability with settlngs being difficulty form~d.
,~.. ,. - :
` ~ lo - ~253006 It 18 seen that the case of the equatlon (1) is dlfferent from that of the equation (2) ln that the proportlon of finely divided particles is higher and there are minimum points F13 and F14 where the weight proportion becomes minimum.
~hus, the present inventors varied the values of DL, Ds and q in the equations (1) and (2) to study their influences upon the viscosity and stability of slurry, whereby many findings could be obtained.
From these findings, coal-water slurry of the present invention is preferably composed so that diameter distribution of coal particles having particle diameters in the range of 1,000 ~um to 0.005 ~m substantially satisfies the following equation and the following ranges of numeral values:
/ D - D ~q (1) U(D) = s x 100 D - D
(2) DL = 44 ~ 1,000 ~m (3) Ds = 0.005 ~ 0.1 ~um (4) q = 0.25 ~ 0.50 wherein D represents a.particle size of coal particles; DL, the maximum particle size thereof; Ds, the minimum particle size thereof; ana q, an index of particle size distribution~
Further, the slurry is preferably composed so that coal paricles of 1 um or less can be present ~ 25 in an-amount of 5 to 46 % by weight and those of 0.05 ~m or `~ less can be present in an amount of 0.5 % or more, more preferably 1 % or more.
I ' .
!
2s3Qo6 Further, it is preferable that the coal-water has a coal content of 60 to 80 % by weight and a vi~cosity of S,00~
cP or less, in terms of numeral values obtained when an inner cylinder-rotation type viscometer is rotated at a shear rate of 90 sec l for 5 minutes.
Coal-water slurry of the present invention may contain at least one kind of anionic dispersant selected from the group consisting of naphthalenesulfonic acid, orthophosphoric acid, polyphosphoric acids represented by Hn+2PnO2n+l (n~ 2) or HnPnO2n tn >3), tartaric acid, oxalic acid, citric acid, ethylenediamine tetraacetate, ligninsulfonic acid, salts or condensates of the foregoing, tannins including quebracho-tannin and metal salts of carboxymethylcellulose, as a dispersant for coal particles in an amount of 3 % by lS weight, or less, preferably 1.5 % or less, based on the weight of the coal weight.
Further, at least one kind of pH-adjustors selected from the group consisting of sodium hydroxide, potassium hydroxide, bari~m hydroxide and sodium carbonate is added to the slurry as a pH-adjustor for rendering the pH value of the slurry 7 or more, in an amount of 3 % or less, preferably 1.5 % or less, based on the coal weight.
The present invention will be described in more detai]
by way of Examples.
Example l .
With coal A (bltuminous coal, ash content 9-.5 %), the proportions of the respective ractions were adjusted 1 . . . .- .
., - , ~.253006 according to the above-mentioned method to prepare 20 kinds of coal samples having particle size distributions corresponding to DL = 297 ~m and 149 ~m, Ds = 0.01 ~m and q = 0.15, 0.20. 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55 and 0.60 in the equation (1), followed by preparing a slurry having a coal concentration of 72 ~ by adjusting water content from the respective samples, thereafter adding a poly-sodium naphthalenesulfonate as dispersant in an amount of 0.5 %
based on the coal weight and sodium hydroxide as pH adjustor in an amount of 0.1 % based thereon and measuring their slurry viscosities. The results are shown in Fig. 3. It was observed that the viscosities became minimum at q = 0.40 ^J 0.45 irrespective of DL.
The same studies were made as to the equation (2) to similarly give the minimum viscosities at q = 0.40 ~ 0.45.
Further, it was observed that the viscosity values, too, accorded nearly with the above in the case of the same values f DL' Ds and q-Further, the same studies were made on other kinds of coals to give the minimum viscosities at q = 0 40 rV 0 50 Example 2 With the same slurries as in Example 1, their stabilities were studied. Each of the slurries was placed in a 500 ml graduated cylinder up to a depth of 170 mm, followed by allowing a glass stick o 5 mm in diameter and 10 g ln weight to penetrate thereinto only by its self weight to observe the change in the penetration time during which the stick reached B
~.253006 the bottom of the cylinder. Fig. 4 shows the relationship between the penetration time at the time when 30 days lapsed after preparation of the slurries (the penetration time just after the preparation being made 1), and the q value.
