CA1210555A - Process for pearling sulfur - Google Patents
Process for pearling sulfurInfo
- Publication number
- CA1210555A CA1210555A CA000437112A CA437112A CA1210555A CA 1210555 A CA1210555 A CA 1210555A CA 000437112 A CA000437112 A CA 000437112A CA 437112 A CA437112 A CA 437112A CA 1210555 A CA1210555 A CA 1210555A
- Authority
- CA
- Canada
- Prior art keywords
- sulfur
- water
- channel
- pearling
- lambda
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0237—Converting into particles, e.g. by granulation, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adornments (AREA)
- Glanulating (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Farming Of Fish And Shellfish (AREA)
Abstract
ABSTRACT
The invention is concerned with a process and apparatus for pearling sulfur. Water is fed to a linear channel means of rectangular cross-section having sidewalls and a bottom, and is circulated in constant movement in the channel. The velocity of the circulat-ing water in the channel is controlled. The level of the circulating water in the channel is also controlled by gate means extending between the sidewalls. At least one stream of liquid sulfur in the form of lambda sulfur is fed into the circulating water in the channel, and the temperature of the stream containing lambda sulfur is controlled up to a maximum temperature of about 157°C. The lambda sulfur is pearled in the circulating water to form a pearled sulfur product having a granulometry controlled by the water level.
The pearls are then recovered and dried.
The invention is concerned with a process and apparatus for pearling sulfur. Water is fed to a linear channel means of rectangular cross-section having sidewalls and a bottom, and is circulated in constant movement in the channel. The velocity of the circulat-ing water in the channel is controlled. The level of the circulating water in the channel is also controlled by gate means extending between the sidewalls. At least one stream of liquid sulfur in the form of lambda sulfur is fed into the circulating water in the channel, and the temperature of the stream containing lambda sulfur is controlled up to a maximum temperature of about 157°C. The lambda sulfur is pearled in the circulating water to form a pearled sulfur product having a granulometry controlled by the water level.
The pearls are then recovered and dried.
Description
~2i(~5SS
Specification of the Patent of Invention of a "Process for Pearling Sulfur"
The present invention relates to a process for pearling sulfur and, as shown hereinafter, features simplicity, small investment costs and production of perfectly spherical and homogeneous sulfur pearls affording also the possibility of granulometric control of the product.
The handling of sulfur has always implied serious problems related to safety, pollution and contamination of adjacent areas.
The problems of handling sulfvr commence at the site where sulfur is mined. In mines using the PRASCH process liquid sulfur is pumped through pipes to solidify into enormous blocks of product.
When commercialized, the sulfur must be broken away from these enormous blocks with heavy machinery and prepared by grinding in order to exhibit better homogeneity and be more acceptable to clients.
In practice the grinding of sulfur has always presented a big problem.
Because of the numerous safety problems involved and a strong propensity for incipient fusion grinding operations are an almost exclusive attribution of the big producers.
~2~055S
The difficulties inherent to the grinding of sulfur have induced producers to do research with the object of developing safer and more efficient equipments.
The Freeport Sul~ur Company in the U. S. A. developed a mill according to the U.S. Patent 2 656 123.
In reality, sulfur producers generally do not guarantee the granulometry of the product and having accompanied said probl~m for many years we are in a position to say that commercial sulfur displays a great variety of granulometry.
The grinding of sulfur as well as the heterogeneity of the product imply a series of disadvantages:
- The dust generated during the grinding process and transportation.
Like all poor conductors of electricity sulfur rapidly accumulates static electricity.
For these reasons the system must be provided with the necessary protection, e.g., by adopting a confined system.
- ~round sulfur is generally corrosive, particularly when it is not very dry, which implies using compatible construction material.
- The system calls for additional safety measures such as constant flow of steam at sites of greater incidence of dust in order to prevent explosions.
;
lZlQ55S
- All metallic equipments must be buried to prevent accumulation of static electricity.
- Maintenance operations involving welding or use of manual tools can only be carried out after all the - 5 sulfur has been removed from the area.
- Use of tractors and loading shovels for the sole purpose of this operation and consequently additional consumption of fuel.
- Heterogeneous granulometry.
The product displays a granulometry varying from fine powder to lumps of 15 (fifteen) cms, aggravated by the fact that a reduction of the granulometry implies a substantial increase of fines.
- The grinding operation calls for great care and atten-tion on the part of the operator.
- And lastly, the make-up of the products makes market-ing more difficult.
The producers of sulfur recovered from petrochemical sources are using various methods to get rid of the 20 problem caused by the big blocks of sulfur.
Sulfur scalers of different types and capacities perform satisfactorily but require substantial investments as well as permanent maintenance.
~21Q555 Sulfur pearlers in pearling towers where the sulfur falls through nozzles at a certain height, usually with air in counter-current, are sometimes used with satisfactory results, but the cost is considerable.
Processes based on fragmentation in stron~ water jets with fall from a certain height, making the product fall on rotating obstacles to prevent agglomeration, were developed.
However, notwithstanding that the continuous operation of these fragmentation devices is reliable and the investment substantially small, the process exhibits the disadvantage of an excessively fine granulometry and the retention of a very great amount of water in the sulfur obtained because of the great number of recesses formed in the fragmented product. The extremely fine granulometry of the product as well as the porosity and the excessive retention of water make commercialization more difficult and raise the cost of transportation.
It is, therefore, of vital importance that the processiny of sulfur originating in conventional methods be carried out in such a way as not only to eliminate or reduce the above mentioned problems, i.e., handling, safety, maintenance of equipment, granulometry and product marketing etc., but also to provide a system which is simple and economically viable.
Therefore, one of the objects of the present invention is to provide a process for pearling sulfur originating in con-ventional methods of obtaining sulfur which overcomes the above mentioned inconveniences and renders a pearled sulfur product with the desired improved characteristics.
12~S5 5.
Particularly, the process according to the present invention af~ords a pearled sulfur product whose gra-nulometry can be adequately controlled during the process.
According to one aspect of the invention, there is provided a process for pearling sulfur, comprising feeding water to a linear channel means of rectangular cross-section having sidewalls and a bottom, and circulat-ing the water in constant movement in the channel. The velocity of the circulating water in the channel is con-trolled. The level of the circulating water in the channel is also controlled by gate means extending between the sidewalls. At least one stream of liquid sulfur in the form of lambda sulfur is fed into the circulating water in the channel, and the temperature of the stream containing lambda sulfur is controlled up to a maximum temperature of about 157C. The lambda sulfur in the circulating water is pearled to form a pearled sulfur product having a granulometry cvntrolled by the water level, and the pearls are then recovered and dried.
