Method of transportation, storage of elemental sulfur, methods of its extraction and composition

FIELD: transportation of sulfur.

SUBSTANCE: according to proposed method of transportation of elemental sulfur, elemental sulfur is mixed with anhydrous ammonia and/or sulfur dioxide to form fluid mixture which is then transported in container. Method of extraction of elemental sulfur from sulfur containing geological formation, mainly water-free, includes blowing through of geological formation with anhydrous ammonia, obtaining liquid solution of elemental sulfur dissolved in anhydrous ammonia and extraction of elemental sulfur from liquid solution. Method of extraction of elements sulfur from sulfur-containing mineral formation, mainly water-free, includes blowing through of mineral formation with liquid anhydrous ammonia with obtaining liquid solution of elemental sulfur in anhydrous ammonia and extraction of elemental sulfur from liquid solution. Method of storing elements sulfur includes mixing of elemental sulfur and liquid anhydrous ammonia with obtaining liquid solution or suspension and forming deposts from solution or suspension in underground formation, mainly water-free. Composition consisting mainly of solution or suspension is essentially mixture of elemental sulfur with liquid sulfur dioxide.

EFFECT: improved economic characteristics of industrial chemical processes which include presence of sulfur either in elemental or chemically boded form.

32 cl, 9 ex, 4 dwg

 

This application relates to provisional patent application of the United States No. 60/476082 filed June 4, 2003, and claims all benefits that lawfully may offer provisional patent application. The contents of the provisional patent application in its entirety is incorporated herein by reference.

The technical field to which the invention relates.

This invention relates to a technology related solutions and suspensions of sulfur and sulfur-containing compounds, with special interest are the methods of transportation of sulfur when using pipelines and other containers, where attempts are being made to prevent, eliminate or remove deposits of a solid phase, either intentionally form deposits of a solid phase. Among the many applications of this invention are chemical processes that produce elemental sulfur as a product of chemical processes and products in which sulfur is used in combination with ammonia or other nitrogen-containing compounds and when removing as suitable numbers of hydrogen and sulfur numbers in chemical processes designed to combat environmental pollution by emissions of hydrogen sulfide, including those in which sulfur dioxide or get m which can be obtained as a by-product, associated product, intermediate product or waste product in the production of hydrogen.

Prior art

As Western Canada and the United States alone each year producing approximately 1×107metric tons of elemental sulfur, mainly as a by-product of natural gas extraction and processing of oil, and with the advent of the company NAFTA in comparable quantities began to contribute and Mexico due to the production there of natural gas and the availability of the mining industry mining of native sulphur. Sulfur is also produced as a by-product and operations, oil refining operations at coal thermal power plants, the development of tar Sands in any process industry, which provides reduction of the sulphur content of the fuel or the flow of exhaust environments in order to achieve compliance with the air quality standards.

Despite the fact that industrial chemicals and commercial products can be transported over long distances when using the pipeline, which in many cases will be more cost effective in comparison with transportation by rail or other forms of delivery, pipeline Tran is the port for sulfur is not used or used at most, only short distances. This is due to the high melting temperature of sulphur corrosive sulphur when dissolved in common solvents, or when getting in contact with air or moisture observed for sulfur tendency to fall out of solution in the sediment. In transportation, in the form of a solution or suspension of sulfur has a tendency to the formation of deposits on the pipe walls, which results in the formation of the coating, clogging and blocking of the line, while the result for all of these cases will be unreliable, high maintenance costs and excessive energy consumption.

Piping system, generally similar energy systems lose heat to the environment due to radiation. Thus, in the temperate zones under normal environmental conditions the friction heat and the pulse energy flow generated over time in the piping system, in combination with the heat losses that occur on the outer surface due to radiation, is the reason that the mass in the inner space of the pipeline will be warmer in comparison with the pipeline. This leads to the fact that the wall of the pipeline becomes more cold or gives her the opportunity to be present when the matter is in transition temperature in comparison with the mass of the moving product in the inner space. As is known to experts in the relevant field, the ratio between the amounts of solute and solvent in the solution is not static, and instead, it represents the ratio determined by a dynamic equilibrium due to continued precipitation and re-dissolution in stable conditions. The solubility of the solute in most hydrocarbon solvents or in water or in aqueous media decreases significantly with decreasing temperature. As a result, over time the dissolved substance will form deposits and larger deposits will occur in the colder regions of the mass of the fluid. All it really takes place in the case of sulphur, which, as it was discovered, precipitates faster than dissolved in areas that are close to is usually more cold heat transfer surfaces, such as a pipe, flanges, fittings and connections. The resulting deposits are clogging the communicating sections, unless you will be brought energy, which will cause the mass of the fluid to move quickly enough to prevent formation zakuporivanija. Methods of heating pipelines are complex and expensive

Until recently, a significant proportion of sulphur produced in the United States, received in the result of the mining of deposits of native sulfur, especially resources of the Gulf coast, when using vysokoenergeticheskogo way of Frasa. High energy prices have since led to the reduction or termination of many of the operations implemented by way of Frasa, and a large number of major mineral deposits of native sulfur remains undeveloped.

When storing and disposing of sulfur also face problems, especially those that arise in connection with environmental pollution. Recycling is environmentally safe, yet cost-effective way to achieve difficult. Currently, recycling is the conversion of molten sulfur in solid blocks for storage on the earth's surface, the injection of sulfur in the form of H2S in geological formations or the oxidation of hydrogen sulfide to form sulfur oxides and discharge of sulfur oxides into the ground for storage.

Sulfur, mainly used in the sulfuric acid, which then is used to produce phosphoric acid and derivatives of phosphates in locations close to major mineral deposits of phosphate rock. Data IU is the one mainly found in Australia, Brazil, Florida, Idaho, the Middle East and North Africa. Receive operation phosphates are usually carried out at a very large distance from the equipment and facilities for the extraction of sulfur, and conducting many operations receiving phosphate was reduced or discontinued due to high prices of energy or power failures caused by the lack of new capacity for power generation despite the growing demand. This is especially true for the Western United States.

In the Middle East, where the cost of energy is extremely low, sulfur is transported using a long pipe, which is provided with electric heating for keeping sulfur at elevated temperature and to facilitate re-start the thread when the pipeline will be blocked due to the solidification of sulfur during abnormal operating conditions. Railway transport is used in Alberta, Canada, for transportation of dry sulfur using cargo uniform structures with direct connections to ports on the Pacific coast and to transport molten sulfur, which is prone to premature solidification, to destinations in the East and South. Transportation using trucks unified with the frames direct message requires multiple locomotives, high-quality railway cars and railway network, designed to work in harsh conditions, and it is inherently inefficient due to the need to return empty rail cars to the source of supply of sulfur. When molten sulfur is transported over significant distances, rail tank cars must be processed using the action of water vapor, as soon as they reach their destination, to any number of solidified sulfur can be re-melted before it will be unloading sulphur.

In addition, the potential with respect to this invention is the prior art associated with the production of ammonia. Enterprises for the production of ammonia are often located close to the location of the natural gas fields, where the sulfur is recovered as a by-product. Anhydrous ammonia is transported by many transportation options, including using modified tankers, barges, pipelines, Railways and trucks, and large quantities of ammonia import from different parts of the world. The main share of the production capacity of ammonia in North America currently decommissioned due to the high cost of natural gas as raw material and low prices.

Properties of mixtures of sulfur and anhydrous ammonia are described in the works Ruff, O., and Hecht, L., in "Concerning Sulfammonium and Its Relation to Sulfar Nitride (writer's translation)," Zeitschrift für Anorganische Chemie, Vol.70, p.49-69, Leopold Voss, Leipzig, 1911, and Ruff and Geisel, E., published under the same title in the journal Berichte der Deutschen Chemische Gesellschaft, Verlag Chemie, Berlin, v.38, p.2659, 1905. In these descriptions, the authors Ruff et al. reported that sulfur and liquid anhydrous ammonia react to form sulfur nitride in accordance with the reaction:

10S+4NH3←→6H2S+N4S4

This reaction is a generally accepted way of synthesis of sulfur nitride. With resistance on the air, this nitride (which in Chemical Abstracts also referred to as "sulfide nitrogen") is an explosive substance which is transformed into the elements during the course of a violent reaction, when subjected to a shock or rapid heating under certain conditions. Due to this explosive nature there is little, if at all anything, messages regarding research polimernogo sulfur nitride.

In addition, the potential with respect to this invention has a modern level of technology relating to sulfur dioxide. In the sulfur dioxide felt a great need in raw materials intended for the manufacture of sulphuric acid, but limiting factoranalysis the high costs of transportation of sulfur dioxide, as explained in the monograph Rieber, M., Smelter Emissions Controls: The Impact on Mining and the Market for Acid, prepared for US Department of the Interior Bureau of Mines, March, 1982, as quoted in US Congress, Office of Technology Assessment, Copper: Technology and Competitiveness OTA-E-367 (Washington, DC: US Government printing Office, September 1988, page 165, Box 8-A): "the demand for the liquid SO2in the United States felt in a very limited extent, but due to its relatively high cost per unit mass it can be transported over considerable distances. However, transportation is still extremely expensive because it requires special pressure rail tank cars, which are usually returned empty. The market is too small to justify measures to reduce costs, such as freight unified compositions direct messages or special ocean tankers."

In addition, the potential with respect to this invention has a modern level of technology associated with the production of natural gas from natural gas fields, characterized by a high content of hydrogen sulfide. Clogging and damage to the wells and pipelines, due to the occurrence of premature deposits of sulphur are common place and result in the emergence of problems associated with expensive maintenance (servicing ywaniem, and by lost productivity due to outages and long periods of idle time required for inspection, cleaning or replacement.

In addition, the potential with respect to this invention has a modern level of technology related to hydrogen sulfide and the extraction of hydrogen sulfide as the sulfur numbers and numbers of hydrogen. The hydrogen sulfide produced as a byproduct in the production of natural gas, and also as a byproduct in the refining operations and in many ways that are designed to remove sulfur from fuels. Canada and the United States separately produce approximately 1×107metric tons of hydrogen sulfide per year. Due to their extremely strong toxicity, Flammability, disgusting smell, asymptomatic developing the suppression of the senses of smell and corrosion activity of almost all the amount of hydrogen sulfide is transformed into elemental sulfur and water in that place or near the place where the hydrogen sulfide receive. The transformation achieved in the use of the method Claus, in which one mole of hydrogen sulfide are oxidized to produce water and one mole of sulfur dioxide, which is then injected into the reaction with two additional moles of hydrogen sulfide with the floor is rising elemental sulfur and an additional quantity of sewage or water vapor. Thus, all the number of hydrogen hydrogen sulfide is lost, leaving the waste water and low water vapor. In North America, for example, every year thus lost approximately 1.2×106metric tons of hydrogen. The Economics of hydrogen sulfide are summarized by the authors Zaman and Chakma in the "Production of hydrogen and sulfur from hydrogen sulfide," Fuel Processing Technology 41 (1995), 159-198, Elsevier Science B.V., as follows:

"Attack from various directions aimed at obtaining from the hydrogen sulfide of the two products, with sales, is amazing. Every year a large number of potential resources is lost in vain, and the need to stop this no doubt. Success in the development of appropriate technology for producing hydrogen and sulfur will be a three objectives as to minimize waste, use of resources and reduction of environmental pollution."

