FI59262B - FRAMEWORK FOR THE FRAMEWORK OF ENVIRONMENTAL BRAENNOLJA - Google Patents

Description

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Patent- ocn rs | litsntyrslnn AnsOksn utltfd och uti4krtftm put> Uc «r * d 31.03.8l (32) (33) (31) Requested * tolik * u» —Begird prloritet 12.05.72 USA (US) 252787 (71) Universal Oil Products Company, Ten U0P Plaza, Algonquin & Mt. Prospect Roads, Des Plaines, Illinois, USA (72) Newt Morris Hallman, Prospect Heights, Illinois, Bernhard Albert Oeltgen, Prospect Heights, Illinois, USA (7 ^) Berggren Oy Ab (51 *) Method for the Sulfur Poor The present invention relates to a process for the production of fuel oil containing less than about 1.5% by weight of sulfur from a feedstock of heavy black oil.

Catalytic desulfurization is a well-known process described in detail in crude oil technology, with a full literature on suitable desulfurization catalysts, catalyst preparation methods, and various uses. The phrase "desulfurization" refers to the removal of sulfur-containing compounds by decomposition by reacting them to hydrogen sulfide and hydrocarbons and is often included in the broad definition of "hydro-refining". Hydroraffinization processes are carried out under operating conditions under severe conditions which primarily promote the removal of nitrogen and sulfur and, to a lesser extent, the conversion of asphaltenes, the conversion of non-distilled hydrocarbons, hydrogenation and hydrocracking. Thus, the terms "hydrorefining" and "desulfurization" are generally used synonymously for a process in which a hydrocarbon charge is purified to produce a feedstock suitable for end use in a subsequent hydrocarbon conversion system or to intentionally recover a product having direct use. The combined process of claim 1 is preferably used to produce a fuel oil containing less than about 1.5 weight percent sulfur and often less than about 0.5 weight percent sulfur while simultaneously reacting at least a portion of the feed charge to lower boiling hydrocarbon products.

A relatively recent observation is that it is necessary to prevent the spread of various pollutants into the atmosphere and this has led the government to impose numerous restrictions. The most notable of these concerns the combustion of high-sulfur fuels, mainly coal and fuel oil, which results in the release of very large amounts of sulfur dioxide into the atmosphere. As for fuel oils derived from crude oil, their demand has increased significantly as a result of growing global energy needs. More importantly, however, laws have already been enacted which limit the sulfur content of fuel oil, calculated as elemental, to a maximum of 1.5% by weight. The most prominent experts in this field have recently predicted that in the next few years there will be a reduction in the sulfur content of fuel oil to a maximum of 0.5% by weight. The present invention and the combination process according to it are particularly directed to this, i. for the production of fuel oils containing less than about 1.5% by weight? sulfur and, if necessary, less than about 0.5 weight percent? sulfur. The increased demand for sulfur-poor fuel oils has also created the need to convert the "base products" of crude rock oils. In other words, the increased need for fuel oil has in turn made it necessary to use crude crude oil substantially 100.0%.

The object of the invention is to provide a process for the production of fuel oil which does not suffer from the drawbacks of the corresponding processes known from the prior art, which is particularly suitable for thorough desulfurization of heavy hydrocarbon black oils and thus enables the production of fuel oil with a sulfur content of less than 1.5% by weight. and if desired less than 0.5 weight? with the highest possible yield of fuel oil and which can be carried out by simple means and with a high degree of reliability under mild operating conditions.

The invention thus means a process of less than about 1.5% by weight? for the production of sulfur-containing fuel oil from a feedstock feedstock of heavy black oil, in which process 3,5262 (a) the feedstock feedstock and hydrogen are reacted in a first catalytic reaction zone under desulfurization conditions; the vaporous fraction and the first substantially liquid fraction; and (c) at least a portion of the first liquid fraction is reacted under desulfurization conditions with hydrogen-rich gas in a second catalytic reaction zone to which fresh hydrogen is also fed to compensate for additional hydrogen losses and consumption; (d) the effluent from the second reaction zone is separated in the second separation zone into a second vaporous fraction; and and (e) at least a portion of the second vaporous fraction is returned to the first reaction zone to react with the feedstock, and the fuel oil is recovered from the second liquid fraction, and the process is characterized by separating hydrogen sulfide from the first vaporous fraction to provide % desulfurization of the feedstock charge, and the hydrogen-rich vapor fraction thus obtained is passed to the second reaction zone to react with a portion or portions of the first liquid fraction fed thereto to provide less than 25% desulfurization of the feedstock charge.

