The method of processing sulfur-containing gases and a device for its implementation
(57) Abstract:Claimed a method of sample processing gas containing sulphur, which includes dehydration of the sample gas to obtain samples of the dried gas having a water content of less than 100 parts per million, and then storing samples of the dried gas in a container that does not react with sulphur in gas, and sustainable for the implementation of this method. 2 C. and 17 C.p. f-crystals, 4 Il. The present invention relates to a method and device for processing a sample gas containing sulfur and, in particular, a method and device for processing a sample gas containing sulfur, thus, to prevent reduction in the sulphur content of gas over time during storage.One of the important tasks facing the industry today, is the control of environmental pollution. One of the most harmful pollutants present in process gases that are used and/or produced by the industry, are sulfur compounds. The undesirability of sulfur compounds is not only due to environmental pollution caused by the combustion gas containing sulfur, but also corrosion of the factory and elaborate above, there is an urgent need for accurate analysis of process gases, etc., and sulphur content to ensure proper handling of these gases in order to avoid the harmful effects of sulfur in such process gases. To date, this issue remains unresolved sampling and storage of sulfur-containing gases. The main reason for this is that the sulphur content in the gas sample, which is analyzed is reduced over time, and therefore, the measured volume is less than the actual amount of sulfur in the gas, which is commonly used in various commercial situations. This collapse of sulfur was observed even when the sulfur concentration below 5% and there are all types of gases, whether natural gases, process gases or air.There have been attempts in relation to the above problems. In the publication  quantitities a number of difficulties encountered during storage of sulfur compounds, including the difficulty of measuring the concentration of sulfur compounds in comparison with various other compounds, as well as the most rapid time decay of sulfur compounds over time. Although it was found that the Raney, the decay occurs within a fairly short period of time. Thus, even with proper selection of materials, effective long-term storage is not possible.In addition to the difficulties of storing sulfur compounds, is also difficult to make an accurate measurement of the concentration of sulfur compounds in gases.One of the most reliable methods currently available for the quantitative determination of sulfur content, is the method of Dragør. Although this method allows measurements in the workplace, however, it has several limitations, namely, low accuracy, it is sensitive only to some samples of sulfur, requires great skill of the operator and in addition, there is an optical interference whenever there is more than one sulfur compounds. In addition, the method of Dragør does not provide any means for the storage of gas samples.Developed other methods for the analysis of sulfur compounds.In the patent  describes how the analysis of sulfur in hydrocarbons by first decomposition of hydrocarbons into simpler molecular structure.In the patent  describes 2">Thus, the sulfur compounds in gases is very difficult to measure over time due to decomposition of compounds during storage. However, because the harmful effects of these compounds occur even at very low concentrations, it is desirable to determine the sulfur concentration in parts per billion. There is a need for simple methods and device for sampling and storage of gases containing sulfur compounds with little or no decomposition of compounds during storage, resulting in sulfur concentration can be accurately measured at a later time. In addition, for more efficient use of such a device should be portable, so that could be delivered to the place of supply of gas. There are many applications that require precise indication of the sulphur content after some time, however, none of the known solution does not solve the problem.Therefore, as noted above, there is an urgent need for an effective method and device for the processing of sulfur-containing gases in order to prevent the degradation of sulfur containing gases over time, making the school the present invention is to provide a method and a device for the storage of sulfur-containing gases so, to prevent the reduction of the sulphur content in gas over time.In addition, the present invention is to provide a method as above, in which the sulfur-containing gas is pre-processed before storage to prevent degradation of sulfur in it over time.Another object of the present invention is to provide containers for storage, which does not react with sulfur contained in the sample gas.Still another objective of the present invention is the processing of sulfur-containing gas in such a way as to prevent decrease over time due to dehydration gas and its storage in inert containers.Other objectives and advantages of the present invention will be