Namely Fig. 4 shows comparison of stabilities as to the slurries having viscosities shown in Fig. 3 and DL = 297 ,um.
The penetration time became minimum at q = 0.25 ^~ 0.35, and , it is seen that the penetration time is shorter and the stablility is superior in the case of the equation (1) as compared with those in the case of the equation (2).
Other kinds of coals were studied varying ~L~ etc. to obtain similar results.
It was found through Examples 1 and 2 that slurries according to the equation (1) were superior in stability to those according to the equation (2) and they exhibited equal values as to viscosity. Further it was found that in view of viscosity and stability, particle size distrib~ticns at q = 0.25 ^~ 0.50 in the equation (1) were preferable.
Example 3 With coal B (bituminous coal, ash content 13.6 %), Example 1 was repeated to prepare a slurry having a partiçle size distribution corresponding to DL ='297 ~m, Ds = 0.01 ,um and q = 0.40 in the equation (l) and a coal çoncentration , of 70 %. A condensate of sodium'naphthalnne suIfonate as dispersant was added,to the slurry to observe the relation-ship between its amounts add,ed and the slurry viscosities.-The results are shown in Fig. 5. In this casej the addition :,, -, , .
~253006 amounts are values based on the coal weight, and sodium hydroxide was added as pH adjustor in an amount of 0.1 based on the coal weight.
The~viscosities became minimum in an addition amount of 0.5 % of the dispersant, and more amounts resulted in an adverse effect.
Other kinds of coals were similarly studied, and the viscosities became minimum in addition amounts of 0.2 ^~ 1.2 ~.
When other anionic dispersants were added, slurries having a minimum viscosity was similarly obtained in addition amounts of 0.1 ~ 1.5 %.
Example 4 With coal B ~bituminous coal, ash content 13.6 ~), the same slurry as in Example 3 was prepared, followed by varying the amount of sodium hydroxide added, in a fixed amount of a condensate, of sodium naphthalenesulfonate added of 0.5 ~
to adjust the pH of slurry to thereby study the influence of pH upon slurry viscosity. The results are shown in Fig. 6.
Up to pH 8, the higher the pH, the lower the slurry viscosity, and at higher pHs, the viscosity is almost unchanged. Taking into consideration the amount of sodium hydroxide consumed and corrosion of material, a pH of 7 ~ 9 is preferred. In the case of coal, although the pH of slurry prepared therefrom varies depending on the kind of coal and the oxidation degree of its surface, the amount of sodium hydroxide added, necessary for adjusting the pH to 7 ~v 9, is about 0 to 1.0 based on the weight of coal.
~253006 Example 5 Ultrafine paricles having passed through a millipore filter of 0.05 ,um were further added to a slurry of coal B
having a particle size distribution expressed ~y the equation (1) and corresponding to DL = 297 ~m, Ds = 0.01 ~m and q = 0.40, to study the influence of the ultrafine particles upon the stability of the slurry. The results are shown in Fig. 7. In this figure, the penetration time of the oridinate axis refers to a ratio of the penetration time in 30 days after preparation of slurry to that just after the preparation, and the amount of ultrafine particles added refers to a proportion thereof based on the total weight of coal after the addition.
The stability is best in an amount of the ultrafine particles added of 3 %, and it is seen that particles of 0.05 ~m or less contributed to the slurry stability. Studies were carried out varying the particle diameter distribution and the kind of coal. As a`result it was found that the viscosity was unchanged when the weight of particles of 0.05 ~um or less effective for improving the slurry stability fell within the range of about 0.5 to 6.5 % (preferably 1.0 to 4.0 %).
Further, it was found that this tendency was unchanged even when the kind of coal, its concentration and DL were varied.
Example 6 With coal A (bituminous coal, ash content 9.5 %), a process for preparing a slurry having a particle size distribution coresponding to the equations (1) and (2~, by ~3 , ~253006 means of a tube ball mlll (650 mm in diameter x 250 mm in length) was studled. The apparatus and flow in this case are shown in Fig. 8. Coal stored in a bunker l was fed into a mill 3 through a feeder 2, and at the same time, water and additives were fed into the mill through a feed pipe 4. At that time, conditions were established so as to give a coal concentration of 70 % and average retention times of coal in the mill, of 90 minutes and 120 minutes, and when a stationary state was attained, the resulting slurries were taken to observe their particle size distributions. The results are shown in Fig. 9. It is seen that the slurries had particle size distributions corresponding to DL = 420 ,um, Ds = 0.04 ~um and q = 0.40, and DL = 300 ~m, Ds = 0.01 ~um and q = 0.40 in the equation (2).