The first vaporous fraction is preferably separated in the third separation zone into a third vaporous fraction and a third liquid fraction, whereby at least part of the fuel oil is recovered from the third liquid fraction.

It is also preferred that at least a portion of the third liquid fraction is combined with the first vaporous fraction prior to the removal of hydrogen sulfide therefrom.

Crude oils, atmospheric tower bottom products, vacuum tower bottom products, heavy circulating feedstocks, crude oil residues, pre-distilled crude oils, hydrocarbons / oils obtained from tar sands and oils containing heavy hydrocarbons and oils derived therefrom, etc. are used as raw materials. and sulfur-containing compounds in remarkably large amounts, * 59262 the latter generally being between about 2.5 and about 6.0 weight percent of elemental sulfur. In addition, these heavy hydrocarbon fractions, sometimes referred to in oil technology as heavy mineral lubricating oils (black oils), contain organic metal impurities that primarily contain nickel and vanadium in the form of porphyrins and a high molecular weight asphalt-containing material. Examples of feedstocks with which the present invention can be applied include a vacuum tower bottom product having a specific gravity of 1,020 and containing * 4.05 wt.% Sulfur and 23.7 wt.% Asphaltenes, a pre-distilled Middle Eastern crude oil having having a specific gravity of 0.993 and containing 10.1% by weight of asphaltenes and 5.20% by weight of sulfur, and a vacuum residue having a specific gravity of 1.008 and containing 3.0% by weight of sulfur, * 4300 ppm by weight of nitrogen and having a specific gravity of 20.0% by weight. The volumetric distillation temperature of # is about 566 ° C. Using the process of the present invention, maximum recovery of sulfur-poor fuel oil is obtained from these heavier hydrocarbonaceous feedstocks.

The present invention uses at least two catalytic fixed bed reaction systems in conjunction with a specific set of separation auxiliaries, which allows for more efficient use of tandem hydrogen throughout the process. It is to be understood that each reaction system may have one or more reaction vessels with suitable heat exchange devices between them. In short, the combination r s s i is obtained by initially reacting the feedstock with a relatively impure (in terms of hydrogen sulfide content) sulfur stream in the first separation zone. In this first reaction zone, in fact, the relatively light removal of sulfur from the lower-boiling sulfur-containing compounds is achieved. The effluent product stream is separated at substantially the same temperature and pressure to provide a normally boiling liquid phase which is reacted with a relatively pure hydrogen phase in a second reaction system. Operating conditions for both reaction systems include about 1 * 4-210 ik man cme trip ai, a hydrogen content of about 88-5280 m / m hydrocarbons, a liquid volume rate per hour of about 0.20-2.50, and a catalyst bed temperature of up to about 3l6- * 482 ° C. In order to allow actual serial flow of the substance in the process, the second reaction zone is often maintained at a predetermined pressure, which is at least about 1.75 ik mannar pressure higher than the pressure assigned to the first reaction zone. Similarly, because more severe desulfurization reactions are performed in the second reaction zone, the maximum temperature of the catalyst bed therein is often about 12 ° C higher than in the first reaction zone.

The benefits of the present process are numerous. The most important of these, however, is the significant reduction in the maximum catalyst mattress temperature required to achieve the desired degree of desulfurization. Thus, although the maximum temperature of the catalyst bed may be about 316-482 ° C, it is not uncommon for the present combination process to be performed when the maximum temperature of the catalyst bed is below about * J5 * 4 ° C. The present combination process further allows the use of a relatively impure hydrogen stream to release lower boiling sulfur-containing compounds from the sulfur in the first reaction zone. Another advantage relates to the prolongation of the effective acceptable life of the catalyst mixture used in both reaction zones.