Hydrogen is usually produced by carrying out steam reforming reactions of conversion of water when using natural gas (methane) or other reducing agents are carbon based, including petrochemicals and coal. However, natural gas supplies are insufficient, and the scarcity and high prices, it seems, will continue to exist in the foreseeable future. In addition, it is jdy mol consumed methane way leads to the production of one mole of carbon dioxide. Thus, for example, upon receipt of the ammonia from hydrogen and nitrogen for every million tons of the obtained ammonia produce approximately one million tons of carbon dioxide (based on stoichiometry) in addition to the carbon dioxide resulting from combustion to provide energy to other technological needs. A certain portion of the carbon dioxide can be spent as the raw material intended for producing urea, but the economic benefit, which is obtained in the use of carbon dioxide in this way is insufficient for economic compensation for loss of methane as CO2is readily available from other sources in ways that do not include consumption of methane. In addition, it is known to specialists familiar with the proposals in the hydrogen economy, hydrogen will continue to increase and, thus, exacerbate serious problem associated with excessive emissions of CO2in the environment, which are recognized factor contributing to global warming. This is due to the fact that large-scale production of hydrogen uses reducing agents carbon based and will continue to do so in the foreseeable future despite significant advances in technology in the renewable energy sources. Thus, upon receipt of the hydrogen in the reforming of methane in the best conditions for each ton of hydrogen will receive at least five and a half tons of carbon dioxide. The urgency of the situation would ease the production of hydrogen from non-carbonate sources according to the method, a byproduct of which is solid minerals, such as gypsum, and not gases that cause the greenhouse effect.

Known circuits for producing hydrogen from hydrogen sulfide are the following:

H2S+WITH←→COS+H2(reaction 1)

H2S+NO←→NOS+H2(reaction 2)

H2S←→1/2S2+H2(reaction 3)

Reaction 1 is described in U.S. patent No. 4618723 (Herrington et al., October 21, 1986), while reactions 1 and 2 are discussed in U.S. patent No. 3856925 (Kodera et al., December 24, 1974). The most striking recent development related to reaction 1, is partially funded by the National science Foundation and assigned Lehigh University, as described in U.S. patent No. 6497855 (Wachs, 24 December 2002). The author of the patent Wachs reports that the internal thread COS may be subjected to catalytic oxidation under the action of O2with the formation of SO2in accordance with the reaction:

COS+O2→WITH+SO2(reaction 4)

with the simultaneous regeneration and is race on recycling internal thread, which is used to produce more hydrogen from the source of the flow of fresh hydrogen sulfide in accordance with the above reaction 1. The total reaction represents the following:

H2S+O2→N2+SO2(reaction 5)

The practicality of this scheme is limited to the additional load in the form of utilization of SO2. The author's description Wachs for the disposal of SO2offers two alternatives: 1) use in the production of sulfuric acid and 2) the departure of SO2on recycling in order to restore two additional moles of hydrogen sulfide to obtain elemental sulfur and water, as, for example, by the method Claus. The first of them, reportedly, is an attractive option in areas close to large consumers of sulfuric acid, such as refineries. However, unfortunately, the inefficiency and high cost of transportation of sulphuric acid makes it impractical in the case of remote sources of supply of hydrogen sulfide, such as deposits of sour gas in Wyoming or Alberta. Large remote sulphuric acid production also must compete with the production of sulphuric acid as a by-product of metallurgical whom is the inat. The disposal of excess acid in remote locations leads to problems with environmental protection, because the acidification of the massive deposits of carbonates, such as limestone, leads to a wide range of problems, including excess emissions of CO2.

Utilization of SO2the result of departure for recycling when using the method of clause limits the yield of hydrogen from hydrogen sulfide, in the best case, about one third in the calculation of gross stoichiometry (the combination of the Claus reaction, reaction 5) as follows:

3H2S+O2→N2+2H2O+3/8S8(reaction 6)

A reaction scheme 6 also becomes a source of problems related to economy and ecology, which is caused by the receipt in her excess of elemental sulfur in remote locations. This leads to a decrease in the economic benefits that could be derived from hydrogen sulfide.

Summary of invention

Currently, it was found that anhydrous ammonia and sulfur dioxide are applied and achieve the unexpected benefits as fluid media to elemental sulfur or as a result of dissolution of elemental sulphur solution or suspension ale is nternal sulphur suspension. This applicability stems from still not conscious of the chemical and physical properties as anhydrous ammonia and sulfur dioxide in liquid form. In the case of anhydrous ammonia data properties include atypical inverse temperature solubility, reduced tendency to korrodirovaniju black metal and the preferred dissolution of existing deposits of sulfur and sulfur deposits in the moment of their formation on the internal surfaces exposed to the environment of pipelines and other containers. In the case of sulfur dioxide data properties include the unexpectedly low rate of change of solubility depending on the temperature in a wide temperature range, and similarly reduced tendency to korrodirovaniju black metal. In the case of both media feedback data properties is to reduce or eliminate deposition of sulfur in the vessel, which otherwise would be caused by the flow of heat exchange between the tank and the environment, and, accordingly, reducing the occurrence of clogging, education cover any obstacles to the flow inside the tank caused by deposition, in comparison with the methods of the prior art, in which the liquid media use water, water races the thieves or hydrocarbons. Thus, the invention relates to a method of transporting sulfur when using pipelines and other containers and to methods of removing elementary sulfur from geological formations, including soil and rock formations, the extraction of sulfur from naturally occurring materials such as ore, waste rock, and oil or oils, extraction of sulfur from essentially anhydrous carbonate solid phases, sulfur-containing mineral formation, essentially containing no water, and underground formations, essentially containing no water, and extraction of sulphur from industrial mixtures of any of the industrial equipment, which is the introduction, deposition, dispersion or dissolution of sulfur. The invention also relates to methods for sulfur storage in geological formations and, in particular, in underground formations, such as voids or porous formations, such as Sandstone or porous rock. In addition, the invention relates to solutions and suspensions of sulfur in liquid sulfur dioxide as new compositions of related substances.

In many embodiments of the invention include the simultaneous delivery of sulfur and ammonia or sulfur and sulfur dioxide in places where one or both representatives of them use isout or commercial or for industrial purposes, e.g. as fertilizer or raw materials, and transportation of sulfur from remote sources of supply operations oxidation for use as fuel, as, for example, in power plants that serve the population centers with high energy needs. The opening also facilitates the transportation of sulfur to equipment for the production of phosphoric acid and phosphates, and in General to any equipment that uses sulfur, while minimizing the formation of sulfur dust, explosion or fire, dust, bacterial decomposition, moisture, acid contamination, corrosion and the cost of transportation. The invention also finds use in the methods of fighting pollution, emissions of hydrogen sulfide, in which the extraction of hydrogen in the form of gaseous H2accompanied or may be accompanied by formation of SO2that can be removed only by the reaction with an additional number of H2S with the formation of elemental sulfur and water, which thus leads to the transformation of the hydrogen number in the H2's in the water, and not to its recovery in the form of molecular H2.

Brief description of drawings

1 before the hat is a histogram comparing the rate of change of the solubility of sulfur in different liquids depending on the temperature.

Figure 2 is a graph of the solubility of sulfur from temperature for solutions of sulfur in various liquid media, maps anhydrous ammonia with organic liquids.

Figure 3 is a map of a technological route for multi-operational scheme of processing of raw materials from natural gas fields and deposits of native sulfur when using the principles of the present invention.

Figure 4 is a map of a technological route for additional multi-operational processing flow of gas from the field serviceconnected natural gas when using the principles of the present invention.

Detailed description of the invention

Solutions and suspensions are accessed in this description and the attached claims of the invention are described in connection with the substances from which they are obtained, that is, elemental sulfur and either anhydrous ammonia or sulfur dioxide. Molecular forms of these substances may change, as only the latter will be combined, resulting in either complexation, or passing a chemical reaction, usually reversible, and any such transformation can take place to a greater or lesser extent in C the dependence on external conditions, such as temperature and pressure. Thus, elemental sulfur, for example, may be present in ammoniacal solution or suspension in the form of the product of the reaction between sulphur and ammonia. Solutions and suspensions are addressed in this document include any of the transformed state of matter that result from combining them. Thus, the term "solubility" when it denotes gross solubility, which includes the transformation of substances in liquid form as a result of either reaction or complexation, or simple dissolution. Despite the fact that the presence of transformation products or the degree of conversion can be detected using conventional analytical methods, the effectiveness and applicability of the present invention such conversions negative influence, since these transformations in General are reversible when removing elemental sulfur from solutions or suspensions. In some cases the substances are applied in combination, and do not require separation or retrieve one from the other. However, the combination does not suggest the inclusion of products, which are formed by the interaction of any of these three substances with other substances, or which are formed when using the catalytic action or extended reaction conditions, such as fever.

In this description and in the annexed claims certain substances and systems are characterized as "essentially anhydrous" or "essentially does not contain water. The term "essentially" in these characteristics indicates that these substances either in the system or completely devoid of water, or contain, at most, trace amounts, that is, that any quantity of water that will be present will be insufficient to adverse influence on the properties of sulfur, ammonia or sulfur dioxide or a solution or suspension in any way, which would lead to a significant reduction in economic benefits from the use of a solution or suspension in the practice of this invention. In the case of ammonia, the term preferably refers to the level of the water content of approximately 0.3 wt.% or less, more preferably approximately 500 hours/million (wt.) or less, and most preferably approximately 100 hours/million (wt.) or less. In the case of sulfur dioxide, the term preferably refers to the level of the water content of approximately 200 hours/million (wt.) or less, more preferably approximately 100 hours/million (wt.), and most preferably approximately 50 hours/million (wt.).