apparent from the following description.In accordance with the present invention the foregoing objectives and advantages are readily achievable.The present invention relates to a method and device for processing and storage of gas samples containing sulfur and, in particular, a method and device for processing a sample gas containing sulfur, wherein prevented the decrease containing the gas, containing sulfur, is subjected to dehydration to obtain the dried sample gas with a water content of less than 100 parts per million. In accordance with the present invention it was found that the sample must be processed dehydrating agent in a quantity greater than or equal to 1.5 kg dehydrating agent per liter of water removed from the sample gas. After that dehydrated dried sample of gas is placed in storage in the reservoir, which does not react with sulfur containing gas and which is also waterproof, thereby preventing the ingress of water stored in the sample gas. In accordance with the method of the present invention dehydrating agent used in the process is selected from the group consisting of carbon, magnesium perchlorate, glycol, silica gel, aluminum oxide, and a mixture thereof with magnesium perchlorate is preferred. In accordance with another feature of the method of the present invention, the temperature, pressure and flow rate of the sample gas in the dehydration zone maintained under controlled modes in order to maximize the drying effect of the drying agent in the sample gas.The device in accordance with izaberete the UNT, which passes through the gas sample. In accordance with the preferred embodiment of the present invention dewatering zone contains a large number of traps, which selectively serves the sample gas upon detection of the saturation of the dehydrating agent in any of the traps. The device of the present invention also includes the use of storage tanks that do not react with sulfur contained in the sample gas and are impervious to water. The most preferred storage tanks can be selected from among litrownik plastic bags, such as selling the company Trademark Calibrated Systems and aluminum cylinders with spectral processing of the seals, sold under the trademark Airo.The method and apparatus of the present invention allow to obtain accurate readings of the sulphur content of gas samples for many days after taking samples from their source. Improved precision of the device of the present invention, provides a number of advantages, including quality control upon receipt of natural gas; the precise guarantees the quality and composition of natural gas suppliers and customers; less corrosion of the transport pipeline is the use of sulfur-containing gases.The present invention is illustrated the accompanying drawings.Fig.1 schematically illustrates the apparatus and method of the present invention;
Fig.2 is a graph showing the degradation of sulfur over time in wet and dehydrated samples of the gas;
Fig. 3 is a graph showing the effect of various storage tanks on the degradation of sulfur in dehydrated samples of the gas;
Fig. 4 is a graph showing the effect of velocity for storage on the degradation of dehydrated gas samples over time.In Fig. 1 schematically shows a system of the present invention for implementing the method for dewatering and storage of sulfur-containing gas without degradation of sulfur over time.The system 10 is equipped with a connection 12 for connection to the gas mains and take it to the sample gas. The gas sample may be obtained from any source, such as oil wells, environment, etc., Usually depending on the source of the moisture content in the sample can exceed 20,000 parts of water per million, and the sulfur content may not exceed 10 parts per million. The gas is directed through conduit 14, preferably it is a steel Teflon type, which are sequentially connected m the amount of gas flow in the dehydration zone 22. The sample gas is taken preferably at a pressure of about 0.7 0.03 kg/cm2temperature not above 60oC and a flow rate of about 0.2 to 2.0 l/min. and the Reasons must be supported by the above values are as follows: when the pressure is higher than 2.9 kg/cm2the drying device must increase; at a temperature exceeding 60oC, the shape of the grain drying agent used in this way, will deteriorate and therefore, will not be effective for dewatering and at high flow rates the gas sample will not have enough time required to locate a drying agent to implement the desired dehydration. The drying agent may be selected from the group of well-known substances, such as silica gel, aluminum oxide, magnesium perchlorate, carbon, glycol, and mixtures thereof with magnesium perchlorate are preferred.In line 14 upstream from the elements 16, 18 and 20 built-in drain valve 24 that is designed to remove all the liquid, which may be in the sample gas. Most natural gas contains a liquid phase composed mainly of fraction C6-C14that Perrin is bukovinka the pressure difference between the main gas line and the system.The valve 24 has two positions: a) for connecting the piping 14 drying zone 22, or (b) for the connection of