Although catalyst mixtures in many cases differ in their physical and chemical properties, they can be identical. Nevertheless, the starch alloy compositions used in the present combination process contain metal components selected from the metals of groups VT-B and VITI of the Periodic Table and their compounds. Suitable metal components are thus E.II. According to the Periodic Table of the Elements of Sargent Co., 1996, the following elements are chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum. In addition, recent studies have shown that catalyst mixtures, especially those used for the conversion of high sulfur feedstocks, are improved by the addition of a zinc and / or wax component. In this context, the use of the term "ingredient" when referring to a catalytic active metal or metals is to include the presence of the metal as a compound, such as an oxide, sulfide, etc., or in the elemental state. Nevertheless, the concentrations of the metal components are calculated as if the metal were present in the elemental state in the mixture. Although precise assembly or method of preparation of the various catalyst mixtures is not considered essential to the invention, certain aspects are preferred. Because the feedstock feed to the process, e.g., is generally high boiling in nature, it is preferred that the catalytically active ingredients tend to provide a limited degree of hydrocracking while promoting the conversion of sulfur-containing compounds to hydrogen sulfide and hydrocarbons. The concentration of the catalytic active metal component or components depends on the primary metal in question as well as the physical and / or chemical properties of the feedstocks. Group VI-B metal components · e.g. are generally present in an amount of between about 4.0 and about 30.0 wt.%. , the metals of the iron group are present in an amount of between about 0.2 and about 10.0% by weight, while the noble metals of group 8 are preferably present in an amount of between about 0.1 and about 5.0% by weight. When a zinc and / or viscin component is used, this is generally present in an amount between about 0.01 and about 2.0% by weight. All concentrations are calculated as if the constituents were present in the catalyst mixture in the elemental state.

The porous support with which the catalytically active metal component or components are combined is a refractory inorganic oxide of the type described in detail in the literature. Of the amorphous type, alumina or alumina together with 10.0 to 90.0 wt.% Of silica are preferred. When handling heavier feedstocks containing a significant amount of hydrocarbons having a normal boiling point above about 510 ° C, it may be appropriate to use a carrier containing 7,596,262 crystalline aluminosilicates or zeolite molecular sieves. In most cases, such a carrier is used in the treatment of a partially desulfurized feedstock which enters another reaction zone. A suitable zeolite material is mordenite, fajacite, type A or type U molecular sieves, etc., and these can be used in a substantially pure state. It is to be understood, however, that the zeolite material may be used in an amorphous matrix such as silica, alumina, and mixtures of alumina and silica. In addition, it is conceivable that the catalyst mixtures may contain a halophenic component such as fluorine, chlorine, iodine, bromine or mixtures thereof. The halocene component is mixed with the support so that the final catalyst mixture contains about 0.1-0.0% by weight.

The metal components may be added to the catalyst mixture by any suitable means, e.g. by co-precipitation or co-elution with a support, ion exchange or impregnation of the support or during a co-extrusion process. After the addition of the metal components, the support is dried and subjected to calcination at a high temperature of about 399-70 ° C, when crystalline aluminosilicate is used in the support, the upper limit of the calcination technique is preferably about 538 ° C.

As for the operating conditions of the catalytic reaction zones, they are selected primarily so that the sulfur-containing compounds are reacted to hydrogen sulfide and hydrocarbons. As described above, the operating conditions used in the second reaction zone often lead to more stringent treatment, although such a technique is not essential. Variations in the severity of the operating conditions between the two reaction zones can be achieved by adjusting the pressure, the maximum temperature of the catalyst bed and the volume rate of the liquid per hour. The more severe use in the second reaction zone is usually accomplished at a higher pressure, a higher maximum catalyst bed temperature, and a slightly higher liquid volume rate per hour, or some combination thereof.