The stream of liquid sulfur is preferably formed by heating a solid sulfur charge.
According to a preferred embodiment of the invention, the water flows out of the channel through the gates and the granulometry of the pearls is controlled by adjusting the velocities of the water in and out of the channel.
The present invention also provides, in a further aspect thereof, an apparatus for pearling sulfur. The apparatus of the invention comprises linear channel ,~
5a.
means of rectangular cross-section having sidewalls - and a bottom, means for feeding water to the channel, means for circulating the water in constant movement in the channel and for controlling the velocity of the circulating water' and gate means extending between the sidewalls for controlling the level of the water circulating in the channel. The apparatus further includes means above the channel for feeding at least one stream of liquid sulfur in the form of lambda sulfur into the circulating water in said channel, means for controlling the temperature of the lambda sulfur up to a maximum temperature of about 157C;
- and means for recovering and drying sulfur pearls formed in the circulating water.
Preferably, the movement of the water in the channel is controlled by a flow homogenizer.
According to a preferred embodiment, a plurality of flow openings is arranged for providing a plurality of liquid sulfur streams into the circulating water.
The symbols used in the description are the following:
S~ = Rhombic sulfur S~ = Monoclinic sulfur S~ = Liquid free-flowing pale-yellow sulfur predominant at low temperatures S,u = Liquid viscous dark brown sulfur predominant at high temperatures S~ - Plastic sulfur ~ote: l- When S~ solidifies, it changes into S~ and S~, both of which are crystalline and soluble in carbon sulfide.
~21~555 - 5b -
Specification of the Patent of Invention of a "Process for Pearling Sulfur"
The present invention relates to a process for pearling sulfur and, as shown hereinafter, features simplicity, small investment costs and production of perfectly spherical and homogeneous sulfur pearls affording also the possibility of granulometric control of the product.
The handling of sulfur has always implied serious problems related to safety, pollution and contamination of adjacent areas.
The problems of handling sulfvr commence at the site where sulfur is mined. In mines using the PRASCH process liquid sulfur is pumped through pipes to solidify into enormous blocks of product.
When commercialized, the sulfur must be broken away from these enormous blocks with heavy machinery and prepared by grinding in order to exhibit better homogeneity and be more acceptable to clients.
In practice the grinding of sulfur has always presented a big problem.
Because of the numerous safety problems involved and a strong propensity for incipient fusion grinding operations are an almost exclusive attribution of the big producers.
~2~055S
The difficulties inherent to the grinding of sulfur have induced producers to do research with the object of developing safer and more efficient equipments.
The Freeport Sul~ur Company in the U. S. A. developed a mill according to the U.S. Patent 2 656 123.
In reality, sulfur producers generally do not guarantee the granulometry of the product and having accompanied said probl~m for many years we are in a position to say that commercial sulfur displays a great variety of granulometry.
The grinding of sulfur as well as the heterogeneity of the product imply a series of disadvantages:
- The dust generated during the grinding process and transportation.
Like all poor conductors of electricity sulfur rapidly accumulates static electricity.
For these reasons the system must be provided with the necessary protection, e.g., by adopting a confined system.
- ~round sulfur is generally corrosive, particularly when it is not very dry, which implies using compatible construction material.
- The system calls for additional safety measures such as constant flow of steam at sites of greater incidence of dust in order to prevent explosions.
;
lZlQ55S
- All metallic equipments must be buried to prevent accumulation of static electricity.
- Maintenance operations involving welding or use of manual tools can only be carried out after all the - 5 sulfur has been removed from the area.
- Use of tractors and loading shovels for the sole purpose of this operation and consequently additional consumption of fuel.
- Heterogeneous granulometry.
The product displays a granulometry varying from fine powder to lumps of 15 (fifteen) cms, aggravated by the fact that a reduction of the granulometry implies a substantial increase of fines.
- The grinding operation calls for great care and atten-tion on the part of the operator.
- And lastly, the make-up of the products makes market-ing more difficult.
The producers of sulfur recovered from petrochemical sources are using various methods to get rid of the 20 problem caused by the big blocks of sulfur.
Sulfur scalers of different types and capacities perform satisfactorily but require substantial investments as well as permanent maintenance.
~21Q555 Sulfur pearlers in pearling towers where the sulfur falls through nozzles at a certain height, usually with air in counter-current, are sometimes used with satisfactory results, but the cost is considerable.
Processes based on fragmentation in stron~ water jets with fall from a certain height, making the product fall on rotating obstacles to prevent agglomeration, were developed.
However, notwithstanding that the continuous operation of these fragmentation devices is reliable and the investment substantially small, the process exhibits the disadvantage of an excessively fine granulometry and the retention of a very great amount of water in the sulfur obtained because of the great number of recesses formed in the fragmented product. The extremely fine granulometry of the product as well as the porosity and the excessive retention of water make commercialization more difficult and raise the cost of transportation.
It is, therefore, of vital importance that the processiny of sulfur originating in conventional methods be carried out in such a way as not only to eliminate or reduce the above mentioned problems, i.e., handling, safety, maintenance of equipment, granulometry and product marketing etc., but also to provide a system which is simple and economically viable.
Therefore, one of the objects of the present invention is to provide a process for pearling sulfur originating in con-ventional methods of obtaining sulfur which overcomes the above mentioned inconveniences and renders a pearled sulfur product with the desired improved characteristics.
12~S5 5.
Particularly, the process according to the present invention af~ords a pearled sulfur product whose gra-nulometry can be adequately controlled during the process.
According to one aspect of the invention, there is provided a process for pearling sulfur, comprising feeding water to a linear channel means of rectangular cross-section having sidewalls and a bottom, and circulat-ing the water in constant movement in the channel. The velocity of the circulating water in the channel is con-trolled. The level of the circulating water in the channel is also controlled by gate means extending between the sidewalls. At least one stream of liquid sulfur in the form of lambda sulfur is fed into the circulating water in the channel, and the temperature of the stream containing lambda sulfur is controlled up to a maximum temperature of about 157C. The lambda sulfur in the circulating water is pearled to form a pearled sulfur product having a granulometry cvntrolled by the water level, and the pearls are then recovered and dried.
The stream of liquid sulfur is preferably formed by heating a solid sulfur charge.
According to a preferred embodiment of the invention, the water flows out of the channel through the gates and the granulometry of the pearls is controlled by adjusting the velocities of the water in and out of the channel.