the pipe 14 with the atmosphere, resulting in three parameters /temperature, pressure and flow rate can be controlled, and excess gas pressure can descend from the system. It should be borne in mind that the system of the present invention is a dynamic system, which means that the gas constantly flows through the entire system. When the valve 24 is in the position of /b/, it is possible to measure the sulfur content in the sample gas to obtain the original value of sulfur content, resulting in sulfur content measured after dehydration and every few days storage can be compared and thus, is estimated characteristic of the system. The sulfur content is measured in a known manner by connecting to the valve 24 tubes of Dragør. When the valve 24 is in the position of /a/, the sample gas can reach the distribution valve 28. The latter is a valve with one input and multiple output apertures, and preferably five way valve. The control valve 28 provides selective direction of the sample gas in any of the numerous plexiglass lo the s content of moisture in the sample gas. Each output of the distribution valve 28 is connected to one of plexiglass trap 30 through lines 26 so that only one trap 30 is used at any point in time. Thus, the number Plexiglas traps 30 corresponds to the number of outputs of the divider 28. In a preferred variant embodiment of the present invention only one of the trap 30 is used for dehydration of the sample gas passing through it, however, if you want, you can use several plexiglass trap 30. An important feature is that the sample gas leaving the trap 30, had a moisture content of below 100 parts per million as described below.The control valve 32 having one input and multiple outputs, connects each hook 30 with the humidity sensor 34, where the sample gas is removed moisture content.The saturation point dehydrating agent in any of the trap 30 can be observed on the humidity sensor 34 by measuring the moisture content in the gas leaving the trap. When reaching the saturation point of the agent in the trap, it is necessary to rotate the control valve 28 in order to direct the flow of gas from the trap 30, made rich dehydrating agent, is as to the content of the agent of the water in the sample gas must be maintained above than 1,50 CL/l in order to achieve effective dewatering in the developed system.The valve 30 is installed downstream from the moisture sensor 34 to /but/ connection line 38 leading from the humidity sensor 34 to the tank 40 or /b/ for connecting the system to the atmosphere to reduce the pressure in the system. The valve 36 in the position of /a/ adjusts the volume of gas in the tank 40. Last used in the present invention, is connected with the rest of the system using airtight coupling devices 42. The containers used in the device and method of the present invention, are selected on the basis of materials that do not have the ability to react with sulphur and which are waterproof in order to increase the moisture content of sulfur in the storage process. The containers preferably used in the present invention are plastic bags with alteromonas outer surface and aluminum cylinders, covered with plastic, for example, epoxy resin, etc.Example 1.In order to show the influence of water content on degradation of sulfur in the sample gas during storage, the sample of natural gas having a water content of 100 parts of millage 100 parts per million, it is considered a break of the very dry gas compared with samples of conventional natural gas. The sample gas was supplied under a pressure of 2.1 kg/cm2temperature 55oC and a flow rate of 1.5 l/min in the dehydration zone containing magnesium perchlorate. The last number in the drying zone is sufficient to reduce the water content in the sample gas is approximately 90% (i.e., in the amount of 1.5 kg per liter of removed water. The sulfur content in the sample dehydrated dry gas was measured and amounted to 12 parts per million.After this, the sample of dry gas was fed to alteromonas container, the inner surface of which has a coating applied by an electrolytic method. The cylinder is on the market and is served by the company Airo. The untreated sample gas having a moisture content of 100 ppm, was also stored in the same container. After three days of storage was again measured sulfur content in the sample gas and the sulfur content in the treated dehydrated gas sample was 11.9 ppm, which is essentially identical to the original dehydrated sample gas, while the sulfur content in the raw wet sample gas having an initial concentration of moisture 100 parts per million, 1.9 cha who has a beneficial effect on the degradation of sulfur in the sample gas. The results are graphically presented in Fig. 2.Example 2.This example was carried out in order to show the effect of storage on the degradation of sulfur over time during storage. In this example, the gas sample from example 1, which was dehydrated, stored in three different containers. The first container was alteromonas plastic bag, supplied by the firm Calibrated System. The second sample was stored in a steel cylinder with Teflon