The change in the solubility of sulfur in various liquid media, the temperature dependence shown in figure 1, it is necessary to take into account that the term "solubility" is used in the present invention to denote a combination of elemental sulfur and a carrier to form a liquid environment, regardless of whether the combination will cause the chemical reaction or complexation between the gray and the carrier or to the simple dissolution of sulfur in the media. Figure 1 is a histogram where each bar represents the angle dependence of the solubility of sulfur from temperature for seven different solvents, with all determinations were performed within the temperature range from -20 to +30°C. Two rightmost column on the histogram represent sulfur dioxide and ammonia, respectively, while the remaining bars represent carbon disulphide, benzene, toluene, cyclohexane and heptane. The height of each column indicates the increase in the solubility of elemental sulfur in hours/million (wt.) one degree Celsius increase in temperature, i.e. the temperature coefficient of solubility. As shown in the histogram, all media are characterized by a positive temperature coefficient of solubility with the exception of ammonia, which is characterized by a negative coefficient, and sulfur dioxide is characterized by a positive,but extremely small coefficient. The coefficients represent the following:

CS25300 h/million/°
Benzene467 hours/million/°
Toluene330 hours/million/°
Cyclohexane249 hours/million/°
Heptane111 hours/million/°
Sulfur dioxide3 hours/million/°
Anhydrous ammonia3386 hours/million/°

In embodiments of the present invention, which include the use as a carrier of anhydrous ammonia, the invention relates to unusual and unexpected characteristics gross solubility of sulfur in anhydrous ammonia. In commonly used media of the prior art, such as carbon disulfide and various hydrocarbons, the solubility of sulfur increases significantly with increasing temperature, as illustrated in figure 2. The sloping line, sharply rising upward in figure 2, is carbon disulphide, and below the line combines benzene (represented by unfilled circles), toluene (represented by open squares) and cyclohexane (represented by x). Line with a slope down is anhydrous ammonia. This slope is the bottom takes place in the temperature range from about -20 to about +40° C. At temperatures below -20°C, the solubility of sulfur in anhydrous ammonia remains approximately constant at a level corresponding approximately 38 wt.% sulfur. Above -20°solubility decreases gradually with increasing temperature, reaching approximately 20% at 35°C.

The data shown in figure 2, shown below in tabular form together with the data obtained by using as a carrier of other fluids.

The solubility of sulfur (mass%) in different liquid environments depending on the temperature (in degrees Celsius)
Anhydrous NH3CS2BenzeneToluene
°%°%°%°%
are-20.538,1-201201,0-210,38
032,3-10 15101,3-100,576
16,425,6019201,7131,52
30of 21.21023,5252,1201,83
4018,52030302,4352,72
30a 38.5403,2
4050
CyclohexaneHeptaneOlive oil
° %°%°%
11,10,7200,12152,2
22,21,02250,36304,1
26,11,09350,51406,2
44,22,02
40*1,8*
*after interpolation.

It was also found that in contrast to the views showing the prior art, a solution of sulfur-ammonia contains no perceptible to the of icest sulfur nitrides. Sulfur dissolved in anhydrous ammonia, shows absorption spectrum having bands in the areas 580, 430, and approximately 295 nm. The intensity of the two bands with shorter wavelengths with increasing temperature decreases, while the intensity of the band in the range of 580 nm when increasing the temperature increases. This suggests that, when dissolved in anhydrous ammonia are present, at least two compounds of sulfur. If, as anticipated by prior art, ammonia and sulfur will react with each other with the formation of hydrogen sulfide (H2S) and tetranitride tetrasomy (N4S4), then both connections must be separately observed in the absorption spectrum. The hydrogen sulfide dissolved in anhydrous ammonia, shows a strong absorption band in the region of 270 nm - band, which is absent in the absorption spectra of solutions of sulfur in anhydrous ammonia. Similarly, when anhydrous ammonia dissolved N4S4the band appears in the region of 254 nm and over time disappears, leaving themselves a band in the region of 360 nm due to the conversion of tetranitride in the ammonia adduct of the dimer, i.e., N2S2·NH3. None of these bands are not observed in solutions of sulfur-ammonia corresponding to the present image the structure.

System sulfur-ammonia, corresponding to the present invention include liquid solutions in which all sulfur is in liquid form, and no sulfur particles does not remain, and suspension of sulfur in ammonia or most often in ammoniacal solutions containing dissolved sulfur. Solutions and suspensions are herein collectively referred to as "fluid mixtures". The amount of sulfur contained in these fluid mixtures can vary and is not critical in the practice of the present invention. However, in most cases, best results will be obtained when using systems in which sulfur is at most approximately 65 wt.% when calculating the mass of a fluid mixture or preferably is in the range from about 20% to about 65 wt.%, more preferably from about 40% to about 60 wt.%, and most preferably from about 50% to about 60 wt.%. In the case of transportation using pipelines or any other vessel through which perepuskat fluid mixture, such as a pipeline for pumping or piping for loading or unloading of a stationary container, such as a storage tank, truck tank, tank or ship's hold, the temperature of the tanks for transport is investing preferably equal to 35° With or less, and more preferably 20°or less.

As mentioned above, the application of the invention to achieve particularly significant economic benefits, is the transportation of sulfur in ammonia when using the pipeline. Due to the presence of the temperature - solubility of sulfur in ammonia negative slope of the need for heating pipelines to maintain flow of solutions or suspensions of sulfur is eliminated or significantly reduced, as is the need for the adoption of emergency measures aimed at preventing the occurrence of corrosion problems. In addition, because of the sulfur, and ammonia is produced from natural gas as sulfur and ammonia can be obtained from the same source. In addition, since as sulfur and ammonia are important raw materials for receive operations of fertilizers and phosphates on the same object, then the solution or suspension of sulfur in anhydrous ammonia are effective and beneficial means of delivery of these raw materials to such transactions.

As mentioned above, the solubility of sulfur in anhydrous ammonia increases significantly with decreasing temperature. Therefore, preferably, will dissolve the sulfur crystals, which are formed close to the colder surfaces of the heat is peredachi pipeline system, and not those in warmer areas. Thus, in areas adjacent to the generally more cold surfaces of the heat transfer anhydrous ammonia is the best solvent and the sulfur concentration is further lowered below the saturation concentration compared to areas that will be removed from the surfaces of heat transfer. When caused by radiation heat loss occurs on the outer surface of the pipeline, particularly in the presence of diurnal effects, system of ammonia solution and suspension will wash away any deposits of sulfur with the inner surface. Thus, the outer cooling pipe may be a result of radiative cooling in air or convection cooling in air, in soil formations in the case of underground pipelines or water in the case of underwater pipelines.

If sulfur will either dissolving or dispersing in anhydrous ammonia, any solid-phase sulfur, which can be formed in the form of sediment, by their nature, will easily succumb to processing, to demonstrate the behavior of loose sediment and will not be neither sticky nor tarry, but instead it will be easy to be re-dispersion after long periods of deposition. The dissolved sulfur is characterized by evitando low tendency to form coatings or deposits on heat transfer surfaces, especially when the vessel containing the solution or dispersion, will be cooled below the ambient temperature.

Saturated liquid phase in suspension sulfur-ammonia has a color close to purple-black. If you produce a slow release of gaseous ammonia for dropping pressure, then the solid sulfur that will remain, will change the first color to orange, and then to greenish-yellow or light yellowish-brown, and you can feel the emergence of a rapidly changing smells formed sulphides and ammonia. Sulfur which is removed in a dry form from a solution in anhydrous ammonia has a more vivid and bright color, and if the manipulation will be carried out by means of a closed system that minimizes the impact on the mix of air and moisture, no noticeable odors sulphides will not be noticed.

The use of sulfur dioxide as a carrier for elemental sulfur, corresponding to this invention, despite the absence of a negative temperature coefficient of solubility, as its advantages shows a very low degree of decreasing solubility with decreasing temperature within the temperature range from about -20°C to approximately +35°C. the solubility of the element is Noah sulfur in sulfur dioxide at -20° With is extremely low, and the degree of its increase is equal to approximately 3 hours/million per degree Celsius increase in temperature. In accordance with this saturated solution of sulfur in the sulfur dioxide in the case of curing at a temperature in the range from about -20°C to approximately +35°will not form sulfur deposits on the vessel walls. At temperatures higher than 35°C, the solubility of elemental sulfur in liquid sulfur dioxide increases with increasing temperature in degree, which is significantly higher than the level observed at temperatures below 35°C. Increase increase the solubility of one degree Celsius at temperatures exceeding 35°With, in the General case exceed 50 hours/million, and is typically in the range from approximately 50 hours/million to approximately 130 hours/million Due to this higher degree of increase in sulfur in a saturated solution of sulfur in the sulfur dioxide in temperatures exceeding 35°will have a pronounced tendency to form deposits in small decreases in temperature.

Therefore, in the case of curing at a temperature in the range from about -20°C to approximately +35°With a saturated solution of sulfur in the sulfur dioxide or solutions that are slightly supersaturated, can be transported when used and pipelines, railway tanks and other containers without the occurrence of clogging or other negative phenomena that accompany the formation of sediment solid phase, simply by keeping the vessel at a temperature within this range. Thus, this capacity can be exposed to environmental conditions, changing in a wide range, which usually are containers for transportation or which may arise in different environments, through which sulfur will need transport to get to destinations, where sulfur will find yourself the most economically viable commercial application, with little risk or if the risk of clogging due to the presence of the wall temperature, which is lower than the temperature in the mass of the fluid. For this reason, the advantages achieved by the use of sulfur dioxide as the fluid for transporting sulfur, in some cases, there may be a few less, but in the General case is similar, in comparison with the advantages obtained in the use of anhydrous ammonia.

System sulfur - sulfur dioxide, corresponding to the present invention include liquid solutions in which all sulfur is dissolved in sulfur dioxide and so will the seeking in liquid form in the absence of the remaining particles of sulfur, and suspension of sulfur in the sulfur dioxide or most frequently in the solution of sulphur dioxide, which contain dissolved sulfur. As in the case of mixtures of sulfur - ammonia solutions or suspensions sulfur - sulfur dioxide herein collectively referred to as "fluid mixtures". The amount of sulfur contained in these fluid mixtures can vary and is not critical in the practice of the present invention. However, in most cases, best results will be obtained when using systems in which sulfur is from about 1800 hours/million (wt.) to about 65 wt.% when calculating the mass of a fluid mixture, preferably from about 1% to about 60 wt.% or more preferably from about 10% to about 50 wt.%. In the case of transportation using pipelines or any other vessel through which perepuskat fluid mixture, such as a pipeline for pumping or piping for loading or unloading of a stationary container, such as a storage tank, truck tank, tank or ship's hold, the temperature of the vessel for transportation of preferably equal to 40°or less, and more preferably 20°or less.

This included opening and facts, namely, that any solid-phase CE is a, which is formed as a precipitate in liquid sulphur dioxide, by their nature, will easily succumb to processing, to demonstrate the advantageous behavior of loose sediment and will not be neither sticky nor tarry, but instead it will be easy to be re-dispersion even after long periods of deposition. Sulfur is characterized by unexpectedly low tendency to form coatings or deposits on heat transfer surfaces, when with mixes will manipulate or mixture will be maintained at temperatures below about 35°and, in particular, lack of tendency to the formation of coatings or deposits when tanks for transportation will be cooled below the ambient temperature.