The present invention also provides, in a further aspect thereof, an apparatus for pearling sulfur. The apparatus of the invention comprises linear channel ,~
5a.
means of rectangular cross-section having sidewalls - and a bottom, means for feeding water to the channel, means for circulating the water in constant movement in the channel and for controlling the velocity of the circulating water' and gate means extending between the sidewalls for controlling the level of the water circulating in the channel. The apparatus further includes means above the channel for feeding at least one stream of liquid sulfur in the form of lambda sulfur into the circulating water in said channel, means for controlling the temperature of the lambda sulfur up to a maximum temperature of about 157C;
- and means for recovering and drying sulfur pearls formed in the circulating water.
Preferably, the movement of the water in the channel is controlled by a flow homogenizer.
According to a preferred embodiment, a plurality of flow openings is arranged for providing a plurality of liquid sulfur streams into the circulating water.
The symbols used in the description are the following:
S~ = Rhombic sulfur S~ = Monoclinic sulfur S~ = Liquid free-flowing pale-yellow sulfur predominant at low temperatures S,u = Liquid viscous dark brown sulfur predominant at high temperatures S~ - Plastic sulfur ~ote: l- When S~ solidifies, it changes into S~ and S~, both of which are crystalline and soluble in carbon sulfide.
~21~555 - 5b -
2- When S~ solidifies, it changes into sr, i. e., plastic, amorphous and insoluble in carbon sulfide.
3- Therefore, the proportion of sulfur soluble and insoluble in carbon sulfide in solidified sulfur depends on the relative quantities of S~ and S~u present in the liquid at the moment of solidification and is a function of the temperature of liquid sulfur.
',' ``~.
~Z105SS
The process in accordance with the present invention is based on the characteristic that the suIfur in the lambda-form (S ~ ) solidifies passing through the forms of S
and S~ .
In the present invention the sulfur in the lan~bda-form is defined as sulfur whose temperature is comprised between the sulfur melting temperature and a temperature of approximetely 157C.
At temperatures above 157C significant amounts of sulfur are formed in the ~ form which upon solidifying form S y .
The~ form of sulfur, which is predominant at the above mentioned temperatures, affects not only the pearling process preventing the formation of sulfur pearls due to the plastic nature of SY and possibly causing obstruction, but also the pumping operation, since the viscosity of sulfur at high temperatures is not suitable for operations of this kind.
On the other hand, it was established that a liquid charge of sulfur of the specific type S ~ when added to water in constant movement affords the formation of solid sulfur pearls with satisfactory sphericity and homogeneity. It was also established that the granulometry of the pearls thus obtained can be adequately controlled during the pearlin~ process by adjusting the velocity of the water flow established during the process and/or adjusting the water level in the vessel where the charges of sulfur in the ~ form and of water co~e into contact, and/or adjusting the variation of the size of the openings for introducing the fulfur charge.
The process for pearling sulfur in accordance with the present invention is carried out by means of the following steps:
lzlasss 7.
a~ providing a charge of liquid sulfur in the form of lambda-sulfur; `
b~ adding said sulfur charge to water in constant movement, thereby forming sulfur pearls; and 5c) recovering and drying said pearls.
The liquid sulfur charge from step a~ can be obtained by heating a liquid or solid sulfur charge to a maximum temperature of about 157C. However, a sulfur charge in a liquid state is preferred.
The addition of sulfur to water described in step b) is normally carried out by means of devices comprising openings localized in a position and at a water level previously established. Preferred devices and arrangements of this step of the present invention are shown in the examples.
Step c), related to recovering and drying the pearls, consists in recovering the pearls by means of different forms, depending on the type of equipment that is used for pearling, and then drying the recovered pearls, generally by exposing them to air.
The equipment for carrying out the pearling process in accordance with the present invention can be of different geometrical forms, the preferred types being those in the shape of cylindrical vessels or channels with rectangular section. These preferred equipments as well as dispositions and auxiliary devices particularly used in the process of the invention are shown in figures of the invention.
.
lZlOS55 8.
Figure 1 is a schematic view of the basic initial system of the sulfur pearling process in accordance with the invention;
Figure 2 is a graph showing the variation of the increase of the temperature of water in the process, with relation to the inlet water temperature and the proportion of the feeding charged of sulfur and water;
Figure 3A, 3B and 3C show a sulfur pearling system of the channel type with a rectangular cross-section;
Figure 4 shows another sulfur pearling system of the type that uses an elevation device for transporting the pearled product;
Figure 5 shows a section of the portions of a nozzle which can be used in the process of the invention;
Figure 6 shows another sulfur pearling system, and Figure 7 shows a lay-out of the latter system.
These figures will be more fully defined in the illustrative examples of the invention.
As already cited, the granulometry of the sulfur pearls can be adequately controlled during the pearling process. This control can be carried out by controlling the velocity of the water flow established in the process. The intensity of the induced water flow is essentially a function of either the degree of water movement generated by devices such as ..
121(~SS5 9 agitator, flow homogenizer and similar types, or of the degree of movement generated by the inlet velocity of the wa*er charge and/or the outlet velocity thereof, or is a function of both. By adjusting the velocity prevalent at these points a controlled granulometry is obtained for the formed pearled product.
Moreover, the granulometry control can be also carried out by adequate adjustment of the water level in the vessel where the sulfur and water charges come into contact and/or by varying the size of the openings through which the sulfur charge is fed in the process.
In the specific embodiment shown in figures 6 and 7 the feeding and outlet water charge itself establishes a desired water flow by forming a vortex, induced by tangential inlet of water and by the outlet thereof. Variations of these velocities as well as adequate adjustment of the water level afford the necessary alteration of the established water flow and the adjustment of the water level, thereby obtaining the desired control of the granulometry of the formed pearled product.
Besides exhibiting evident advantages such as, on the one hand, the simplicity of the process and of the equipment used for carrying it out, and, on the other hand, the reduced cost of the material used for pearling, i.e.: water, the pearling process in accordance with the present invention imparts to the pearled sulfur product satisfactory properties 12~555 10 .
such as perfect sphericity and homogeneity, controlled granulometric range, excellent resistance, quick drying etc., without displaying the incoveniences inherent to the conventional methods of sulfur processing.
The sequence of experiments which gave origin to the pearling process of the present invention will now be described in the form of illustrative examples.
The initial tests which led to the development of the present process consisted in adding S ~ to water under mechanical agitation and consequent establishment of the S~ property of producing particles in water, giving origin to S~ which in a few hours changes into S~ , as it does in every other S ~ process.
The property of S Ato produce sulfur pearls was then studied and the test was repeated numerous times in many different ways. The basic ex~eriment is described hereinafter and is followed by other examples describing various alternatives as well as the industrially tested process put into continuous operation.
~he following examples are illustrative of the ivention but not limitative.