With the exceptions mentioned above, the suitable ranges of different operating variables are generally the same for both reaction systems. Thus, the pressure is about 14-210 ik gauge pressure, the hydrogen content is about 88-5280 n? / N? hydrocarbons, the maximum temperature of the catalyst bed is about 316-482 ° C and the volume volume of the liquid per hour varies from about 25, to about 2.50. Given that the reactions obtained are in principle exothermic in nature, an increasing temperature gradient is observed in both reaction zones as the reactants pass through the catalyst skin. The method of operation provides that the elevated temperature gradient is limited to a maximum of about 38 ° C, and cooling streams, either usually liquid or usually gaseous, are added in accordance with the invention, which are added at one or more intermediate stages of the catalyst bed. Before further describing the invention, it will be apparent that several definitions are needed, particularly with respect to the embodiment described in the accompanying drawing, so that the invention will be clearly understood. In this context, the phrase "substantially the same pressure as" or "substantially the same temperature as" means the pressure or temperature in the downstream vessel, allowing only the normal pressure drop due to fluid flow through the system and the normal temperature drop due to substance transfer from one zone to another. For example, when the pressure at the inlet end of the first reaction zone is about 16 μl gauge pressure and the temperature is about 371 ° C, the first separation zone operates at substantially the same pressure and temperature of about 154 μm gauge pressure and 371 ° C. Likewise, the phrase "at least a portion" when referring to a substantially vapor phase or a substantially liquid phase means both an aliquot portion and a selected portion.

Thus, at least a portion of the first substantially vaporous phase is fed to the second reaction zone after the hydrogen sulfide has been removed therefrom, whereby at least a portion (in this case an aliquot) of the first substantially liquid phase can be recycled and combined with the fresh feedstock.

Other conditions and preferred uses are provided in connection with the description below of the present process. In the further description of this composite desulfurization process, reference is made to the accompanying drawing, which shows a particular embodiment. In the drawing, the embodiment is shown as a simplified flow diagram, in which details such as compressors, pumps, heating and cooling devices, instruments and regulators, heat exchange and heat recovery cycles, valves, actuator pipes and the like are omitted as irrelevant to the understanding of the art. The use of such miscellaneous auxiliary devices is self-evident to a person skilled in the art.

To illustrate the described embodiment, a drawing will be described in connection with the conversion of a gas oil feedstock in an industrial scale unit. It is to be understood that the feedstock, 9 59262 flow mixtures, operating conditions, the structure of fractionators, separators, and the like are only examples and can be varied within wide limits.

Referring to the accompanying drawing, an embodiment is described in connection with an industrial scale unit designed to produce maximum amounts of fuel oil containing less than about 1.0 weight percent sulfur from a gas oil feedstock having a specific gravity of 0.958. Other properties of the gas oil feedstock feed are: sulfur content 4.0 wt.%, 60.0 ppm w / w vanadium and nickel, 2.4 wt.% Heptane insoluble matter, Conradson carbon factor 3.2 and volumetric distillation temperature of 65.0 # ca. 566 ° C. The feedstock feed is fed to process 1 in tube 1 at about 740.35 moles per hour. The feedstock is mixed with the recycled gas phase from the hot (366 ° C) tube 2, the latter containing about 76.0 volumes of hydrogen. The mixture continues through line 2 and is fed from there to reactor 3 at a temperature of about 347 ° C and a pressure gauge of about 155.

Reactor 3 contains a catalyst mixture of 2.0 wt.% Nickel and 16.0 wt.% Molybdenum together with an amorphous support containing 88.0 wt.% Alumina and 12.0 wt.% Silica, with a liquid volume rate per hour through it is about 1.0. The flow from the reaction zone 3 is removed in the pipe 4 at a temperature of about 366 ° C and a pressure of about 151 μm of manometer material and fed to the heat separator 5 at substantially a word temperature and pressure. Moon separation zone 5 supplies a substantially liquid phase to tube 6 and a substantially effervescent phase to tube 7. The component analyzes of the flow out of the first reaction zone (tube 4), the heat separator liquid phase (tube 6) and the heat separator vapor phase (tube 7) are shown below.