Sulfur dioxide, intended for use in obtaining fluid mixtures sulfur/sulfur dioxide, can be obtained by partial oxidation of sulfur or hydrogen sulfide by commonly used methods, for example, in a plant for the processing of sour gas. After that, the obtained product sulfur dioxide shipped directly as a product or mixed with elemental sulphur and enrich it with the receipt suspension of sulfur in the sulfur dioxide. Then the solution or suspension is transported when using the pipeline is an ode or other conventional means for transporting fluid. The solution or suspension can be used directly to obtain sulfuric acid or to share in industrial or commercial purposes using conventional techniques. If the pipelines will occur premature formation of deposits of sulfur, the operator can switch the mode of operation using a system based on ammonia to dissolve the deposits as described above. In case of contact with anhydrous ammonia and anhydrous sulfur dioxide in close proximity to each other in gaseous or liquid phase quickly formed a hygroscopic salt. In those operations in which these salts would be undesirable, to minimize contact between the ammonia and sulfur dioxide can be used in ways well known to experts in the respective field.

Therefore, in General, sulfur dioxide plays the role of an effective and efficient environment for transportation of elemental sulfur. In addition, the possibility of sulfur dioxide by so effective transportation of sulfur demonstrate a hitherto unrealized advantages in operations to combat pollution by emissions of hydrogen sulfide, due to the elimination of the need of spending valuable hydrogen in the conversion of all dioc the IDA sulfur back into elemental sulfur and waste water. Hydrogen gas output can be increased by the conservation of the total number or part of the sulfur dioxide or otherwise as a result of receiving the combination of sulfur dioxide and elemental sulfur and transportation of sulfur dioxide and sulfur in combination, when using the pipeline or otherwise, to the place where one representative of them or both can be used for economically viable and effective use. Thus, in operations that use the method Claus or any other way to combat environmental pollution by emissions of H2S, which leads to the obtaining or can be modified to obtain as gaseous hydrogen, and sulfur dioxide, the practice of this variant of the invention results in obtaining even three useful products is gaseous hydrogen, elemental sulfur and sulfur dioxide, while gaseous hydrogen is produced from the output, which is larger than that achieved in the prior art.

Containers for transportation in accordance with this invention can be transported solutions or suspensions of sulfur or ammonia or sulfur dioxide, can vary widely in size, configurations and materials for the reconstruction. Due to less corrosion activity of these compounds in comparison with solutions or suspensions of the prior art containers for transportation can be made from materials that are less inert to corrosive liquids and therefore less expensive in comparison with the materials of the containers, which are designed to resist corrosion. For example, a tank with a lining of glass or lining of the special-purpose resins are not required, the same applies to tanks constructed of special vysokomorozostoykoy alloys. Perhaps the use of pipelines and other containers having an inner surface made of black metal, such as in the General case alloyed steels. As for the variants of the invention include use as a carrier of ammonia, the advantages of the invention can be identified in case of pipeline transport, regardless of whether the pipeline to be outdoors, to be buried under the ground or going through the water column. For information corrosion to a minimum solutions or suspensions of the present invention are at least essentially anhydrous, and preferably completely anhydrous. Similarly obtained at the Kie formation, of which remove sulfur or sulfur stored in accordance with this invention are at least essentially not containing water, and preferably completely devoid of water.

Figure 3 represents a technological map of the route showing one example of the implementation of some of the discoveries of this invention in operation during transportation energy, sulphur and other commercial products as a medium for transportation use anhydrous ammonia.

Raw materials in the form of natural gas from natural gas fields 11 is subjected to processing operations in the processing of natural gas, including installation for removing sulphur 12, designed to remove naturally occurring sulfur-containing pollutants, mainly hydrogen sulfide, according to well known methods to obtain separate streams of products in the form of elemental sulfur, low-quality water vapor or wastewater and is suitable for sale of methane (natural gas). Part cleaned from pollutants natural gas is fed to the receive operation of anhydrous ammonia 13, where natural gas is processed by well-known methods of the prior art with the receipt of raw materials in the form of hydrogen and by-product in the form of carbon dioxide the ratio, representing at least five and a half tons of CO2per tonne desired molecular hydrogen. The thus obtained hydrogen combine with atmospheric nitrogen by well-known methods of obtaining anhydrous ammonia. Part of the anhydrous ammonia operation produce ammonia 13 served in the module mixing with sulfur 14, where the ammonia combines with sulfur from the unit for removing sulphur 12 obtaining unsaturated solution of sulfur in ammonia. Unsaturated solution when using pipeline perepuskat in the booster mixer 15, which represents the combined mixing and pumping station. Booster mixer 15 also receives a suspension of native sulfur in anhydrous ammonia operations, which are described hereinafter, to obtain a suspension of particles of sulphur in the sulphur solution in anhydrous ammonia.

Suspension of the booster mixer 15 passes through the pipeline to the module mixing with sulfur 16, which also receives the elemental sulfur from the processing plant, oil 17, and sent to recycling the ammonia as and when necessary. The slurry from the mixing module with grey 16 channel further along the process flow in the sump sulfur 18, where part of the liquid phase 19 of the suspension is decanted in the form of a solution not containing the suspended solid is the basics, and served in the underground storage of sulfur 20. The remaining slurry with high solids send another further along the process flow through the pumping station 21 in the mixing module with gray 22. This module takes an additional amount of sulphur as a by-product module for processing bituminous Sandstone 23. An additional amount of sulfur is mixed with a suspension, which is then pumped to the final destination 24.

On the final destination 24 part of the suspension load in bulk vessel 25 for transportation on a receive operation phosphates outside the United States. The remaining suspension perepuskat in the separating installation 26. Part 27 of the liquid phase of the suspension separation plant 26 decanted and sent in the form of a solution in another bulk vessel 28, which, for example, can deliver a solution in the place of farming to be used as fertilizer for direct application.

On separation plant 26 anhydrous ammonia is distilled using compressors and the like and sent forth by the processing circuit 31 for use as feedstock or process flow 32 back in the order of departure in recycling. At the moment, the ammonia can be sold in anhydrous f is RME in the quality of the product or it can be combined with water for sale or use as an aqueous solution of ammonia. Separation system 26 also provides the production of elementary sulfur 33 for transportation to markets around the world when using the sulfur carrier 34. In addition, elemental sulfur 35 is fed to the plant for sulphuric acid 36 for use as feedstock. The plant for acid 36 generates water vapor 37, not containing oxides of carbon. Water vapor is directed to steam turbine power plant 38. Part 39 is received in the form of a product of sulfuric acid from plant production of acid 36 is sent to the neutralization is set to 40, another part 41 is sent to the plant for sulfates 42, and the third portion 43 is sent to the plant for phosphate 44. Currently available is sulfuric acid for sale.

On the plant producing sulfates 42 sulfuric acid can be used for the conversion of non-carbonate materials raw materials in products such as building materials, or salts of sulfuric acid of various metals without the formation of carbon oxides. In the case of materials of carbonaceous raw materials such as limestone, released carbon dioxide 45 perepuskat on the plant for urea 46 as a source of raw material for urea, which is useful for use in improving photosynthesis forests and crops and in different the other use cases, including the absorption of carbon dioxide. On the plant producing phosphates 44 prevent the formation of carbon oxides due to the processing of non-carbonate ore with production of phosphoric acid, ammonium phosphates and other phosphatic products and gypsum used for construction materials or long-term storage of sulphur in the number.

If you go back to separation plant 26, 31 ammonia, which is distilled from the plant and perepuskat further technological scheme, can be sent directly to any of the various operations involving the use of nitrogen, including: (a) neutralization installation 40, which produces water vapor and fertilizer/soil amendment on the basis of ammonium sulfate, (b) on receipt acid 47, which produces steam for the power plant 38 and nitric acid, and (C) for the plant for urea 46, which uses ammonia and carbon dioxide from the processing plant oil or plant producing sulfates 42. Another part of this is directed further along the technological scheme of ammonia 31 of the separation unit 26 perepuskat installation of obtaining nitrates 51 together with the nitric acid from plant production of acid 47 to obtain the safe explosives and other nitrates. The plant for urea-shumilkin) is the first nitrate 52 produces solutions of urea-ammonium nitrate when using the original streams from the plant for urea 46 and installation of obtaining nitrates 51.

Products from the data located further along the technological scheme of the units 38, 42, 44, 51 and 52 are suitable for use in manufacturing and agriculture 53. The electric energy obtained by using a steam turbine power plant 38, has been feeding in the unified power system 54. The power plant can be improved by installing a module running on coal, and from the point of view of air quality, it can allow your operator to obtain quotas for emissions to compensate for previous emissions of oxides of carbon, sulfur and nitrogen.

If you go back to the upper left side of the map processing route, you can see that part of the ammonia with the operation of obtaining anhydrous ammonia 13 is directed through the compressor 61 and down the well in the field of brimstone 62. Dissolved elemental sulfur pumped from extraction wells in the hub sulfur 63. Anhydrous ammonia is distilled off from the hub 63 and sent for recycling through the compressor 61 back into the well 62. A suspension of the product perepuskat from the hub sulfur 63 through the booster pump station 64 for supply to the piping system in place booster mixer 15.

The solution from the sump sulfur 18 is pumped into geological formations in the storage pool 19. When will precede the flax load solution anhydrous ammonia 65 underground distilled off and collect when you use a compressor router 66 through a gas well. If desired, laid deposited sulfur is extracted from the pores of the earth in the by-passing the underground fresh liquid anhydrous ammonia through the compressor circuits 66, extraction mixture containing dissolved sulfur through (67) extraction wells 68 and direction of the extracted mixture isolecithal the hub 69. Anhydrous ammonia 71 distilled from sulcatas hub 69 and sent for recycling in various modules located on technological scheme previously, including the operation of receiving anhydrous ammonia 13 modules mixing with sulfur 14, 16, 22 and into the sump sulfur 18, while the extracted suspension product 72 perepuskat further technological scheme when using the pipeline system.

The operation of obtaining anhydrous ammonia 13 provides a flow of ammonia to the plant for suspension at the final point of the grain 73, and the suspension of grain pipes send further technological scheme in grain separator 74, where anhydrous ammonia is sent for recycling in the final paragraph of receiving grain 73. The extracted grain sent in on the market mills 75 or more options for commercial use.

The operation of obtaining anhydrous ammonia 13 similarly, the supply of ammonia in the plant for coal slurry 76, and the coal slurry from us is anouki when using pipeline transported to the separator coal 77, where the coal is separated from the ammonia and sent for coal thermal power plant 78 performing submission to a power grid 54. Ammonia is sent for recycling from the separator coal 77 back to the plant for coal slurry 76.

In order generalization of the ways in which the present invention is realized in this multistage method, we can say that the ability of the invention to provide transportation suspensions sulfur-ammonia through the pipes without clogging makes it possible to transfer between the first two modules of mixing with grey 14 and 16 when using a booster pump 15, the transmission from the hub sulfur 63 to the second mixing module with grey 16 when using two booster pumps 64, 15, transferred from the second mixing module with grey 16 to the sump sulfur 18, the transfer from the sulfur settler 18 to the third module mixing with grey 22 when using a booster pump 21 and the transfer from the third module mixing with grey 22 to the final destination 24. All modules card processing route are usually used for design and operation.