The basic experiment of sulfur pearling as shown in figure 1, consisted in adding sulfur in the ~ form ~from a vessel (1), through an opening (2) having a diameter of 2mm placed in the botton of said vessel and at a height of lOcm from the water level, directly on the half the radius of a Becker cup ~3) having a capacity of 2.5 litres and a diameter of 19dm. The water level in the Becker being two-thirds of the height o said Becker.
lZ~O~SS 11.
2.0 litres of water at room temperature were added to the Becker cup and an agitator system (4) with 4 (four) 5 cm long, turhin-shaped stainless steel blades (5~ connected thereto. The blades entered two-thirds of the height of the water column.
The addition of S~was initiated at an agitation of lOOrpm, obtaining a pearled, perfectly spherical material with satisfactory granulometry, 100% of the product being comprised in the range of 0.25mm to 4.0 mm.
The product was submitted to friability tests showing excellent resistance moments after production (S~ ) as well as two days after production (S~).
The amount of water necessary for cooling the S was then verified and it was established that even under adiabatic conditions there could be various recirculations, evidencing that in practice the increase of the water temperature does not constitute a limiting factor for the process because it is not necessary to use very expensive cooling systems.
Assuming an adiabatic system, i.e. under the worst condi-tions, and using a proportion of six kilos of water at 20 ~C
for each kilo of sulfur , the resulting temperature will be approximately 49~C, as shown in figure 2 for adiabatic conditions.
It is seen that the amount and temperature of water do not constitute obstacles for the present invention.
` ~Z1~55S 12.
By using a sulfur pearling system as shown in figures 3A, 3B and 3C sulfur was added through six openings (8) having a diameter of 3 mm, from a height of 30 cm direct to the central part of the water level of a channel (6) with a flow homogenizer (7). The water level was adjusted to 4 cm by a set of gates (9') extending between the sidewalls of the channel (6) and held by laths (9). The set of laths ~9) and gates is shown with greater details in figures 3B and 3C.
Figure 3B shows a side view of the lower part of said pearling system which comprises 8 sets of laths (9) for mounting the gates (g') spaced from each other by 25 cm. The height of said channel is 32 cm and the length 5.9 m. Figure 3C shows a section of the lower part of said pearling system which evidences the disposition of the gate-holding laths (9) in the channel (6). me system also comprises a water inlet (10) and a steam input coil device (11), as shown in figure 3A.
The product obtained was well pearled. Because of its granulometry it afforded rapid water drainage and rapid loss of the residual free moisture, displaying a good grade of dryness.
The granulometry of the product obtained was as follows:
~a ~ ?i~ s l;~lQ555 ~y~er Mesh Opening (mm) % Retained % Accumulated
',' ``~.
~Z105SS
The process in accordance with the present invention is based on the characteristic that the suIfur in the lambda-form (S ~ ) solidifies passing through the forms of S
and S~ .
In the present invention the sulfur in the lan~bda-form is defined as sulfur whose temperature is comprised between the sulfur melting temperature and a temperature of approximetely 157C.
At temperatures above 157C significant amounts of sulfur are formed in the ~ form which upon solidifying form S y .
The~ form of sulfur, which is predominant at the above mentioned temperatures, affects not only the pearling process preventing the formation of sulfur pearls due to the plastic nature of SY and possibly causing obstruction, but also the pumping operation, since the viscosity of sulfur at high temperatures is not suitable for operations of this kind.
On the other hand, it was established that a liquid charge of sulfur of the specific type S ~ when added to water in constant movement affords the formation of solid sulfur pearls with satisfactory sphericity and homogeneity. It was also established that the granulometry of the pearls thus obtained can be adequately controlled during the pearlin~ process by adjusting the velocity of the water flow established during the process and/or adjusting the water level in the vessel where the charges of sulfur in the ~ form and of water co~e into contact, and/or adjusting the variation of the size of the openings for introducing the fulfur charge.
The process for pearling sulfur in accordance with the present invention is carried out by means of the following steps:
lzlasss 7.
a~ providing a charge of liquid sulfur in the form of lambda-sulfur; `
b~ adding said sulfur charge to water in constant movement, thereby forming sulfur pearls; and 5c) recovering and drying said pearls.
The liquid sulfur charge from step a~ can be obtained by heating a liquid or solid sulfur charge to a maximum temperature of about 157C. However, a sulfur charge in a liquid state is preferred.
The addition of sulfur to water described in step b) is normally carried out by means of devices comprising openings localized in a position and at a water level previously established. Preferred devices and arrangements of this step of the present invention are shown in the examples.
Step c), related to recovering and drying the pearls, consists in recovering the pearls by means of different forms, depending on the type of equipment that is used for pearling, and then drying the recovered pearls, generally by exposing them to air.
The equipment for carrying out the pearling process in accordance with the present invention can be of different geometrical forms, the preferred types being those in the shape of cylindrical vessels or channels with rectangular section. These preferred equipments as well as dispositions and auxiliary devices particularly used in the process of the invention are shown in figures of the invention.
.
lZlOS55 8.
Figure 1 is a schematic view of the basic initial system of the sulfur pearling process in accordance with the invention;
Figure 2 is a graph showing the variation of the increase of the temperature of water in the process, with relation to the inlet water temperature and the proportion of the feeding charged of sulfur and water;
Figure 3A, 3B and 3C show a sulfur pearling system of the channel type with a rectangular cross-section;
Figure 4 shows another sulfur pearling system of the type that uses an elevation device for transporting the pearled product;
Figure 5 shows a section of the portions of a nozzle which can be used in the process of the invention;
Figure 6 shows another sulfur pearling system, and Figure 7 shows a lay-out of the latter system.
These figures will be more fully defined in the illustrative examples of the invention.
As already cited, the granulometry of the sulfur pearls can be adequately controlled during the pearling process. This control can be carried out by controlling the velocity of the water flow established in the process. The intensity of the induced water flow is essentially a function of either the degree of water movement generated by devices such as ..
121(~SS5 9 agitator, flow homogenizer and similar types, or of the degree of movement generated by the inlet velocity of the wa*er charge and/or the outlet velocity thereof, or is a function of both. By adjusting the velocity prevalent at these points a controlled granulometry is obtained for the formed pearled product.
Moreover, the granulometry control can be also carried out by adequate adjustment of the water level in the vessel where the sulfur and water charges come into contact and/or by varying the size of the openings through which the sulfur charge is fed in the process.
In the specific embodiment shown in figures 6 and 7 the feeding and outlet water charge itself establishes a desired water flow by forming a vortex, induced by tangential inlet of water and by the outlet thereof. Variations of these velocities as well as adequate adjustment of the water level afford the necessary alteration of the established water flow and the adjustment of the water level, thereby obtaining the desired control of the granulometry of the formed pearled product.