TABLE I: Product Distribution of Reaction Zone 3 10 59262

Ingredient Pipe Pipe Pipe moles / h h 6 7

Water 836.39 - 836.39

Hydrogen sulphide 350.37 16.75 334.12

Hydrogen 9663.08 313.60 9349.43

Methane 1358.0¾ 49.6 δ 1308.35

Ethane 139.89 10.26 129.63

Propane 111.16 9.15 102.01

Butasneja 68.01 6.88 61.13

Pentanes 2 4.50 3.11 21.39

Hexanes 18.30 2.79 15.51

Heptane-190 ° C 73.05 17.07 55.98 190 ° C-3 ° C 106.05 53.6¾ 47.42

Light fuel oil 284.18 157.12 127.05

Heavy fuel oil 540.06 527.72 12.33

A total of 13,574.04 1172.77 12,401.27

The predominantly vaporous phase in tube 7 is mixed with 1420.00 moles of cold-expanded liquid circulating stream, the source of which is described below. Meos continues through pipe 7 and. is fed from there to the cold separator 10 in a manometer medium of about 147 ik and at a temperature of about 59 ° C. The hydrogen-rich vapor phase is removed from the cold separator stream 10 by means of a pipe 11 and fed therefrom to a sulfur-hydrogen removal system 12. The substantially liquid phase is removed by means of a pipe 15 and fed from there to the cold separator 16 at substantially the same temperature. The cold expansion zone 16 operates at a gauge pressure of about 14 ik and a temperature of about 57 ° C to feed the exhaust gas stream to tube 17 and to feed a substantially liquid product phase to tube 18, a portion of which is recycled and combined with a substantially vaporous phase in the rod. 7 thus acting as a hydrogen enrichment flow. The analyzes of the constituents of the hydrogen-rich flow in tube 11, the exhaust gas flow in tube 17, and the liquid normally fed to the stabilizers flowing in tube 18 for product recovery are shown in Table TI below: TABLE II: Flow analyzes with cold separation system 11 59262

Ingredient Pipe Pipe Pipe moles / h 11 17 l2

Water 14.76

Hydrogen sulphide 273.51 46.04 8.21

Hydrogen 9155.03 189.42 1.14

Methane 1219.47 83.69 2.93

Ethane 111.17 14.97 1.97

Propane 79.87 13.40 4.92

Butanes 41.19 7.29 7.16

Pentanes 10.47 1.82 5.14

Hexanes 5.00 0.25 5.44

Heptane-190 ° C 2.52 0.39 29.74 190 ° C-343 ° C 0.02 - 26.72

Light fuel oil 0.05 0.01 71.64

Shit fuel oil 0.05 - 7.00

A total of 10,916.04 357.86 172.01

As described below, the process is supplied with wash water in a pipe 8. This water is finally removed from the process system using an immersion pipe fitted to the cold separator 10, which is not shown in the accompanying drawing.

The purpose of the hydrogen sulfide removal system 12 is to increase the hydrogen content of the return gas flowing in the pipe 13 to about 85.9%. Additional hydrogen is fed to line 22 to compensate for total process consumption and solution losses. The hydrogen-rich phase is mixed with the substantially liquid phase in tube 6, to which 809.72 moles of water are added per hour via line 8, the mixture continuing through line 13 to the second reaction zone 14 at about 164.5 μm gauge pressure and about 360 ° C. The reaction zone V1 contains a catalyst-catalyst mixture containing 1.8% by weight of? nickel and 16.0 weight-7 noleybdenum combined with a support having 63.0 naino-7 aluminas and 37.0 weight percent silica, with a liquid volume rate per hour through it of about 1.5. The stream from the reaction zone 14 is removed by a tube 19 and fed to a heat separator 20 at a pressure gauge of about 157.5 ik at a pressure and temperature of about 366 ° C.

i2 59262 The predominantly vaporous phase is removed by tube 2 and recycled and combined with the portion of raw material in tube 1. Usually the liquid phase is removed through line 21 and combined with the normally liquid phase flowing in line 18, the process product being taken to suitable separation equipment to recover the desired fuel oil, Table ITT gives the total reactor 1h (tube 13) charge and effluent (tube 19) : TABLE ITI: Partial analyzes, reactor 14

Ingredient Feed depletion moles / h Pipe 13 creep 19

Water 824.47 829.13

Hydrogen sulphide 47.17 92.46

Hydrogen 11,703,15 11,273,72

Methane 1367.19 1379.76

Iitan 127.92 135.59

Propane 94.25 106.27

Butanes 51.18 61.21

Pentanes 14.43 19.32

Hexanes 8.18 12.10

Heptane-190 ° C 19.77 34.63 190 ° C-343 ° C 58.66 78.62

Light fuel oil 157.18 161.37

Heavy fuel oil 527.72 513.13

Total 15,001.25 14,697.30

The separation in the heat separator 20 is shown in Table IV below.

