US3476441A - Transport of sulphur - Google Patents

Transport of sulphur Download PDF

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US3476441A
US3476441A US659386A US3476441DA US3476441A US 3476441 A US3476441 A US 3476441A US 659386 A US659386 A US 659386A US 3476441D A US3476441D A US 3476441DA US 3476441 A US3476441 A US 3476441A
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sulphur
oil
liquid
vessel
transport
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US659386A
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Herbert James Elliott
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Elliott Associated Developments Ltd
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Elliott Associated Developments Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/0237Converting into particles, e.g. by granulation, milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65GTRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G53/00Conveying materials in bulk through troughs, pipes or tubes by floating the materials or by flow of gas, liquid or foam
    • B65G53/30Conveying materials in bulk through pipes or tubes by liquid pressure
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification

Definitions

  • This invention relates to the transport of sulphur, more particularly in pipe lines.
  • the sulphur is finely ground so that a slurry of sulphur in the oil can be formed. It is an object of the invention to provide a scheme which is more advantageous than this prior proposal.
  • sulphur particles for pipe line transport are produced by precipitation, and/ or by dispersion of molten sulphur, in a liquid medium instead of by mechanical reduction.
  • the sulphur is treated, in preparation for pipe line transport, by introducing it in the molten state into a liquid, e.g. a comparatively light oil fraction such as diesoline, which is a solvent therefor.
  • a liquid e.g. a comparatively light oil fraction such as diesoline
  • the result is a sulphur/solvent mixture which contains a higher or lower proportion of dissolved sulphur according to the temperature of the oil, the remaining sulphur being contained in the oil as solid in a finely dispersed condition.
  • the sulphur is in a state suitable for pipeline transport.
  • the sulphur is separated in finely divided form from the bulk of the solvent and introduced into a carrier liquid such as crude oil prior to transport.
  • a carrier liquid such as crude oil prior to transport.
  • the dissolved sulphur cooling of the solvent oil causes it to form a precipitate which can then be separated, for example by centrifuging.
  • the molten sulphur is pelletised or granulated by the process described in our patent application -No. 48,828/ 64 except that fine pressurised sulphur nozzles are used, the cooling liquid employed in the pelletising vessel is a solvent oil instead of water and the impeller in the vessel rotates in the opposite direction to the swirl created by the peripheral jets. This produces much finer particles.
  • sulphur particles of different sizes produced by both the techniques above are blended upon introduction into the pipe line carrier liquid.
  • FIGURE 1 is a diagram of plant for producing a mixture of sulphur finely dispersed in oil and for blending in a further sulphur particles, and
  • FIGURE 2 illustrates the production of those further sulphur particles.
  • molten sulphur at about 128 C. is delivered into each of four stem-jacketed solvent mix tanks 11 grouped in parallel with one another and containing diesoline maintained at -128 C.
  • Each of the mix tanks has an agitator 26.
  • the resulting oil/ sulphur mixture is pumped by means of submerged centrifugal pumps 12 through two stages 20, 21 of a three-stage countercurrent heat exchanger 14.
  • the oil/sulphur mixture is passed in heat exchange with diesoline returning to the tanks 11 after having been stripped of its sulphur, while in the coldest stage 20 the oil/sulphur mixture is further cooled by heat exchange with cooling Water.
  • the returning diesoline has a temperature at entry to the middle stage 21 of the heat exchanger of about 20 C. to 30 C., and after heat exchange with the sulphur/oil mixture it passes through the third or hottest stage 22 of the heat exchanger, which is steam-heated, Where it is further heated to a temperature of about 128 C. by the time it leaves the heat exchanger.
  • the cooled mixture is delivered into a precipitation vessel 23 fitted with a cooling jacket and from the bottom of the vessel 23 the oil and precipitate is pumped to a hydrocyclone or Super-D-Canter Sharples centrifuge 15 where the sulphur is stripped from the major proportion of the oil.