Besides exhibiting evident advantages such as, on the one hand, the simplicity of the process and of the equipment used for carrying it out, and, on the other hand, the reduced cost of the material used for pearling, i.e.: water, the pearling process in accordance with the present invention imparts to the pearled sulfur product satisfactory properties 12~555 10 .
such as perfect sphericity and homogeneity, controlled granulometric range, excellent resistance, quick drying etc., without displaying the incoveniences inherent to the conventional methods of sulfur processing.
The sequence of experiments which gave origin to the pearling process of the present invention will now be described in the form of illustrative examples.
The initial tests which led to the development of the present process consisted in adding S ~ to water under mechanical agitation and consequent establishment of the S~ property of producing particles in water, giving origin to S~ which in a few hours changes into S~ , as it does in every other S ~ process.
The property of S Ato produce sulfur pearls was then studied and the test was repeated numerous times in many different ways. The basic ex~eriment is described hereinafter and is followed by other examples describing various alternatives as well as the industrially tested process put into continuous operation.
~he following examples are illustrative of the ivention but not limitative.
The basic experiment of sulfur pearling as shown in figure 1, consisted in adding sulfur in the ~ form ~from a vessel (1), through an opening (2) having a diameter of 2mm placed in the botton of said vessel and at a height of lOcm from the water level, directly on the half the radius of a Becker cup ~3) having a capacity of 2.5 litres and a diameter of 19dm. The water level in the Becker being two-thirds of the height o said Becker.
lZ~O~SS 11.
2.0 litres of water at room temperature were added to the Becker cup and an agitator system (4) with 4 (four) 5 cm long, turhin-shaped stainless steel blades (5~ connected thereto. The blades entered two-thirds of the height of the water column.
The addition of S~was initiated at an agitation of lOOrpm, obtaining a pearled, perfectly spherical material with satisfactory granulometry, 100% of the product being comprised in the range of 0.25mm to 4.0 mm.
The product was submitted to friability tests showing excellent resistance moments after production (S~ ) as well as two days after production (S~).
The amount of water necessary for cooling the S was then verified and it was established that even under adiabatic conditions there could be various recirculations, evidencing that in practice the increase of the water temperature does not constitute a limiting factor for the process because it is not necessary to use very expensive cooling systems.
Assuming an adiabatic system, i.e. under the worst condi-tions, and using a proportion of six kilos of water at 20 ~C
for each kilo of sulfur , the resulting temperature will be approximately 49~C, as shown in figure 2 for adiabatic conditions.
It is seen that the amount and temperature of water do not constitute obstacles for the present invention.
` ~Z1~55S 12.
By using a sulfur pearling system as shown in figures 3A, 3B and 3C sulfur was added through six openings (8) having a diameter of 3 mm, from a height of 30 cm direct to the central part of the water level of a channel (6) with a flow homogenizer (7). The water level was adjusted to 4 cm by a set of gates (9') extending between the sidewalls of the channel (6) and held by laths (9). The set of laths ~9) and gates is shown with greater details in figures 3B and 3C.
Figure 3B shows a side view of the lower part of said pearling system which comprises 8 sets of laths (9) for mounting the gates (g') spaced from each other by 25 cm. The height of said channel is 32 cm and the length 5.9 m. Figure 3C shows a section of the lower part of said pearling system which evidences the disposition of the gate-holding laths (9) in the channel (6). me system also comprises a water inlet (10) and a steam input coil device (11), as shown in figure 3A.
The product obtained was well pearled. Because of its granulometry it afforded rapid water drainage and rapid loss of the residual free moisture, displaying a good grade of dryness.
The granulometry of the product obtained was as follows:
~a ~ ?i~ s l;~lQ555 ~y~er Mesh Opening (mm) % Retained % Accumulated
4,00 33,19 33,19 6 3,36 16,22 49,41 7 2,83 7,40 56,81 8 2,38 15,65 72,46 9 2,00 9,99 82,45 1,68 5,95 88,40 12 1,41 2,06 90,46 14 1,19 4,10 9~,56 16 1,00 1,48 96,04 32 0,50 2,60 98,64 0,25 0,64 99,28 -60 ~ 0,25 0,72 100,00 EXAMPL _ Sulfur~ was added through six openings having a diameter of 2mm, at a height of 10 cm above the water level of a system mounted in accordance with figures 3A, 3B and 3C, but the height of the water level was adjusted to 2cm.
The addition of S~was made in the manner described in the foregoing example. The product obtained was well pearled, with a good flow-off of free residual moisture, drying rapidly.
The granulometry of the product obtained was as follows:
~IZ~QSSS
14.
Tyler Mesh Opening (mm) _ Retained ~ Accumulated_ _ 4,00 28,08 28,08 6 3,36 18,78 46,81 7 2,83 8,21 55,07 - 8 2,38 17,51 72,58 9 2,00 12,28 84,86 1,68 5,56 90,42 1~ 1,41 1,53 91,95 14 1,19 3,88 95,83 16 1,00 1,21 97,04 32 n,50 2,21 99,25 0,25 0,48 99,73 -60 ~ 0,25 0,27 100,00 Example 3(1) By using a sulfur prearling system as shown in fi~ure 4, sulfur ~ was added through a nozzle (12) having 4 openings with a diameter of 2 mm, from a height of 40 cm from the water level, on half the radius of a water-containing cy-lindrical vessel (13). The system was worked at 70 rpm by means of a mechanical agitatcr device (14) with turbine-shaped blades (15.). The product was discharged by an elevation device (16) driven by a driving mechanism (17) installed on the conical bottom of the vessel (13) and stored in a container (18). The water drained from the product in said container (18) was transferred to a water receiving container (20) through line 19 and recirculated through lines (21) and (23) to a cylindrical vessel (13) by means of a pump (22). The lower setion (24) of the nozzle (12) as well as the cross section (25) thereof is 30 shown in figure 5. Said nozzle (12) is made of stainless steel 304 with a thickness in excess of 1 mm, haviny 4 openings (26) for sulfur input as well as an inlet (27) and outlet (283 for steam.
lZl(~SSS
The product obtained was very well pearled, with excellent drainage of residual free moisture, drying rapidly when stockpiled.