Figure 4 is a map of the technological route, illustrating another example implementation of some of the discoveries of this invention, this time demonstrating removing the forefront of the lar hydrogen of the previously mined deposits serviceconnected gas, containing a certain amount of raw natural gas at very high levels of hydrogen sulfide and carbon dioxide.

From gas fields 101 submit sour gas 102 for installation of a natural gas processing 103, where gas is extracted hydrogen sulphide 104 and perepuskat in the installation of conversion to hydrogen 105. Installation of gas processing 103 also performs and separation of carbon dioxide 106, which perepuskat in a plant for urea 107. In a plant for processing gas 103 is also separated and methane 108, suitable for sale in the markets of natural gas 109. Installation of conversion to hydrogen 105 uses carbondisulfide modified surfaceanalysis the manner or method of thermal cracking to obtain in the year one hundred thousand tons of molecular hydrogen 111, which perepuskat on the operation of obtaining ammonia 112. The receive operation of the ammonia does not waste a large amount of natural gas, which is for her the raw material, and provides suitable-for-sale environmental quotas on emissions of approximately of 550,000 tons per year prevented the obtaining of carbon dioxide. Installation of conversion to hydrogen 105 also produces sulfur dioxide, a half of which condense and perepuskat (113) in the module paramashiva the Oia with grey 114. The remaining sulfur dioxide is introduced into the reaction with the initial flow of fresh hydrogen sulfide with receiving waste water and elemental sulfur 115. Elemental sulfur perepuskat (115) in the module mixing with grey 114, where it unites with the sulphur dioxide to obtain a suspension containing about 60 wt.% sulfur in suspension in sulfur dioxide (80% of total sulfur, 20% oxygen). Suspension perepuskat when using working in several modes of pipeline slurry 116 destination transport by water 118 (i.e. port of loading), where the suspension is exported using a modified bulk vessel 119 to producers of phosphates outside the United States. Part of the flow of sulfur dioxide can be directed to operations bleaching of wood products and the like.

The operation of obtaining ammonia 112 as a flow of feedstock to produce ammonia uses molecular hydrogen 111. Ammonia can be bypassed when using pipe 121 in connection with operating in multiple modes pipeline for the suspension 116 in place of the module mixing with grey 114 as additional fluid means for transporting the suspension of sulfur, and from there to your destination transport by water 118, where the resulting suspension with multiple media upload is in bulk vessel 122 to export agricultural markets or to the producers of phosphates, outside the United States. Alternatively, the ammonia can be sent (123) as the raw material to the plant for urea 107 or any other operation to add value, including the use of nitrogen. A small part of the flow of anhydrous ammonia is also napravlyayut (124) from operations produce ammonia 112 to the field serviceconnected gas 101, where it is used for periodic dissolution and purification for removal of sulfur deposits from the internal surfaces of pipes and other heat transfer surfaces.

Thus, the use of the pipeline in this operation makes it possible transportation as sulfur and sulfur dioxide in suspension from remote locations to a destination transport by water 118 without the risk of clogging of the pipeline. All modules card processing route are usually used for design and operation.

The following examples are offered for purposes of illustration and are not intended to limit the scope of the present invention. All percentages and other proportional to the number given in these examples are mass, unless other specified.

EXAMPLE 1

This example illustrates the characteristics of solubility and fluidity of mixtures of sulfur and Bezbog the CSOs ammonia at different temperatures.

Representative models of tanks for transportation were made of transparent 19 mm pipe PVC Schedule 40 or Schedule 80 with suitable lengths that ensures a capacity of approximately 100 ml per one part of the pipeline. Each link on one end was muffled when using the techniques of solvent welding and gluing, and on the other end was placed a ball valve. Each container was weighed to determine its mass container, and then uploaded it with liquid anhydrous ammonia. After this was determined by the weight thus added ammonia in a separate container with the same design placed a predetermined amount of sulfur. Then the tank with ammonia and sulfur were connected through their valves and the valves opened to combine liquid ammonia and sulfur, which are then mixed in the rotation, rolling and shaking each tank.

Observing, has determined that a mixture in which the sulfur level was 50 and 60 wt.%, was a mixture in the form of a very viscous slurries at ambient temperatures, at least less than 20°C (68°F). At 65 wt.% sulfur-containing mixtures are fluid, but they demonstrate a significantly higher viscosity at such temperatures on the physical environment. At 70 wt.% sulfur-containing mixtures included a significant quantity of powder, which had very limited, if at all any, fluidity at temperatures in the range from approximately 0°C (32° (F) to at least 20°C (68°F). When the observance of proper precautions fluidity of the mixture with a sulfur content of 70 wt.% significantly improved in the cooling of the mixture in the bath with dry ice.

EXAMPLE 2

This example illustrates the pumping of solutions and suspensions of sulfur in liquid anhydrous ammonia in a bench model.

Poster piping were made of which has a diameter of 19 mm tube of steel and transparent PVC, forming the total length of the contour, approximately 4 ft. The circuit included a small pump and ~ 0.9-meter universal adapter from steel, bent down at an angle of ninety degrees with the drain valve. Universal adapter was placed on the middle of the path, counting from the pump, and it was attached using a suitable shut-off valves and removable short sleeves below the cut-off valves. The three-link independent vertical tubes was added in the form of tees, directing bends vertically upward from the main circuit. Data vertical pipe disposed at the right intervals between pump and guiding the data down a universal adapter on one side of the path. Vertical pipe had a height of 15 to 25 cm Vertical pipe that is closest to the pump, equipped with a valve connection, leading to the vacuum pump. The second vertical pipe was equipped with a commercial temperature sensor and pressure of ammonia. The last vertical pipe was equipped with a 19 mm ball valve. A return line from the universal adapter to the pump consisted of a 1.5-meter link welded steel 19 mm pipe and a small link pipe made of transparent PVC. Approximately 1.3 meters 1.5-meter long steel return line was equipped with a jacket of PVC with a diameter of 50 mm with cooling water supplied to the input of a gate valve. Between the pump and the first vertical pipe placed one 19 mm ball valve. The whole system is securely attached to a tilting panel length 1.8 meters and vertical pipes attached bracket stiffness.

The system was cleaned and repeatedly rinsed with distilled water and was pumped to dryness in the vacuum. The system was able to withstand a nominal vacuum of 30 inches of mercury (101,6 kPa). The system was further tested for tightness using ammonia, which was introduced in the form of phase saturated gas is equipped with a drain valve universal adapter to any of the lecturers in the vacuum vertical pipe. For better tracking speed environment for transportation of produced and added as visual markers several perforations of small diameter, filled with white high-density polyethylene. These markers were placed in the contour of the vertical pipe and the system is again returned to the nominal 30 inches of mercury (101,6 kPa).

Received excessive amount of sulfur-containing solution and a suspension in anhydrous ammonia using a matched pair is designed for a certain nominal pressure tubular receivers, made of 50 mm pipes, with each receiver had a length of approximately 80 cm, ending on one end of the transitional nipple with thread 19 mm for the connection of rods of different diameter having a threaded cap and at the other end of the transitional nipple with thread 19 mm for the connection of rods of different diameters and steel nipple with thread 19 mm ×6 see All threaded connections are properly sealed when using commercial threaded seal, which passport characteristics corresponded to gas and pressure and, as expected, was compatible with the fittings in both steel and plastic. At each receiver nipple was equipped with a compatible ball valve with wrench thread 19 mm To od the WMD of the valves attach additional threaded nipple for subsequent connection to another receiver.

One receiver was evacuated and weighed to determine the mass of the containers were loaded with liquid ammonia and weighed. Approximately 830 grams of ammonia in the condensate are transferred to the receiver from a commercial cylinder using an ice bath. In another pre-dried in the vacuum receiver quickly translated approximately 830 grams of previously dried powder of purified sulphur filtration fineness in the form of 100% of the material with a particle size of minus 1/32 inch (0,794 mm). The valve was closed and two receivers connected to each other by using a pre-attached threaded nipple. Two valves on the receivers were adjacent to each other. Receiver with liquid ammonia was placed above the receiver with grey. Both valves were opened and the ammonia was given the opportunity to flow over a period of time lasting a few minutes to fill below sulfa receiver at that time, as was an intensive cooling of the upper receiver. The completion of the transfer facilitated the result of careful applying heat to the upper receiver with the accurate use of inkjet drying machine or dryer.

After a few minutes and then, as soon as there was an intensive cooling of the upper receiver, the lower valve for rivali. Two United receiver turned and offers the substance was allowed to drain away from the second valve and nipple. Then the valve was closed. The receivers are very carefully separated in a fume hood or outdoors. The connection was razmenjivali for a slow bleed pressure ammonia while wrapping technical napkins to prevent splashing. Saw the emergence of instant intense smell and wipes the transformation of the fluid with the color from purple to black to yellow-green powder.

After that full or nearly full, containing sulfur and ammonia receiver again choked up at the end and the control valve is securely fixed in the closed position using the plastic. The receiver then represented easily agitated tilting the tube containing approximately 50 wt.% a mixture of solid and dissolved sulfur in 50 wt.% anhydrous ammonia. Sediment solid phase was pliable and relatively easily subjected to the re-dispersion for approximately a few minutes as a result of either riding a tubular vessel or repeated inversion it 180 degrees to stimulate the emergence of currents, even if the vessel remained dormant for periods of time exceeding ESAT days.

Ammonia and sulfur receiver in which the result of the repeated tilting and rotation for 15 minutes. The receiver then quickly under vacuum was attached to fitted with a valve vertical pipe above the pipe circuit. Both valve is quickly opened and the piping was downloaded mixture. Tilting the panel on one edge quickly raised and lowered several times to eliminate air bubbles and the system has fully loaded. Included the supply of cooling water flow, run the pump and the system further obessively in fast currents. The valves between the vessel containing sulfur/ammonia, and a vertical pipe was closed and reopened several times. The top container carefully, evenly and gently heated over a period of time lasting for three minutes at a time until the fluid medium with the color from dark blue to violet continued to merge into the main circuit. After that, both valves were closed. The control valve slowly partially closed so that the speed of the fluid would be approximately 150 cm per second, based on observations of white markers polyethylene through previously measured and marked the parts of the pipe.

After that, a gate valve for cooling water was opened and regulated to achieve the equilibrium is temperature, approximately 9° (48°F), as evidenced by the sensor for ammonia. The temperature of the ambient air was 5° (41° (F) in the presence of moderate wind. The pump was stopped after two hours. Shut-off valves universal adapter was closed. Through the drain valve made of plums from a universal adapter in pre vakuumirovaniya tubular receiver for shipment to recycling or reuse.