Next, 10 % of the slurry of the average retention time of 120 minutes discharged from the exit of the mill was returned to the inlet of the mill and again ground. When a stationary state was attained, particle sizes were measured to give a particle size distribution correspond-ing to DL = 300~um, Ds = 0.01~um and q = 0.40 in the equation ~l). See Fig. 10.
Other kinds of coals were similarly studied. As a result, it was found that in order to prepare a-slurry having a particle size distribution according to the equation (l) and a good stability, it was impossible to achieve the object merely by adjusting the retention time in the mill, but a process fo recycling 10 ~ 50 % of the product slurry (i.e.
:.
,.~ ,~ .
~2~;300~;
recycling feed) was effective.
In view of the above-mentioned Examples, it has been found that in order to obtain a CWM having a high coal concentration, a low viscosity and a good stability, if a S strict and systematic control of the particle size distribution is conducted by means of sieves and the particle size distribution is caused to comply with the following equation, then the viscosity and stability of the resulting slurry becomes optimum:
( D - D ~q ~ D - D J
wherein q = 0.25 to 0.50 D~ = 44 to 420 ~m Ds = 0.005 to O.l~um Further it has been found that when finely divided particles of 0.05 ~m or less are present in an amount of 0.5 to 6.5 % (preferably 1.0 to 4.0 %), the slurry stability becomes optimun.
Furthermore it has been found that the amount of the dispersant added is optimum in 0.1 to 1.5 % and it i5 preferred to add a pH adjustor so as to give a pH of 7 to 9.
When this invention is conducted, there is exhibited an effectiveness of rendering a mixture of water with powdered coal, a water-coal slurry having-a high coal concentratlon, a low viscosity and a good stability with settlngs being difficulty form~d.
Claims (10)
1. A process for producing a coal-water slurry having a coal content of 60 to 80 % by weight and a viscotiy of 5,000 cP or less, which process comprises causing the slurry to have a composition of coal particles, then when the coal particles are divided into 8 fractions F1, F2, ---- and F8, having a particle diameter range listed below,((DL/4~DL), (DL/42~less than DL/4), ---- (DL/47~0), wherein DL
represents the maximum particle diameter of the coal particles), then the proportions by weight of the coal particles contained in the respective fractions, relative to the total weight of the coal particles contained in the slurry fall within the following ranges of numeral values:
F1: (DL/4 to DL) --- 29.0 to 50.0 % by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0 % by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0 % by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0 % by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0 % by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2 % by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0 % by weight F8: (DL/47 to 0) --- 0.7 to 9.0 % by weight
represents the maximum particle diameter of the coal particles), then the proportions by weight of the coal particles contained in the respective fractions, relative to the total weight of the coal particles contained in the slurry fall within the following ranges of numeral values:
F1: (DL/4 to DL) --- 29.0 to 50.0 % by weight F2: (DL/42 to less than DL/4) --- 20.0 to 25.0 % by weight F3: (DL/43 to less than DL/42) --- 12.0 to 15.0 % by weight F4: (DL/44 to less than DL/43) --- 6.0 to 10.0 % by weight F5: (DL/45 to less than DL/44) --- 3.0 to 12.0 % by weight F6: (DL/46 to less than DL/45) --- 1.5 to 5.2 % by weight F7: (DL/47 to less than DL/46) --- 0.8 to 4.0 % by weight F8: (DL/47 to 0) --- 0.7 to 9.0 % by weight
2. A process according to claim 1, wherein the particle diameter distribution of coal particles having particle diameters in the range of 1,000 µm to 0.005 µm substantially satisfies the following equation and the following ranges of numerical values:
(1) U(D) = x 100 (2) DL = 44 ~ 1,000 µm (3) Ds = 0.005 ~ 0.1 µm (4) q = 0.25 ~ 0.50 wherein D represents a particle diameter of coal particles;
DL, the maximum particle diameter thereof; Ds, the minimum particle diameter thereof; and q, an index of particle size distribution.