The granulometry of the product was as follows:
Tyler Mesh Opening (mm) % Retained % Accumulated 3,5 5,66 0,85~ -4,00 3,05 3,90 6 3,36 11,25 15,15 7 2,83 8,75 23,90 8 2,38 35,66 59,56 9 2,00 18,89 78,45 1,68 8,09 86,54 12 1,41 3,05 89,59 14 1,19 4,71 94,30 16 1,00 1,63 95,93 32 0,50 2,55 98,48 0,25 0,30 98,73 -60 ~0,25 1,21 100,00 EXAMPLE 3 (2) Sulfur~ was added to the same system as described in the example 3 (1), but in order to change the granulometry, the velocity of the agitator was changed to 100 rpm, obtained a finer product, as it is seen in the granulometry analysis:
~;~lQ555 16.
Tyler Mesh Opening (mm) ~ Retained % Accumulated 3,5 5,66 - -4,00 6 3,36 5,20 5,20 7 2,83 10,30 15,50 8 2,38 30,20 45,70 9 2,00 45,00 90.70 1,68 3,70 94,40 12 1,41 1,05 95,45 10 14 1,19 1,30 96,75 16 1,00 1,83 98,5 32 0,50 0,22 98,8 0,25 0,87 99l67 -60 <0,25 0,33 100,00 EXAMPLE 4(1) By using a sulfur pearling system as shown in figure 6, sulfur,~ was added through a nozzle shown in figure 5, but having 8 openings with a diameter of 3 mm each, on half the radius of a cylindrical vessel (28). The cylin-drical vessel (28) is provided with a tangential waterinlet (30) and has a lower conical portion .(31). The vessel (28) has further a bottom-valve with a 2-inch opening mounted in the lower portion (31) thereof. Said system also comprises a channel (33) for receiving pearled material and water, situated below said valve (32) and a movable trough (34) which transports the product coming from the cl~annel (33) for an appropriate site.
~21~5SS
17.
The process was started by adding water to the vessel (2~), in sufficient amounts for operating the system with a vortex induced by tan~ential entrance of water (30) and so that the height and the velocity of the water flow in the vessel (28) would be controlled by opening the bottom valve (32).
The vortices in the southern hemisphere were given a clockwise direction.
The S~ was added giving origin to a pearling similar to the pearling described in examples 3 (1) and 3 (2), the pearled product being automatically removed with the water by the valve (32) of the vessel (28) and arranged in the best way at the storage site with the help of a moving conveyor (34) trough. The lay-out of the above system is shown in fi.gure 7, in which the sulfur is introdu~ed through line (35) through the nozzle (12) direct into said cylindrical vessel (28).
The system has a base portion (34) for supporting the equipments and indicates the range of said movable trough (34). The other references shown in this figure are as already defined in this example.
The pearled product displayed excellent granulometry as well as very good conditions for draining the residual free moisture affording natural drying to the stocked product.
The granulometry of the product obtained was as follows:
~;~lOS55 18.
~y_er Mesh Opening (mm) % Retained % Accumulated ~,00 10,97 10,97 6 3,36 10,05 21,02 7 2,83 2,26 23,28 8 2,38 4,81 48.09 9 2,00 24,03 72,12 1,68 12,51 ~4,63 12 1~41 2,96 87,59 14 1,19 6,16 93,75 16 1,00 1,62 9~,37 32 0,50 2,88 98,25 0,25 0,77 99,02 -60 ~0,25 0,98 100,00 EXAMPLE 4 (2) Sulfur ~ was added to the same system as in example 4(1) but adjusting the water level of the vortex .induced by the bottom valve so as to maintain the water level at a dis-tance of 15 cm from the nozzle with the object of obtaining a product with coarser granulometry. As seen in the gra-nulometric analysis this object was fully achieved and asexpected the product having coarser granulometry dried more quickly than the products with finer granulometry.
The granulometry of the product obtained was as follows:
~Z~0555 19.
Tyler Mesh Opening (mm) % Retained ~ Accumulated 3,5 5,66. 8,75 8,75 4,00 30,59 39,34 6 3,36 12,68 52,02 ~ 2,83 3,67 55,69 8 2,38 19,24 74,93 9 2,00 10,52 85,17 1,68 6,39 91,S6 12 1,41 2,09 g3,65 14 1,19 1,90 95,55 16 1,00 0,49 96,04 32 0,50 0,61 96,65 0,25 2,21 98,86 -60 ~0,25 1,14 100,00 The experiment described in examp].es 4 (1) and 4 (2) was texted on an industrial scale and put into operation in a petrochemical sulfur recovery unit (Claus process) with a production capacity of 57 t/d.
The addition of S~was made in the manner described in the foregoing example. The product obtained was well pearled, with a good flow-off of free residual moisture, drying rapidly.
The granulometry of the product obtained was as follows:
~IZ~QSSS
14.
Tyler Mesh Opening (mm) _ Retained ~ Accumulated_ _ 4,00 28,08 28,08 6 3,36 18,78 46,81 7 2,83 8,21 55,07 - 8 2,38 17,51 72,58 9 2,00 12,28 84,86 1,68 5,56 90,42 1~ 1,41 1,53 91,95 14 1,19 3,88 95,83 16 1,00 1,21 97,04 32 n,50 2,21 99,25 0,25 0,48 99,73 -60 ~ 0,25 0,27 100,00 Example 3(1) By using a sulfur prearling system as shown in fi~ure 4, sulfur ~ was added through a nozzle (12) having 4 openings with a diameter of 2 mm, from a height of 40 cm from the water level, on half the radius of a water-containing cy-lindrical vessel (13). The system was worked at 70 rpm by means of a mechanical agitatcr device (14) with turbine-shaped blades (15.). The product was discharged by an elevation device (16) driven by a driving mechanism (17) installed on the conical bottom of the vessel (13) and stored in a container (18). The water drained from the product in said container (18) was transferred to a water receiving container (20) through line 19 and recirculated through lines (21) and (23) to a cylindrical vessel (13) by means of a pump (22). The lower setion (24) of the nozzle (12) as well as the cross section (25) thereof is 30 shown in figure 5. Said nozzle (12) is made of stainless steel 304 with a thickness in excess of 1 mm, haviny 4 openings (26) for sulfur input as well as an inlet (27) and outlet (283 for steam.
lZl(~SSS
The product obtained was very well pearled, with excellent drainage of residual free moisture, drying rapidly when stockpiled.
The granulometry of the product was as follows:
Tyler Mesh Opening (mm) % Retained % Accumulated 3,5 5,66 0,85~ -4,00 3,05 3,90 6 3,36 11,25 15,15 7 2,83 8,75 23,90 8 2,38 35,66 59,56 9 2,00 18,89 78,45 1,68 8,09 86,54 12 1,41 3,05 89,59 14 1,19 4,71 94,30 16 1,00 1,63 95,93 32 0,50 2,55 98,48 0,25 0,30 98,73 -60 ~0,25 1,21 100,00 EXAMPLE 3 (2) Sulfur~ was added to the same system as described in the example 3 (1), but in order to change the granulometry, the velocity of the agitator was changed to 100 rpm, obtained a finer product, as it is seen in the granulometry analysis:
~;~lQ555 16.