Universal adapter was disconnected and was shocked with the examination, taking precautions to prevent splashing. Observed no sediment or sediment, although random exfoliating grains yellow-green sulfur and present. On the walls of the steel pipe, it was possible to distinguish between friable powder coating formed from the dust of the yellow-green sulfur in the presence of a certain number of crystals with high reflectivity. Universal adapter gently tapped using a small wrench, and loose powder and grains of sulfur spilled from the adapter. The remaining sulfur dust was carefully blown out using compressed air. The universal adapter is thoroughly dried before reaching a stable baseline weight 1492,5 grams.

In the pipes throughout the system at a depth of approximately one shall die diameter remained intensely colored purple-red-black precipitate. Gaseous ammonia at about 60 pounds per square inch (413,7 kPa) was slowly stravovali in water for use as fertilizer. As the pressure decreased, the color of the remaining sulfur over time was changed from maroon to orange and yellowish-brown with orange okaikoi. When active grazing was close to its end, the system, carrying out the evacuation, was pumped up to 30 inches of mercury (101,6 kPa) for about one hour. The coloring layer of sulfur addition was Svetlanas to obtain a light yellowish-brown powder. Then the vacuum was thrown.

EXAMPLE 3

This example is an illustration of the perspectives method of suspension pumping, storage of solid sulfur, the method of extraction of solid sulfur and additional experiments on screening for petroleum from bituminous shale, crude oil, coal, grain and bituminous Sandstone.

The way a dropping funnel to transfer the suspension into a pipe system described in example 2 can be replaced on the container of the cartridge filter with overhead valves that do not have an internal filter cartridge located in line with by-pass circuit. In the container of the filter can be downloaded separately sulfur and separately download the ammonia. In suitable is oment time ammonia was washed in sulfur and from there to the circuit or in the form of a suspension, either in the form of a simple solution. Also can be used and combined with the static pipe mixer fitted with septa, and flow indicator with vane wheel. The tendency of the system to the formation of deposits can be defined using a steel pipe immersed in agitated vessel with suspension when run through a pipe cold or hot fluid heat transfer medium.

For research applications of the present invention to mining, storing and retrieving sulfur may use a modified ammonia refrigeration circuit including a compressor and tank/boiler anhydrous ammonia. The contour of the mass transfer similar to the existing apparatus liquid chromatography high pressure, you can place located in line with the side outlet of the compressor with high pressure/temperature for the direction of liquid pure ammonia or solutions, not suspensions) sulfur in ammonia in the column or pipe. The pipeline extraction can be routed back to the tank/boiler ammonia. The flowsheet directly in front of the column or further technological scheme at the entrance to the boiler ammonia can position the valve-restrictor/flow meter. May require valve throttling Gazai link return current, leading from the boiler to the side inlet of the compressor with a low pressure/temperature. The capacitor can be placed on the flowsheet in front of the column and the flowsheet after the outlet of the compressor. In the lower section of the boiler ammonia can be set equipped with a drain valve, with or without the heater.

The operation of mining or extraction from stored reserves can be modified to the load in the column of molten sulfur and cooling the loaded column while maintaining the possibility of expansion during solidification. In the sulfur layer, you can drill a borehole with a pre-specified diameter and depth. As an example, in drilling a well placed pipe of small diameter, is coaxially surrounded by a tube of larger diameter. The small diameter pipe was attached to the flow of liquid ammonia from the condenser. An outer pipe of large diameter were sent to the boiler ammonia. The sulfur layer and the above-mentioned system of pipes was made in a sealed outer tube of large diameter. Plain steel tee can be drilled with obtaining a suitable hole for a small tube located above and opposite facing down riser tee (connected to a larger coaxial about the interface pipe). One shoulder tee will lead to the above-mentioned heater, while the other shoulder can be plugged or fitted with instrumentation equipment.

A closed system can be modeled as a result of pumping for degassing columns, then load the columns and create the pressure, using anhydrous ammonia from the drain valve of the boiler. The compressor can download the capacitor and thus pumping the fluid in the hardened layer of elemental sulfur to enter in contact with elemental sulfur, her wetting and dissolution. Dissolved solids in the ammonia solution was pumped upward through the outer coaxial tube and sent to the boiler. The compressor sucked gaseous ammonia from the tank/boiler, thereby concentrating the sulfur and sending ammonia for recycling to condense and re-use, for the purpose of dissolving and transporting larger amounts of sulfur from the layer inside the column.

To use the column as a model for sulfur storage column was rebuilt, giving the geological formation, comprising porous minerals, such as sand or diatomaceous earth. The bypass circuit is supplied by a tank of ammonia solution of sulphur, was positioned between the outlet of the compressor and the column. The system was loaded and in the-Odile in operation, feeding first, which is the solvent of pure anhydrous ammonia with subsequent supply of ammonia solution of sulphur, and then purge pure ammonia. At a suitable point in time, the operation mode was switched to translate the column at a reduced pressure (vacuum), and gaseous ammonia was collected from the columns to send on recycling, thus forming inside the column sediments of solid elemental sulfur to store in the pores of the earth, but at some distance from the point of introduction due to the purge action of the environment. A system of pipes in the column can be modified, for example, by including perforation zones for better placement and formation of sulfur deposits and extraction of ammonia. A system of pipes for placement and retrieval can be configured as one or more pipes (wells), and can be used in a wide range of arrays of extraction wells. Removing the thus laid deposited sulfur was accompanied by the blowing of the formation with the use of ammonia, as in the case of mining.

Suspensions or solutions, which were extracted as described above, can be sold as commercial products. For sale as commercial products can also be obtained and molten sulfur resulting from the use of the lower heater to melt nakaplivalsya sulfur as as it will be deposited, with simultaneous distillation of ammonia at a temperature close to its critical temperature. Molten sulfur can be removed from the heated drain valve.

EXAMPLE 4

This example illustrates the characteristics of solubility and fluidity of mixtures of sulfur and sulfur dioxide at different temperatures.

Sulfur dioxide was obtained by conducting reactions involving sulfuric acid and sodium sulfite at commonly used for this reaction the reaction conditions and collected at -20°C, were subjected to a double distillation from the ambient temperature at the saturation pressure and collected in the container in a cold bath. At a temperature of -20 collection°With no moisture was observed.

Finely crushed freeze-dried fine powder of elemental sulfur USP dried for several days over concentrated sulfuric acid. The tare weight was determined for thick-walled ampoule equipped with a seal PTFE and threaded caps, and sulfur tolerated in these vials and weighed. After that closed ampoule was cooled to -20°in a bath of ice and salt. Liquid sulfur dioxide was cooled to the same temperature in a closed vessel and quickly translated in sulfur capacity. Then both tanks quickly again closed to prevent escape of hazoor the importance of sulfur dioxide. The resulting mixture contained a 1.8 parts of sulfur dioxide relative to 1.0 part of sulfur or 35,7 wt.% elemental sulfur.

Additional results of the observations consisted of the following.

Suspension sulfur/sulfur dioxide was vysokoletuchie, supple and bright yellow in color.

Excess powdered sulfur can be easily atomized even when it was left to stand for seven days. Besieged excess sulfur was a slowly falling, forming loose sediment, crystalline non-caking re-dispersible mass, below the layer transparent liquid supernatant.

During the period of ten days did not observe any formation of a coating of sulfur particles or adhesion of solid sulfur to the surfaces of the heat transfer, the same thing applies to the observation agglomerating, tasmaania or polymerization of sulfur particles. During this ten-day period of suspension regularly manipulation and kept at temperatures ranging from -20 to +37°and twice subjected to intensive cooling at approximately -70°C for short periods of time.

Subjected to the test tank having a capacity volume of approximately 10 ml, for anjali to approximately half its volume, using a suspension of sulfur in liquid sulfur dioxide. After intensive stirring capacity on the inner surface of the vessel both above and below the liquid level and across the inner surface, including in the free space above the liquid, formed a relatively homogenous powder coating of elemental sulfur. Powder coating is easily washed away with a simple careful rotation capacity, then clean the surface without coating. Removing the coating thus continued to be possible for more than ten days. Solid-phase excess sulfur remained bright yellow in color within a temperature range from about -70°C to approximately +37°without the formation of the coating on the inner surface of the vessel or sticking to it.

EXAMPLE 5

This example illustrates the characteristics of solubility and fluidity fraction of particles of sulfur other than fractions from the previous example, and the characteristics of solubility and fluidity of sulfur dioxide, which was obtained from a commercial source of supply, and subjected to further processing.

A known amount of sulfur dioxide was obtained from a commercial container for lectures in the ozonation of gas through concentrated sulfuric acid for removal of trace to which icest gaseous sulfur trioxide. Liquid sulfur dioxide was collected by condensation in a cold bath.

Elemental sulfur was obtained by melting freeze-dried fine powder sulfur USP in an inert atmosphere by commonly used methods and brimstone upon cooling gave the opportunity to precrystallization with the formation of the block shape. The resulting rigid solid phase sulfur with some difficulty crushed into powder and selected various factions sifting. One fraction of screening, in particular, consisted of 100% of the material passing through the woven grid with square holes of 0.7 mm, and 100% of the material remaining on the sieve with square openings of 0.5 mm, and was dried over concentrated sulfuric acid.

Samples of the suspension mixture containing a known quantity of the fraction of particles of elemental sulfur and liquid sulfur dioxide, gently and quickly received by commonly used methods designed for a certain nominal pressure thick-walled ampoule equipped with threaded caps from phenolic resin and seals PTFE. In particular, the sample containing about 65 wt.% particles of sulfur in liquid sulfur dioxide, showed fluidity for more than seventy days.

Additional results of the observations consisted of the following.

Fluid suspension sulfur/sulfur dioxide was pliable and having a color ranging from light yellow to light yellowish-brown and remained so for more than seventy days.

Particles of excess sulfur remained easily dispersible even when they were left to settle for about ten days. Particles of excess sulfur was quickly dropped from a liquid suspension, but remained crystalline non-caking and easily dispersible mass below a thin layer of clear supernatant liquid, even when they were left to settle for another six weeks.

Particles of sulfur remained elastic and nitrosamines after periodic intensive stirring for a period of sixty days with a slight decrease in size occurs in the stirring very small number of small crystalline particles. During the whole period of observations there was no appreciable formation of a coating of sulfur or adhesion of crystals to surfaces of a container.

EXAMPLE 6

This example illustrates the characteristics of solubility of mixtures of sulfur and sulfur dioxide under more severe temperature conditions.

Characteristics of solubility was investigated in exposed test containers, which were representative models of tanks for transportation, suitable for manipulation at elevated temperatures. Conditions were similar to those found in pipes and other vessels during operations in mo is ulah, such as pumping stations, separators, mixers for suspensions and the like, including conditions of high temperature and pressure. Due to the perceived threat of explosion and inhaling as tanks shall be tested, used threaded thick-walled cylindrical glass ampoules for a centrifuge having an internal cavity of conical shape with a capacity approximately equal to 0.25 ml. threaded cap phenolic resin were drilled and equipped with discontinuous disks PTFE as a seal to bleed pressure.