  • the stripped diesoline passes from the hydrocyclone 15 into a tank 16 at 2030 C. whence it is pumped back via the heat exchanger 14 to the tanks 11.
  • the tank 16 may be fitted with a cooling or heating jacket, as desired, to obtain the correct heat balance in the plant.
  • the concentrated sulphur precipitate from the hydrocyclone or centrifuge 15 is delivered into a blending tank 24.
  • the solubility of the sulphur in the oil is about 10% by weight at 128 C. Bearing this in mind, a suitable ratio of oil to sulphur is 15:1. Visible precipitation commences at about 50 C.
  • the precipitation vessel 23' may be equipped with an agitator 25.
  • the heat exchanger 14 is preferably a De Laval plate heat exchanger; these have corrugated plates so that fluid flowing through is caused to follow a sinuous path, which may be beneficial for conditioning the precipitating sulphur.
  • the oil in the solvent mix tanks may be maintained at a considerably lower temperature, say in the range 2050 C., sulphur being dispersed in the oil in a finely divided solid state rather than being dissolved in the oil.
  • the molten sulphur is fed in streams through fine jets into the oil so as to obtain a high degree of dispersion. Strong agitation is needed.
  • the same ratio of oil to sulphur, i.e. 15 to 1, may be used as before.
  • a second sulphur stream is treated in a pelletising vessel 27 (FIGURE 2).
  • the general principle of operation of this vessel is similar to that described in our patent application No. 48,828/64 but it has some important modifications.
  • One is that the cooling liquid in the vessel is not a liquid entirely immiscible with molten sulphur,
  • nozzles for delivering the molten sulphur streams downward into the body of cooling liquid are finer than those employed in the prior patent application and are pressurised, being generally similar to those used in prill towers.
  • a multidisc rotary impeller 28 is provided in the vessel 27 which impeller rotates in the opposite direction to swirl induced in the liquid in the vessel by means of tangentially discharging peripheral oil jets 29.
  • the object is to create shear at the region where the liquid dragged round by the impeller encounters the oppositely-directed swirl due to the jets, thereby to produce a tendency for the solidifying sulphur droplets in the liquid to break down to a finer sizing.
  • the diameter of the impeller discs should be approximately one third that of the vessel.
  • the pelletising vessel 27 produces unusually small-sized pellets or granules and these are delivered from the bottom of the vessel in a stream of the oil to a centrifuge 30 where they are separated from the major proportion of the oil.
  • the pellets or granules separated by the centrifuge 30 are fed to the aforementioned blending tank 24 (FIGURE 1), while the stripped die'soline is recycled.
  • overflows from the pelletising vessel, containing fines may also be delivered to the centrifuge.
  • the pellet-bearing stream from the bottom of the vessel may be passed to a screen, for example a wedge wire screen, instead of directly to the centrifuge, oversize pellets being removed and only the screen underflow then reaching the centrifuge.
  • the sulphur particles from the precipitation vessel on the one hand, and from the pelletising vessel on the other hand are both mixed into the carrier liquid, e.g. crude oil, which is to transport the sulphur through the pipe line.
  • the flows of the two types of sulphur particles are mutually proportioned so as to achieve the optimum blend for pipe line transport, and the flow of the carrier liquid is likewise regulated to obtain the optimum density of sulphur particles therein.
  • oil fraction such as diesoline
  • other liquids also act as solvents for sulphur and the invention is to be considered as extending to the use of such other solvents.
  • a method of preparing sulphur for transport by pipe-line in a carrier liquid including the steps of: introducing molten sulphur into a liquid medium different from the carrier liquid thereby to create a dispersion of solid sulphur particles in said different liquid medium, separating said sulphur particles from at least the bulk of said dieifrent liquid medium and blending the separated sulphur particles into the carrier liquid for transport.
  • said different liquid medium is a solvent liquid in which sulphur is soluble to an increasing extent with rising temperature, and the sulphur is caused to precipitate therefrom by reducing the solvent liquid temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)