Tyler Mesh Opening (mm) ~ Retained % Accumulated 3,5 5,66 - -4,00 6 3,36 5,20 5,20 7 2,83 10,30 15,50 8 2,38 30,20 45,70 9 2,00 45,00 90.70 1,68 3,70 94,40 12 1,41 1,05 95,45 10 14 1,19 1,30 96,75 16 1,00 1,83 98,5 32 0,50 0,22 98,8 0,25 0,87 99l67 -60 <0,25 0,33 100,00 EXAMPLE 4(1) By using a sulfur pearling system as shown in figure 6, sulfur,~ was added through a nozzle shown in figure 5, but having 8 openings with a diameter of 3 mm each, on half the radius of a cylindrical vessel (28). The cylin-drical vessel (28) is provided with a tangential waterinlet (30) and has a lower conical portion .(31). The vessel (28) has further a bottom-valve with a 2-inch opening mounted in the lower portion (31) thereof. Said system also comprises a channel (33) for receiving pearled material and water, situated below said valve (32) and a movable trough (34) which transports the product coming from the cl~annel (33) for an appropriate site.
~21~5SS
17.
The process was started by adding water to the vessel (2~), in sufficient amounts for operating the system with a vortex induced by tan~ential entrance of water (30) and so that the height and the velocity of the water flow in the vessel (28) would be controlled by opening the bottom valve (32).
The vortices in the southern hemisphere were given a clockwise direction.
The S~ was added giving origin to a pearling similar to the pearling described in examples 3 (1) and 3 (2), the pearled product being automatically removed with the water by the valve (32) of the vessel (28) and arranged in the best way at the storage site with the help of a moving conveyor (34) trough. The lay-out of the above system is shown in fi.gure 7, in which the sulfur is introdu~ed through line (35) through the nozzle (12) direct into said cylindrical vessel (28).
The system has a base portion (34) for supporting the equipments and indicates the range of said movable trough (34). The other references shown in this figure are as already defined in this example.
The pearled product displayed excellent granulometry as well as very good conditions for draining the residual free moisture affording natural drying to the stocked product.
The granulometry of the product obtained was as follows:
~;~lOS55 18.
~y_er Mesh Opening (mm) % Retained % Accumulated ~,00 10,97 10,97 6 3,36 10,05 21,02 7 2,83 2,26 23,28 8 2,38 4,81 48.09 9 2,00 24,03 72,12 1,68 12,51 ~4,63 12 1~41 2,96 87,59 14 1,19 6,16 93,75 16 1,00 1,62 9~,37 32 0,50 2,88 98,25 0,25 0,77 99,02 -60 ~0,25 0,98 100,00 EXAMPLE 4 (2) Sulfur ~ was added to the same system as in example 4(1) but adjusting the water level of the vortex .induced by the bottom valve so as to maintain the water level at a dis-tance of 15 cm from the nozzle with the object of obtaining a product with coarser granulometry. As seen in the gra-nulometric analysis this object was fully achieved and asexpected the product having coarser granulometry dried more quickly than the products with finer granulometry.
The granulometry of the product obtained was as follows:
~Z~0555 19.
Tyler Mesh Opening (mm) % Retained ~ Accumulated 3,5 5,66. 8,75 8,75 4,00 30,59 39,34 6 3,36 12,68 52,02 ~ 2,83 3,67 55,69 8 2,38 19,24 74,93 9 2,00 10,52 85,17 1,68 6,39 91,S6 12 1,41 2,09 g3,65 14 1,19 1,90 95,55 16 1,00 0,49 96,04 32 0,50 0,61 96,65 0,25 2,21 98,86 -60 ~0,25 1,14 100,00 The experiment described in examp].es 4 (1) and 4 (2) was texted on an industrial scale and put into operation in a petrochemical sulfur recovery unit (Claus process) with a production capacity of 57 t/d.
Claims (6)
1. A process for pearling sulfur comprising the steps of:
a) feeding water to a linear channel means of rectangular cross-section having sidewalls and a bottom, b) circulating said water in constant movement in said channel;
c) controlling the velocity of said circu-lating water in said channel, d) controlling the level of said circulating water in said channel by gate means extending between said sidewalls;
e) feeding at least one stream of liquid sulfur in the from of lambda sulfur into said circu-lating water in said channel, f) controlling the temperature of said stream containing lambda sulfur up to a maximum temperature of about 157°C, g) pearling said lambda sulfur in said cir-culating water to form a pearled sulfur product having a granulometry controlled by said water level, and h) recovering and drying said pearls.
a) feeding water to a linear channel means of rectangular cross-section having sidewalls and a bottom, b) circulating said water in constant movement in said channel;
c) controlling the velocity of said circu-lating water in said channel, d) controlling the level of said circulating water in said channel by gate means extending between said sidewalls;
e) feeding at least one stream of liquid sulfur in the from of lambda sulfur into said circu-lating water in said channel, f) controlling the temperature of said stream containing lambda sulfur up to a maximum temperature of about 157°C, g) pearling said lambda sulfur in said cir-culating water to form a pearled sulfur product having a granulometry controlled by said water level, and h) recovering and drying said pearls.
2. The process of claim 1, comprising heating a solid sulfur charge to form said liquid stream.
3. The process of claim 1, wherein the water flows out of said channel through said gates and the granulometry of the pearls is controlled by adjusting the velocities of the water into and out of said channel.
4. An apparatus for pearling sulfur, comprising:
linear channel means of rectangular cross-section having sidewalls and a bottom, means for feeding water to said channel, means for circulating the water in constant movement in said channel and for controlling velocity of said circulating water, gate means extending between said sidewalls for controlling the level of said circulating water in said channel, means above said channel for feeding at least one stream of liquid sulfur in the form of lambda sulfur into said circulating water in said channel, means for controlling the temperature of said lambda sulfur up to a maximum temperature of about 157°C, and means for recovering and drying sulfur pearls formed in said circulating water.
linear channel means of rectangular cross-section having sidewalls and a bottom, means for feeding water to said channel, means for circulating the water in constant movement in said channel and for controlling velocity of said circulating water, gate means extending between said sidewalls for controlling the level of said circulating water in said channel, means above said channel for feeding at least one stream of liquid sulfur in the form of lambda sulfur into said circulating water in said channel, means for controlling the temperature of said lambda sulfur up to a maximum temperature of about 157°C, and means for recovering and drying sulfur pearls formed in said circulating water.