The tanks had carefully weighed samples of very finely ground dried fine powder of elemental sulfur USP, and then spent the closing and cooling in chemical glasses Dewar containing dry ice/solvent. Liquid sulfur dioxide was received and twice distilled, as in the above example 4. At a convenient time sulphur dioxide was cooled in a mixture of dry ice/solvent. After that capacity with the sulfur dioxide was removed from the cold and through the rubber sleeve with the plug quickly connected with microtuble PTFE. Sulphur dioxide gave the opportunity to gradually warm up until then, until he started to see a good flow of gaseous product at the exit of the tube, after this is th it was served in a container of chilled grey, where he was given the opportunity to condense and fill the vial with grey (it is necessary to take precautions and to leave sufficient free space above the liquid to prevent hydrostatic explosion resulting from the expansion of liquid sulfur dioxide). Taking precautions to prevent contamination of the ice, the vessel containing sulfur and sulfur dioxide, covered and left to warm up to ambient temperature. After that when using the analytical balance was determined by the number of contained sulfur and sulfur dioxide, providing a representative models of tanks for transportation of containing so certain known concentration of elemental sulfur in liquid sulfur dioxide under pressure.

After that they used the bath with hot water, thermometers and the lens 14-fold increase, using known methods and commonly used means of identifying the actual equilibrium temperature for concentrations of saturation and dependencies temperature - solubility for sulfur in sulfur dioxide. After conducting numerous iterations in relation to predetermined concentrations, and a large number of cycles of heating and cooling with proper precautions against the possibility of explosion and erisoodustuste ventilation received the following observations.

Sulfur dissolved in liquid sulfur dioxide at a concentration of 134 hours/million±20 wt.% when the temperature of 35.5±3°C.

Sulfur dissolved in liquid sulfur dioxide at a concentration of 878 hours/million±10% at a temperature of 47.3±1,3°C.

During the heating data solutions to approximately 85°when shaken, followed by a gradual cooling to ambient temperature in a water bath did not observe any crystals adhering to the inner walls of the vessel. Instead, as if 35,5°and when 47,3°With of the solution to precipitate fell out a long free-floating transparent light yellow needle crystals of sulphur, as described previously.

Attempt dissolution of higher sulfur concentrations in the stirring for longer periods of time at higher temperatures, stimulated the formation on the side walls of the container stubborn deposits of sulfur. For example, in the series of tests using pre-defined concentration of sulfur in the sulfur dioxide approximately 1800 hours/million, the element could not be completely dissolved under good agitation for several hours at temperatures approaching 96°C. Despite the fact that some tests failed due to rupture of the seal is travelmania pressure, successful attempts observed the formation of coatings and deposits of solid sulfur on the side walls, if they gave the sample (containing a certain number of undissolved solid phase) sufficiently subjected to gradual cooling in a water bath to ambient temperature. The formation of coatings and deposits of sulphur was particularly evident at the locations of defects in the inner surface and close them. These deposits could not be removed by intensive stirring of the contents during the period of time lasting approximately one hour.

The rate of change of solubility of sulfur in liquid sulfur dioxide at a one degree Celsius temperature change is very small in the temperature range, less than about 35°C. within experimental error, the degree of change was 2.5±including 0,6/million per degree Celsius. The degree of change is very much increased at temperatures higher than about 40°C. within the range from about 40°With up to approximately 100°With the degree, apparently, remained in the range of 50 to 130 hours/one million degrees Celsius.

As representative models, containers for transportation, such as the pipeline for sulfur in liquid sulfur dioxide should remove ivalsa in the moderate range of operating temperatures, smaller, approximately 40°to eliminate or prevent the premature formation of sulfur deposits on the heat transfer surfaces. Events such as high temperature and distillation of the solvent, can be controlled using conventional means of technical control, such as insulation, nekaitiguma pumps or mixers and the like, in order to avoid sedimentation of the solid phase.

EXAMPLE 7

This example illustrates the solubility of larger particles of elemental sulfur in liquid sulfur dioxide at different temperatures using alternative methods and materials to confirm the results given in the examples above.

Fraction sifting elemental sulfur, which was recrystallized and powdered, namely the fraction representing 100% of the material passed through a mesh with square holes of 0.5 mm, additionally carefully classified by size, sorted and manually separated using the increase with obtaining approximately one hundred elastic solid sulfur particles with similar small size. The particles were dried over concentrated sulfuric acid and carefully weighed both collectively and individually, in order to ensure approximately equal to mA the sah, equivalent to 200 micrograms per particle.

An array of approximately ten thick-walled vials with conical cavity, equipped with threaded caps from phenolic resin having a seal PTFE, dried and carefully weighed to determine the mass of container and to each vial was placed different weights of the above-mentioned particles. Thus, the total predefined mass of sulfur was in the range of from 200 to 2000 micrograms micrograms per vial.

Fresh liquid sulfur dioxide was obtained in the ozonation of gaseous sulfur dioxide from a commercial cylinder lectures through concentrated sulfuric acid by condensation and collection of liquid sulfur dioxide in the cold receiver. Received capsules containing a known mass of particles of elemental sulfur, then cooled and quickly filled using the obtained cold liquid sulfur dioxide, and closed the lid while keeping the free space above the liquid, sufficient for the proposed expansion. After that when using the analytical balance was determined by the total mass, while the resulting samples contained approximately 30 hours/million, 50 hours/million, 70 hours/million, 100 hours/million, 150 hours/million, 190 hours/million, 240 hours/million and 540 hours/million (wt.) accordingly, when calculating the mass of sulfur in liquid is the sulfur dioxide at a pressure of saturation. Samples were grouped with each other for long-term careful stirring at a temperature of approximately 20°C, with periodic examinations. The results consisted of the following.

At 30 hours/million sulfur were completely dissolved in the sulfur dioxide in one day.

At 50 hours/million sulfur were completely dissolved in the sulfur dioxide in two days.

At 70 hours/million sulfur were completely dissolved in sulfur dioxide only after one week.

All other samples with higher levels of sulfur, remained essentially undissolved even after ten days.

Dissolved samples containing 30, 50 and 70 hours/million of sulfur in the sulfur dioxide, then placed in melting ice at 0°for twelve hours, after which in each ampoule was observed by significant amounts of precipitated precipitated sulfur.

Samples containing 100 hours/million or more of elemental sulfur in liquid sulfur dioxide were transferred into the bath with a constant temperature equal to 35°C and kept at this temperature with constant gentle agitation. Sample containing 100 hours/million sulfur, were completely dissolved after two days. After another three days, none of the samples containing 150 hours/million or more of elemental sulfur is not completely dissolved. Attempt policedepartment solubility at higher temperatures as a result led to the expected explosion of the samples due to the action of excess pressure saturation.

In order generalization we can say that this example shows that under the action of liquid sulfur dioxide sulfur particles were dissolved at low concentrations in the temperature range from approximately 0 to 35°C. When using this method it was demonstrated that the solubility of elemental sulfur in liquid sulfur dioxide at a pressure of saturation was inferior to the value of 30 hours/million when 0°With, was in the range of from approximately 50 hours/million to approximately 100 hours/million with 20°and from about 100 hours/million to 150 hours/million with 35°C. the Results of these observations indicate that the temperature coefficient of solubility for elemental sulfur in liquid sulfur dioxide in the range from 0 to 35°C is a value less than 5 hours/million per degree Celsius of temperature change and, apparently, in the range from 2 to 4 hours/million per degree Celsius, which is in good accordance with the conclusion in the above example 6, i.e. with a value of 2.5±0.6 for one degrees Celsius.

EXAMPLE 8

This example illustrates a method of transporting sulfur for modeling multiple operating modes for sulfur in various fluids for transportation, maps the results for the formation of sulfur deposits on the heat transfer surfaces when using a variety of the fluid for transporting and illustrates the as the sulfur deposits can be cleaned and removed with the use of liquid anhydrous ammonia.

As a representative model is designed for a certain nominal pressure vessels for transportation of used link thick-walled glass tube with a closed bottom end, which could either be immersed in a water bath, or to provide an external resistive heater and magnetic stirrer. Made the cover of machined aluminum with two holes and Primachenko top wall, and hurled through the bulkhead fittings, which were appropriately designed for a certain pressure and which made possible the passage in the tube of a tube of small diameter stainless steel with a closed lower end for her role as a closed probe having an aperture opening to the outside and up the walls. After that, the inside of the probe was installed tube still smaller diameter open end while providing sufficient clearance for the passage of a fluid coolant. This tube with a smaller diameter had one hole inside and near the bottom of the probe, and another hole was opened in the external environment. The assembled probe was placed in the tank on the way, which made possible the convenient is provedenie disassembly and inspection, and which made possible the circulation of a fluid coolant inside the tube of the probe, but separately from the content model tanks for transportation. To the intake hole containing fluid coolant probe capacitance attach additional tube that led to the outlet of a small submersible pump placed in an insulated container for flowable fluid with variable temperature. To the outlet of the probe was attached return tube for flowing coolant, which led back into the container for coolant. Another hole of the top cover with the partition used for thermometers partial immersion or valve system that regulates the pressure with a pressure sensor to monitor the inside of the link pipe equilibrium temperature (or pressure saturation) for mixtures of sulfur/fluid medium for transportation.

Thus, the model capacity obtained in this method, designed for the reception of a suspension of sulfur in various fluids for transportation and to control the temperature of the suspensions when using baths or resistive heater. Each tank is also designed to provide stirring and creating opportunities for pumping a fluid coolant through a tube containing a fluid coolant, until the establishment of the desired equilibrium. When externally on the surface of the immersed heat transfer probe was premature formation of deposits of sulfur, this formation could be described as selected conditions related to temperature, pressure and time, conducting the measurement or weighing. If desired, the vessel made it possible to compare between different fluid mediums for transportation of sulfur, including anhydrous ammonia, light amines, sulfur dioxide, hydrocarbons or petroleum fractions. In numerous varieties suspensions containing or not containing introduced contaminants, such as water, oxygen, chloride ion, and the like, conducted trials using metal samples to determine the corrosive effects due to the placement of samples within the agitated vessel during manipulation of the capacity with pre-defined and comparable conditions relating to temperature, pressure or duration. Thus defined and simulated operating conditions and materials of construction suitable for pilot or commercial operation.