Description

Nov 4, 1969 H. J. ELLIO1 'T 3,476,441
TRANSPORT OF SULPHUR Filed Aug. 9, 1967 2 Sheets-Sheet 1 it 2 b :2 5. 6 2 0 Inventor Nov. 4, 1969 H. J. ELLIOTT 3,476,441
TRANSPORT OF SULPHUR Filed Aug. 9, 1967 2 Sheets-Sheet :2
ECENTR/F i @64- Inventor A Hern a United States Patent US. Cl. 302-66 8 Claims ABSTRACT OF THE DISCLOSURE Bulk sulphur is efficiently transported by converting molten sulphur to solid sulphur pellets by dispersion of the molten sulphur into a liquid medium, separating the solid sulphur pellets from the dispersion medium and then planting the separated particles into a carrier liquid for transport therein.
This invention relates to the transport of sulphur, more particularly in pipe lines.
A proposal has been made for the transport of sulphur over long distances by pipe line in the solid state using as a carrier liquid crude oil and condensates. For this purpose the sulphur is finely ground so that a slurry of sulphur in the oil can be formed. It is an object of the invention to provide a scheme which is more advantageous than this prior proposal.
According to the present invention, sulphur particles for pipe line transport are produced by precipitation, and/ or by dispersion of molten sulphur, in a liquid medium instead of by mechanical reduction.
In one technique, the sulphur is treated, in preparation for pipe line transport, by introducing it in the molten state into a liquid, e.g. a comparatively light oil fraction such as diesoline, which is a solvent therefor. The result is a sulphur/solvent mixture which contains a higher or lower proportion of dissolved sulphur according to the temperature of the oil, the remaining sulphur being contained in the oil as solid in a finely dispersed condition. Either dissolved or in finely divided solid form the sulphur is in a state suitable for pipeline transport. Preferably, however, the sulphur is separated in finely divided form from the bulk of the solvent and introduced into a carrier liquid such as crude oil prior to transport. In the case of the dissolved sulphur cooling of the solvent oil causes it to form a precipitate which can then be separated, for example by centrifuging.
In another technique, the molten sulphur is pelletised or granulated by the process described in our patent application -No. 48,828/ 64 except that fine pressurised sulphur nozzles are used, the cooling liquid employed in the pelletising vessel is a solvent oil instead of water and the impeller in the vessel rotates in the opposite direction to the swirl created by the peripheral jets. This produces much finer particles.
As a preferred feature of the invention, sulphur particles of different sizes produced by both the techniques above are blended upon introduction into the pipe line carrier liquid.
These techniques avoid access of moisture to the sulphur and give close control over the blend of particle sizes transported so that an optimum economic mixture with the carrier liquid is readily obtainable. Furthermore, whereas it is common for impurities to find their way into material that is mechanically reduced, e.g. in a ball mill, the absence of mechanical reduction in the techniques according to the invention avoids contamination of the sulphur and results in a particulate product being transported which can be recovered more easily in a pure "ice state from the carrier liquid after transport. A material reduction in the capital and running costs of the recovery plant is thereby achieved.
One particular example of how the invention may be practised will now be described with reference to the accompanying drawings, in which:
FIGURE 1 is a diagram of plant for producing a mixture of sulphur finely dispersed in oil and for blending in a further sulphur particles, and
FIGURE 2 illustrates the production of those further sulphur particles.
Referring firstly to FIGURE 1, molten sulphur at about 128 C. is delivered into each of four stem-jacketed solvent mix tanks 11 grouped in parallel with one another and containing diesoline maintained at -128 C. Each of the mix tanks has an agitator 26. From here the resulting oil/ sulphur mixture is pumped by means of submerged centrifugal pumps 12 through two stages 20, 21 of a three-stage countercurrent heat exchanger 14. In the middle stage 21 of the heat exchanger the oil/sulphur mixture is passed in heat exchange with diesoline returning to the tanks 11 after having been stripped of its sulphur, while in the coldest stage 20 the oil/sulphur mixture is further cooled by heat exchange with cooling Water. The returning diesoline has a temperature at entry to the middle stage 21 of the heat exchanger of about 20 C. to 30 C., and after heat exchange with the sulphur/oil mixture it passes through the third or hottest stage 22 of the heat exchanger, which is steam-heated, Where it is further heated to a temperature of about 128 C. by the time it leaves the heat exchanger.
As a result of the cooling, sulphur which has been dissolved in the hot oil is precipitated in more or less finely divided form. The cooled mixture is delivered into a precipitation vessel 23 fitted with a cooling jacket and from the bottom of the vessel 23 the oil and precipitate is pumped to a hydrocyclone or Super-D-Canter Sharples centrifuge 15 where the sulphur is stripped from the major proportion of the oil. The stripped diesoline passes from the hydrocyclone 15 into a tank 16 at 2030 C. whence it is pumped back via the heat exchanger 14 to the tanks 11. The tank 16 may be fitted with a cooling or heating jacket, as desired, to obtain the correct heat balance in the plant. The concentrated sulphur precipitate from the hydrocyclone or centrifuge 15 is delivered into a blending tank 24.
The solubility of the sulphur in the oil is about 10% by weight at 128 C. Bearing this in mind, a suitable ratio of oil to sulphur is 15:1. Visible precipitation commences at about 50 C. The precipitation vessel 23' may be equipped with an agitator 25.
The heat exchanger 14 is preferably a De Laval plate heat exchanger; these have corrugated plates so that fluid flowing through is caused to follow a sinuous path, which may be beneficial for conditioning the precipitating sulphur.
As an alternative, the oil in the solvent mix tanks may be maintained at a considerably lower temperature, say in the range 2050 C., sulphur being dispersed in the oil in a finely divided solid state rather than being dissolved in the oil. For this purpose the molten sulphur is fed in streams through fine jets into the oil so as to obtain a high degree of dispersion. Strong agitation is needed. The same ratio of oil to sulphur, i.e. 15 to 1, may be used as before.