5. The apparatus of claim 4, wherein movement of said water in said channel is controlled by a flow homogenizer.
6. The apparatus of claim 4, comprising a plu-rality of flow openings for providing a plurality of liquid sulfur streams into said circulating water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI8205991 | 1982-09-20 | ||
| BR8205991A BR8205991A (en) | 1982-09-30 | 1982-09-30 | SULFUR BORING PROCESS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1210555A true CA1210555A (en) | 1986-09-02 |
Family
ID=4031908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000437112A Expired CA1210555A (en) | 1982-09-20 | 1983-09-20 | Process for pearling sulfur |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5992904A (en) |
| AU (1) | AU567114B2 (en) |
| BR (1) | BR8205991A (en) |
| CA (1) | CA1210555A (en) |
| DE (1) | DE3333758A1 (en) |
| ES (1) | ES525738A0 (en) |
| FR (1) | FR2533143B1 (en) |
| GB (1) | GB2127800B (en) |
| MX (1) | MX162875B (en) |
| PL (1) | PL243827A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11185812B2 (en) | 2010-10-29 | 2021-11-30 | Mecs, Inc. | Regenerative recovery of sulfur dioxide from effluent gases |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2185006B (en) * | 1986-01-07 | 1989-10-25 | Reutsky Vladimir F | Process for producing ground sulphur from melt thereof |
| US5801453A (en) * | 1996-06-11 | 1998-09-01 | United Technologies Corporation | Process for preparing spherical energetic compounds |
| DE69818230T2 (en) * | 1997-02-27 | 2004-07-01 | Alberta Research Council, Edmonton | METHOD FOR PRODUCING SULFUR GRANULES IN THE MICROMETER AREA |
| US8329072B2 (en) * | 2010-11-24 | 2012-12-11 | Brimrock International Inc. | Method and system for generating sulfur seeds and granules |
| RU2625863C2 (en) * | 2012-01-31 | 2017-07-19 | САНДВИК ПРОУСЕСС СИСТЕМЗ ЭлЭлСи | Method and system for the formation of gray silicon crystallization in a moving liquid |
| CN114984852A (en) * | 2022-06-15 | 2022-09-02 | 中国石油化工股份有限公司 | Spiral-flow type sulfur submerged granulation kettle |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1969242A (en) * | 1932-02-08 | 1934-08-07 | American Anode Inc | Method of dispersing solids |
| DE969892C (en) * | 1941-05-13 | 1958-07-31 | Wacker Chemie Gmbh | Process for the production of finely divided sulfur |
| FR1244441A (en) * | 1959-09-18 | 1960-10-28 | Aquitaine Petrole | Process and installation for obtaining sulfur in balls or granules |
| GB1119363A (en) * | 1964-04-07 | 1968-07-10 | Elliott Assoc Dev | Improvements in or relating to the treatment of sulphur |
| GB1136901A (en) * | 1964-09-17 | 1968-12-18 | Elliott Assoc Dev | Improvements in or relating to the treatment of sulphur |
| GB1161592A (en) * | 1965-07-13 | 1969-08-13 | Elliot Associated Developments | Improvements in or relating to the Pelletisation of Sulphur |
| GB1119663A (en) * | 1965-07-15 | 1968-07-10 | British Bata Shoe Co Ltd | Shoes and a method of manufacturing same |
| DE1621677A1 (en) * | 1967-08-28 | 1970-07-30 | Chemiefaserkombinat Wilh Pieck | Process for cleaning devices and equipment contaminated with plastic melt |
| US3504061A (en) * | 1968-11-18 | 1970-03-31 | Elliott Assoc Dev | Method of preparing sulphur pellets |
| US3538200A (en) * | 1968-12-26 | 1970-11-03 | Shell Oil Co | Method for prilling molten sulfur |
| US3761136A (en) * | 1971-01-05 | 1973-09-25 | Continental Oil Co | Method of transporting sulfur by pipeline |
| JPS4876796A (en) * | 1972-01-19 | 1973-10-16 | ||
| JPS5028480A (en) * | 1973-07-17 | 1975-03-24 | ||
| JPS5239594A (en) * | 1975-09-26 | 1977-03-26 | Nippon Steel Corp | Production of granular sulfur |
| JPS51112792A (en) * | 1976-03-16 | 1976-10-05 | Elliott Herbert J | Method of pelletizing sulfur |
| JPS5518647A (en) * | 1978-07-26 | 1980-02-08 | Matsushita Electric Ind Co Ltd | Light transmittable particle for forming color images |
| DE3116914A1 (en) * | 1981-04-29 | 1982-11-18 | Chemische Werke Hüls AG, 4370 Marl | IMPROVING THE PRILLING PROCESS FOR MELTABLE SUBSTANCES ON THE PRESENT OF A COOLANT |
-
1982
- 1982-09-30 BR BR8205991A patent/BR8205991A/en unknown
-
1983
- 1983-09-19 AU AU19235/83A patent/AU567114B2/en not_active Ceased
- 1983-09-19 DE DE19833333758 patent/DE3333758A1/en not_active Withdrawn
- 1983-09-19 FR FR8314871A patent/FR2533143B1/fr not_active Expired
- 1983-09-19 MX MX19874883A patent/MX162875B/en unknown
- 1983-09-19 GB GB08325015A patent/GB2127800B/en not_active Expired
- 1983-09-19 ES ES83525738A patent/ES525738A0/en active Granted
- 1983-09-20 CA CA000437112A patent/CA1210555A/en not_active Expired
- 1983-09-20 PL PL24382783A patent/PL243827A1/en unknown
- 1983-09-20 JP JP17401783A patent/JPS5992904A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11185812B2 (en) | 2010-10-29 | 2021-11-30 | Mecs, Inc. | Regenerative recovery of sulfur dioxide from effluent gases |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2533143B1 (en) | 1988-07-22 |
| GB8325015D0 (en) | 1983-10-19 |
| GB2127800A (en) | 1984-04-18 |
| GB2127800B (en) | 1986-09-17 |
| ES8503310A1 (en) | 1985-02-16 |
| DE3333758A1 (en) | 1984-03-29 |
| BR8205991A (en) | 1984-05-08 |
| MX162875B (en) | 1991-07-02 |
| AU567114B2 (en) | 1987-11-12 |
| PL243827A1 (en) | 1984-07-30 |
| ES525738A0 (en) | 1985-02-16 |
| AU1923583A (en) | 1984-03-29 |
| JPS5992904A (en) | 1984-05-29 |
| FR2533143A1 (en) | 1984-03-23 |
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