coating. The third sample was kept in plexiglass syringe that is supplied by the firm of Hamilton. As shown in Fig. 3, the sample stored in alteromonas bag firm Calibrated Systems showed less deterioration than the sample stored in alteromonas the cylinder of example 1.The sample is kept in a steel cylinder with Teflon coating was slightly worse than the samples in alteromonas bag and alteromonas the cylinder. The sample is stored in plexiglass syringe firm Hamilton showed almost complete degradation of sulfur three days later. This example showed that the preferred container to prevent degradation of sulfur in the sample gas is alteromonas bag firm Calibrated Systems.Example 3.Again with a who s over time, conducted another test in which a sample gas having a sulfur content of 25 parts per million, were kept in preferred alteromonas bag mentioned above in example 2. Sample wet gas with a moisture content of 15,000 parts per million is also stored in another alteromonas bag. The sulfur content was measured in both samples after eight days and then again after sixteen days. As shown in Fig. 4, the contents of the sample wet gas completely degraded from the point of view of the sulphur content after sixteen days compared to gas breakdown, processed in accordance with the method of the present invention, which had a 20% reduction in the sulfur concentration.The above examples clearly shows the positive influence of the method of the present invention to prevent degradation of sulfur in the sample over time when stored under optimal container.The present invention may be embodied in other forms or carried out in other ways, but not outside the scope of the invention or its essential characteristics. This embodiment should be considered in all respects only as illustrated and not limiting the scope of this invention to reduce the sulphur content in gas over time, namely, that taking a sample of gas containing sulfur, dehydrate the sample gas to a moisture content of less than or of the order of 100 parts per million and direct the flow of the dried sample gas is deposited in a container that does not react with sulfur gas.2. The method according to p. 1, characterized in that taking a sample of sulfur-containing gas having a known water content of: contacting a sample of gas with a dehydrating agent in a quantity greater than or equal to 1.50 kg dehydrating agent per liter of water removed from the sample gas.3. The method according to PP. 1 and 2, characterized in that the sample gas has a water content of about 20,000 parts per million.4. The method according to PP. 1 and 2, characterized in that the dehydrating agent is selected from the group consisting of carbon, magnesium perchlorate, glycol, silica gel, aluminum oxide and mixtures thereof.5. The method according to PP. 1 and 2, characterized in that the measured water content in the sample gas after it passes the stream through at least one plexiglass trap.6. The method according to PP. 1 and 2, characterized in that the control of temperature, pressure and flow rate of the sample gas before dehydration.7. The method according to PP. 1 and 2, characterized in that obesos the 8. The method according to PP. 1 and 2, characterized in that prior to dehydration of the sample gas to remove the liquid phase.9. The method according to PP. 1 to 3, characterized in that measure the moisture content in the sample gas prior to its dehydration.10. The method according to PP. 1 and 2, characterized in that the measured sulfur content in the sample gas before the dehydration process.11. A device for processing sulfur-containing gas samples to prevent sulfur content decreases over time, which consists in the fact that it comprises means for dewatering gas to a moisture content of less than about 100 parts per million and a means for storing samples of the dried gas.12. The device according to p. 11, characterized in that the means for dewatering contain dehydrating zone, part of which passes the gas sample and which has at least one plexiglass trap containing dehydrating agent.13. The device according to p. 12, characterized in that the means of dehydrating agent further comprises means for distributing gas samples only one of Plexiglas traps and means for collecting samples of dried gas from the one Plexiglas traps.14. The device according to p. collecting means include a valve with multiple inputs and one output.15. The device according to p. 11, characterized in that it comprises means for regulating the pressure of the sample gas, means for regulating the flow rate of the sample gas.16. The device according to p. 11, characterized in that it comprises means for removal of the liquid portion of the sample gas.17. The device according to p. 13, characterized in that it further comprises a moisture sensor for measuring the moisture content of the dried sample gas.18. The device according to p. 11, wherein the storage media include alteromonas plastic bags.19. The device according to p. 11, wherein the means for storing includes pre-treated aluminum cylinders.
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