A second sulphur stream is treated in a pelletising vessel 27 (FIGURE 2). The general principle of operation of this vessel is similar to that described in our patent application No. 48,828/64 but it has some important modifications. One is that the cooling liquid in the vessel is not a liquid entirely immiscible with molten sulphur,
such as water, but is again an oil such as diesoline in which sulphur is soluble to an increasing extent with rising temperature. Another modification is that the nozzles for delivering the molten sulphur streams downward into the body of cooling liquid are finer than those employed in the prior patent application and are pressurised, being generally similar to those used in prill towers. Yet another, and extremely important, change is that a multidisc rotary impeller 28 is provided in the vessel 27 which impeller rotates in the opposite direction to swirl induced in the liquid in the vessel by means of tangentially discharging peripheral oil jets 29. The object is to create shear at the region where the liquid dragged round by the impeller encounters the oppositely-directed swirl due to the jets, thereby to produce a tendency for the solidifying sulphur droplets in the liquid to break down to a finer sizing. The diameter of the impeller discs should be approximately one third that of the vessel.
The result is that the pelletising vessel 27 produces unusually small-sized pellets or granules and these are delivered from the bottom of the vessel in a stream of the oil to a centrifuge 30 where they are separated from the major proportion of the oil. The pellets or granules separated by the centrifuge 30 are fed to the aforementioned blending tank 24 (FIGURE 1), while the stripped die'soline is recycled. If desired, overflows from the pelletising vessel, containing fines, may also be delivered to the centrifuge. And the pellet-bearing stream from the bottom of the vessel may be passed to a screen, for example a wedge wire screen, instead of directly to the centrifuge, oversize pellets being removed and only the screen underflow then reaching the centrifuge.
In the blending vessel 24, which has an agitator 31 and may also be fitted with a heating or cooling jacket, the sulphur particles from the precipitation vessel on the one hand, and from the pelletising vessel on the other hand, are both mixed into the carrier liquid, e.g. crude oil, Which is to transport the sulphur through the pipe line. The flows of the two types of sulphur particles are mutually proportioned so as to achieve the optimum blend for pipe line transport, and the flow of the carrier liquid is likewise regulated to obtain the optimum density of sulphur particles therein.
Many modifications of the process are possible without departing from the scope of the invention. Thus whereas as described two types of sulphur particles produced by different techniques are blended, one could operate with only one type or the other. And there are other ways of obtaining the sulphur particles, such as pelletising in water with a silicone fluid additive under alkaline conditions (pH say 8), or reacting hydrogen sulphide chemically to produce a colloidal sulphur precipitate in alkaline solution. In these last two cases the mixture of sulphur particles and alkaline liquid can be centrifuged and the sulphur then passed through a treatment in diesoline at above C., for example, to get rid of the water content ready for the pipe line. The purpose of pelletising in alkaline water is to enable discrete pellets to be produced at a higher temperature than would otherwise be the case.
Whereas an oil fraction, such as diesoline, will normally be the most convenient liquid to employ, it will be understood that other liquids also act as solvents for sulphur and the invention is to be considered as extending to the use of such other solvents.
What is claimed is:
1. A method of preparing sulphur for transport by pipe-line in a carrier liquid, including the steps of: introducing molten sulphur into a liquid medium different from the carrier liquid thereby to create a dispersion of solid sulphur particles in said different liquid medium, separating said sulphur particles from at least the bulk of said dieifrent liquid medium and blending the separated sulphur particles into the carrier liquid for transport.
2. A method according to claim 1, wherein said different liquid medium is a solvent liquid in which sulphur is soluble to an increasing extent with rising temperature, and the sulphur is caused to precipitate therefrom by reducing the solvent liquid temperature.
3. A method according to claim 2, wherein the precipitated sulphur is separated from the solvent liquid by centrifuging.
4. A method according to claim 3, wherein the solvent is a light oil fraction and the ratio of solvent to sulphur is 15:1.
5. A method according to claim 1, wherein the molten sulphur is introduced through nozzles into a swirling body of said different liquid medium contained in a pelletising vessel, said different liquid medium cooling and solidifying the sulphur globules that result from the dispersion of the molten sulphur produced by the swirl.
6. A method according to claim 5, wherein fine pressurised sulphur nozzles are used, and the cooling liquid employed in the pelletising vessel is at least a partial solvent for the sulphur, such as a light oil fraction.
7. A method according to claim 5, wherein an impeller in the pelletising vessel rotates in the opposite direction to a swirl created in the cooling liquid by peripheral jets.
8. A method according to claim 1, wherein the sulphur particles produced are blended with precipitated sulphur particles produced by cooling a solution of sulphur in a liquid solvent therefor, this blend being introduced into the carrier liquid.
References Cited UNITED STATES PATENTS 2,798,772 7/1957 Redcay 302-44 2,947,578 8/ 1960 Corneil et al. 30266 ANDRES H. NIELSEN, Primary Examiner
US659386A 1966-08-11 1967-08-09 Transport of sulphur Expired - Lifetime US3476441A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532389A (en) * 1968-12-18 1970-10-06 Shell Oil Co Method for making sulfur-oil slurry for pipeline transportation
US3547497A (en) * 1969-04-07 1970-12-15 Shell Oil Co Operating technique for sulfur slurry pipeline
US3547495A (en) * 1968-12-18 1970-12-15 Shell Oil Co Method for making sulfur-oil slurry for pipeline transportation
US3761136A (en) * 1971-01-05 1973-09-25 Continental Oil Co Method of transporting sulfur by pipeline
US3767269A (en) * 1971-03-23 1973-10-23 Shell Oil Co Method of making and pipeline transporting a non-corrosive sulfur-water slurry
US3948565A (en) * 1971-03-23 1976-04-06 Shell Oil Company Method of making and pipeline transporting a non-corrosive sulfur-water slurry
CN103935964A (en) * 2014-05-06 2014-07-23 田晓良 Underwater forming equipment and process of sulphur