In one set of three different variants of comparative experiments involving the use of very finely ground freeze-dried fine powder sulfur USP, when using toluene, cyclohexane and liquid sulfur dioxide, respectively, received a suspension from the market, containing 10 wt.% sulfur. In each experiment as a fluid coolant used water melting ice, characterized by the temperature at the inlet to the pump, approximately equal to 0.5°and the amount of flow passing through the heat-conducting probe, approximately corresponding to 110 ml / min. Around model capacity was partially wrapped 44-watt resistive heater, which functioned at full capacity when periodic regulation during the experiments, the degree of coverage at the wrap to maintain a constant temperature of mixtures of sulfur/environment for transportation, approximately 20°C. For mixing and stirring of the suspensions used egg-shaped magnetic stirrer and tile magnetic stir bar when set to low speed. Thermometer partial immersion was used for experiments with toluene and cyclohexane, and the pressure sensor used in the experiment with sulfur dioxide. In each case, under stirring within less than ten minutes was rapidly established equilibrium temperature and the temperature of the contents of the vessel was kept at a level approximately equal to 20°within three hours, it was taken precautions to regulate the temperature of the mixture in order to avoid heat dissipation, because the experts who the cops with toluene and cyclohexane the heat exchange surface of the heat conductive probe began to acquire the deposits of sulfur.

At the end of each three-hour experiment, the probe was examined to obtain the following results. When used as a fluid media toluene probe was completely surrounded by a coating of crystalline solid sulfur with a thickness of 2.1 mm Thermometer partial immersion, located next separately from the probe, containing a fluid coolant, and parallel to it, did not show any deposits of sulfur. After draining and drying under a vacuum, sulfur were rapidly removed under the action of fresh liquid anhydrous ammonia at very careful shaking. As the fluid for transporting used cyclohexane, for three hours there was a coating of solid sulfur with a thickness of 0.6 mm, which completely surrounds the probe. No deposits of sulfur on thermometer did not arise. Similarly, the coating of sulfur on the probe was easily schedules from the surface after draining and drying when using fresh liquid anhydrous ammonia. In the experiment using as a liquid medium for conveying pressurized liquid sulfur dioxide any tangible sulfur deposits on the heat-conducting probe did not appear within three hours of the experiment under the same conditions. In all three cases, the increase in temperature returning to the current container is its fluid (water melting ice) did not exceed 2° With during the whole experiment. Thus, as has been demonstrated, sulfur dioxide is advantageous fluid carrier, preventing the occurrence of sulfur deposits on the colder surfaces of the heat transfer.

Another set of variants of experiments implemented using two grades of liquid anhydrous ammonia for comparison with the above described experiments and determine the effect of contamination by moisture in ammonia acting as a liquid medium for transportation. Ammonia stamps used for the production of cold, characterized by a moisture content of lower than 200 hours/million (wt.), compared with the brand of anhydrous ammonia for agricultural purposes, characterized by the level of moisture content equal to 3000 hours/million (wt.). In each case, to get in the tank mixtures with sulphur content of 30 wt.% used very finely ground freeze-dried fine powder sulfur USP. Ammonia stamps used for the production of cold, used in the first experiment, and mark anhydrous ammonia for agricultural purposes, resulting from the addition of 2800 hours/million water to the brand of the substances used for the production of cold, used in the second. Because the solubility of sulfur in ammonia in this temperature range is approximately 20%, that is birali loading 30% to get the download undissolved solid phase element, approximately 10 wt.%, that was equivalent to that used in the first set of experiments described in this example. It was necessary to take exceptional precautions, that is caused by high blood pressure, that is, approximately equal 758,4 kPa (110 lb/in2excessive pressure that was necessary to reproduce the desired equilibrium temperature of a fluid mixture, equal to 20°C. Resorted to precautionary measures, including measures for explosion protection. In one example, when the test pressure of approximately 1034,2 kPa (150 lb/inch) gauge pressure, caused the destruction of the glass tube on Primachenko partition. Duplicated all other conditions of the previous example except that the observation in respect of the mixtures were taken using a strong backlight behind, because of their intense purple-black color.

At the end of both three-hour experiments and after the inspection probe containing a fluid coolant, after draining and drying showed tangible, but very light coating formed from the finely ground dust crystals of sulphur. The thickness of the formed dust deposition was impossible to measure, and may be, was an artifact caused evaporated the receiving solvent ammonia at the end of the experiments. Sulfur extracted from ammonia stamps used for the production of cold, with a lower level of moisture it, after drying had a greenish-yellowish-brown color. Sulfur is extracted from the brand of ammonia for agricultural purposes, with higher levels of moisture in it, after drying coloring ranges from light yellowish brown to yellow.

Thus, this example demonstrates that liquid anhydrous ammonia, characterized by the level of moisture content, typically encountered in commercial practice, is the best fluid medium for mixtures of elemental sulfur, preventing the formation of sulfur deposits on the colder surfaces of the heat transfer.

EXAMPLE 9

This example is an illustration of the perspectives method of transportation commercial products for modeling operating modes for coal, grain, petroleum coke or other commercial products in the form of a suspension in various fluids for transportation or mixtures of fluid for transportation.

Representative model tanks for transportation, designed for a certain pressure, formed the same way as in example 8, adding an internal partition plate with many holes, separating capacity for ve is hni and lower compartments of approximately equal volume and characterized by the presence of fastening means to one side of the partition a fine mesh filtering cloth or fiberglass, that makes it possible to run rough content filtering while turning capacity.

After that coal or petroleum coke with a predefined level of sulfur content or grain with a predefined level of nitrogen can be mixed with anhydrous ammonia or other fluid mediums for transportation or mixture and stir using a magnetic stirrer for a certain period of time at a known temperature and pressure as models of operations for the transportation of slurries. At the end of predefined experiments, the capacity can turn in order to enable fluid to drain away from the material of the solid phase, thereby obtaining decanted solid and liquid ammonia or other liquid suitable for shipment to recycling. Anhydrous ammonia, for example, can be etched away and send for recycling, and the capacity of the vacuum pump to dryness. A solid residue, whether it is coal, coke or grain, can be subjected to analysis to determine the degree of enrichment in connection with the lower sulfur level or higher levels of nitrogen under certain conditions, which in time spent in contact with anhydrous ammonia. Sediment from the Bay to the fluid under the service the same way by commonly used methods can be analyzed for the presence of contaminants and the potential departure on recycling as the original threads for example, for facilities burning waste sulfur acid.

Although this description has been described many details of this invention and of the ways in which it could implement and use, specialists in the relevant field will readily become apparent and more variations, modifications and substitutions that use the main discoveries that form the basis of the present invention, and demonstrate their advantages and which, therefore, fall within the scope of this invention.

1. The method of transportation of elemental sulfur, including

(a) mixing elemental sulfur with a nonaqueous liquid carrier, representing the anhydrous ammonia and/or sulfur dioxide, to obtain a fluid mixture, and

(b) the transportation of the fluid mixture in the vessel for transportation.

2. The method according to claim 1, wherein the transport fluid is carried out in the absence of any temperature regulation for capacity, excellent from exposure to environmental conditions.

3. The method according to claim 1, in which the mentioned fluid mixture is a suspension of solid elemental sulfur in liquid sulphur solution, dissolved in a nonaqueous liquid medium.

4. The method according to claim 1, in which the capacity for transportation of the pipeline and transportation of zaklyuche who were pumping the fluid mixture in the pipeline.

5. The method according to claim 4, in which the tubing has an inner surface made of ferrous metal in contact with the fluid mixture.

6. The method according to claim 4, in which the pipe is surrounded by air.

7. The method according to claim 4, in which the pipeline is an underground pipeline.

8. The method according to claim 4, in which the pipeline is an underwater pipeline.

9. The method according to claim 1, in which the nonaqueous liquid carrier is an anhydrous ammonia.

10. The method according to claim 9, in which elemental sulfur is at most approximately 65 wt.% from the total mass of the fluid mixture.

11. The method according to claim 9, in which elemental sulfur is from about 20 to about 65 wt.% from the total mass of the fluid mixture.

12. The method according to claim 9, in which elemental sulfur is from about 40 to about 60 wt.% from the total mass of the fluid mixture.

13. The method according to claim 9, in which elemental sulfur is from about 50 to about 60 wt.% from the total mass of the fluid mixture.

14. The method according to claim 9, in which the transportation takes place at temperatures less than or equal to 35°C.

15. The method according to claim 9, in which the transportation takes place at temperatures less than or equal to 20°C.

16. The method according to claim 1, in which the non-aqueous liquid medium is sulfur dioxide.

17. The method according to clause 16, in which elementary the EPA is at most, approximately 65 wt.% from the total mass of the fluid mixture.

18. The method according to clause 16, in which the aforementioned elemental sulfur is from about 1800 hours/mn (wt.) to about 65 wt.% from the total mass of the fluid mixture.

19. The method according to clause 16, in which elemental sulfur is from about 1 to about 60 wt.% from the total mass of the fluid mixture.

20. The method according to clause 16, in which elemental sulfur is from about 10 to about 50 wt.% from the total mass of the fluid mixture.

21. The method according to clause 16, in which the transportation takes place at temperatures less than or equal to 40°C.

22. The method according to clause 16, in which the transportation takes place at temperatures less than or equal to approximately 20°C.

23. The method of extraction of elemental sulfur from sulfur-containing geological formations, essentially not containing water, including

(a) blowing geological formations anhydrous ammonia, to form a liquid solution of elemental sulfur dissolved in anhydrous ammonia, and

(b) removing elemental sulfur from a liquid solution.

24. The method according to item 23, further comprising sending to recycling to the step (a)at least part of the above-mentioned ammonia remaining after removing elemental sulfur from a liquid solution in stage (b).

25. The method according to item 23, in which geologicas the th formation is a geological mineral formation.

26. The method of extraction of elemental sulfur from sulfur-containing mineral formation, essentially not containing water, including

(a) blowing mineral formation liquid anhydrous ammonia to form a liquid solution of elemental sulfur in anhydrous ammonia, and

(b) removing elemental sulfur from a liquid solution.

27. The method according to p, which further sent for recycling to the step (a)at least part of the ammonia remaining after the extraction of sulfur from the above-mentioned liquid solution in stage (b).

28. The method of extraction of elemental sulfur from essentially anhydrous carbonate solid phases, including

(a) purging the solid phase liquid anhydrous ammonia to form a liquid solution of elemental sulfur in anhydrous ammonia, and

(b) removing elemental sulfur from a liquid solution.

29. The method according to p, which further sent for recycling to the step (a)at least part of the ammonia remaining after the extraction of sulfur from the above-mentioned liquid solution in stage (b).

30. The method of storage of elemental sulfur, comprising a mixture of elemental sulfur and liquid anhydrous ammonia to form a liquid solution or suspension and Deposit formation from a solution or suspension in an underground formation, essentially containing no water.

31. Ways is by item 30, in which optionally selected from underground formations separately from sulfur anhydrous ammonia for reuse.

32. The composition, which consists essentially of a solution or suspension composed of a mixture of elemental sulfur with liquid sulfur dioxide.

The priority of claims 1 to 27 and 32 04.06.2003.

Priority p-31 11.12.2003.



 

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