(1) U(D) = x 100 (2) DL = 44 ~ 1,000 µm (3) Ds = 0.005 ~ 0.1 µm (4) q = 0.25 ~ 0.50 wherein D represents a particle diameter of coal particles;
DL, the maximum particle diameter thereof; Ds, the minimum particle diameter thereof; and q, an index of particle size distribution.
3. A process according to claim 1, wherein coal particles of 1 µm or less are present in an amount of 5 to 46 % by weight and those of 0.05 µm or less are present in an amount of 0.5% or more.
4. A process according to claim 1, wherein said viscosity values are evaluated at a shear rate of 90 sec-1
4. A process according to claim 1, wherein said viscosity values are evaluated at a shear rate of 90 sec-1
Claim 4 continued...
after 5 minutes of rotation of the inner cylinder of an inner cylinder rotation-type viscometer.
after 5 minutes of rotation of the inner cylinder of an inner cylinder rotation-type viscometer.
5. A process according to claim 1, wherein at least one kind of anionic dispersants selected from the group consisting of naphthalene sulfonic acid, orthophosphoric acid, polyphosphoric acids represented by Hn+2PnO2n+1 (n?2) or HnPnO2n (n?3), tartaric acid, oxalic acid, citric acid, ethylenediamine tetraacetate, ligninsulfonic acid, salts and condensates of the foregoing, tannins including quebracho-tannin and metal salts of carboxymethylcellulose, is added to the slurry, as a dispersant for coal particles in an amount of 3 % by weight or less based on the coal weight.
6. A process according to claim 1, wherein at least one kind of pH-adjustors selected from the group consisting of sodium hydroxide, potassium hydroxide, barium hydroxide and sodium carbonate is added to the slurry as a pH-adjustor for rendering the pH value of the slurry 7 or more, in an amount of 3 % less based on the coal weight.
7. A process according to claim 2, wherein coal particles in the slurry is composed so that coal particles of 1 µm or less are present in an amount of 5 to 46 % by
7. A process according to claim 2, wherein coal particles in the slurry is composed so that coal particles of 1 µm or less are present in an amount of 5 to 46 % by
Claim 7 continued ...
weight and those of 0.05 µm or less are present in an amount of 0.5 % or more.
weight and those of 0.05 µm or less are present in an amount of 0.5 % or more.
8. A process according to claim 3, wherein the slurry has a coal content of 60 to 80 % by weight and viscosity of 5,000 cP or less in terms of numerical values obtained when an inner cylinder-rotation type viscometer is rotated at a shear rate of 90 sec-1 for 5 minutes.
9. A process according to claim 4, wherein at least one kind of anionic dispersants selected from the group consisting of napthahalene sulfonic acid, orthophosphoric acid, polyphosphoric acids represented by Hn+2PnO2n+1 (n?2) or HnPnO2n (n?3), tartaric acid, oxalic acid, citric acid, ethylenediamine tetracetate, ligninsulfonic acid, salts and condensates of the foregoing, tannins including quebracho-tannin and metal salts of carboxymethylcellulose, is added to the slurry, as a dispersant for coal particles in an amount of 3 % by weight or less based on the coal weight.
10. A process according to claim 5, wherein at least one kind of pH-adjustors selected from the group consisting of sodium hydroxide, potassium hydroxide, barium hydroxide and sodium carbonate is added to the slurry as a pH-adjustor for rendering the pH value of the slurry 7 or more, in an amount of 3 % less based on the coal weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000457256A CA1253006A (en) | 1984-06-22 | 1984-06-22 | Process for producing a high concentration coal-water slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000457256A CA1253006A (en) | 1984-06-22 | 1984-06-22 | Process for producing a high concentration coal-water slurry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253006A true CA1253006A (en) | 1989-04-25 |
Family
ID=4128150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457256A Expired CA1253006A (en) | 1984-06-22 | 1984-06-22 | Process for producing a high concentration coal-water slurry |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1253006A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937568A (en) * | 2014-04-17 | 2014-07-23 | 中国五环工程有限公司 | Method for preparing high-concentration water-coal-slurry through coal with high oxygen content |
-
1984
- 1984-06-22 CA CA000457256A patent/CA1253006A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937568A (en) * | 2014-04-17 | 2014-07-23 | 中国五环工程有限公司 | Method for preparing high-concentration water-coal-slurry through coal with high oxygen content |
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