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4215996A (en) 1975-11-21 1980-08-05 Union Oil Company Of California Controlling sulfur particle hardness

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798772A (en) * 1953-01-22 1957-07-09 Gulf Oil Corp Transportation of sulfur
US2947578A (en) * 1957-09-20 1960-08-02 Humble Oil & Refining Company Procedure for transporting sulphur

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798772A (en) * 1953-01-22 1957-07-09 Gulf Oil Corp Transportation of sulfur
US2947578A (en) * 1957-09-20 1960-08-02 Humble Oil & Refining Company Procedure for transporting sulphur

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532389A (en) * 1968-12-18 1970-10-06 Shell Oil Co Method for making sulfur-oil slurry for pipeline transportation
US3547495A (en) * 1968-12-18 1970-12-15 Shell Oil Co Method for making sulfur-oil slurry for pipeline transportation
US3547497A (en) * 1969-04-07 1970-12-15 Shell Oil Co Operating technique for sulfur slurry pipeline
US3761136A (en) * 1971-01-05 1973-09-25 Continental Oil Co Method of transporting sulfur by pipeline
US3767269A (en) * 1971-03-23 1973-10-23 Shell Oil Co Method of making and pipeline transporting a non-corrosive sulfur-water slurry
US3948565A (en) * 1971-03-23 1976-04-06 Shell Oil Company Method of making and pipeline transporting a non-corrosive sulfur-water slurry
CN103935964A (en) * 2014-05-06 2014-07-23 田晓良 Underwater forming equipment and process of sulphur

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