TABLE IV: Partial analyzes of the heat separator 20 i3 59262

Ingredient Tube Tube

Moles / h 2 21

Water 829.13

Hydrogen sulfide 88.86 3.60

Hydrogen 10,979.32 294.40

Methane 1338.71 41.05

Ethane 127.46 δ, 14

Propane 99.08 7.19

Butanes 56.09 5.11

Pentanes 17.27 2.0 4

Hexanes 10.55 1.55

Hentane-190 ° C 27.79 6.97 190 ° C-3i; 3 ° C 38.10 40.51

Light fuel oil 78.21 83.16

Heavy fuel oil 11.97 501.16

A total of 13,702.54 994.88

The total product distribution and partial yields are shown in Table V. Included is the material that is removed in the hydrogen sulfide removal system 12, in the exhaust gas stream in tube 17, and mainly in the liquid product stream in tubes 13 and 21.

TABLE V: Total product distribution and yields

Ingredient Moles / h Ti 1-¾

Hydrogen sulphide 304.01

Hydrogen 523.07

Methane 128.85

Ethane 25.08

Propane 25.51

Butanes 19.56 0.56

Pent aans 9, 00 0.32

Hexanes 7.84 0.32

Heptane-190 ° C 37.10 2.00 190 ° C-343 ° C 67.23 5.71

Total fuel oil 662.97 92.52 m 59262

The heptane-190 ° C naphtha intermediate boiling fraction has a specific gravity of 0.765 and contains less than 0.05 residual sulfur, the 190 ° C-393 ° C intermediate fraction has a specific gravity of 0.897 and contains less than about 0.1% by weight of 3 sulfur, total fuel oil, boiling in the range of about 393 ° C, having a specific gravity of about 0.925 and containing 0.3% by weight of sulfur.

The foregoing description and illustrative embodiment illustrate the process by which the present invention is practiced and the advantages achieved by using it to produce higher potential amounts of fuel oil containing less than about 1.5% by weight of sulfur.

Claims (7)

15 59262 A process for preparing a fuel oil containing less than about 1.5% by weight of sulfur from a heavy black oil feedstock, comprising (a) reacting the feedstock and hydrogen in a first catalytic reaction zone under desulfurization conditions to convert sulfur-containing compounds to hydrogen sulfide (b) and hydrocarbons; the effluent from the reaction zone is separated in the first separation zone into a first substantially vaporous fraction and a first substantially liquid fraction, (c) at least a portion of the first liquid fraction is reacted with hydrogen gas to remove to convert additional amounts of compounds to hydrogen sulfide and hydrocarbons, (d) separating the effluent from the second reaction zone to a second heat in the second separation zone; and (e) at least a portion of the second vapor fraction is returned to the first reaction zone to react with the feedstock, and the fuel oil is recovered from the second liquid fraction, characterized in that more than 75% of hydrogen sulfide is separated from the first vapor fraction so that desulfurization of the feedstock, and the hydrogen-rich vapor fraction thus obtained is passed to the second reaction zone to react with a portion or portions of the first liquid fraction fed to it to provide a desulfurization of less than $ 25 from the feedstock. Process according to Claim 1, characterized in that the first vaporous fraction is separated in the third separation zone into a third vaporous fraction and a third liquid fraction. Process according to Claim 2, characterized in that at least part of the fuel oil is recovered from the third liquid fraction. Process according to Claim 2, characterized in that at least part of the third liquid fraction is combined with the first vaporous fraction before the hydrogen sulphide is removed therefrom. Process according to Claims 1 to 4, characterized in that the sulfur is removed in the first and second reaction zones at an overpressure of 14 to 210 μm, a hydrogen content of about 88 to 200 m 2 / m 2 of hydrocarbons, at a temperature of 316 to 482 ° C and a liquid volume rate. 0.25-2.50 per hour. Process according to Claims 1 to 5, characterized in that the first and second reaction zones have a catalyst mixture of a porous support, a Group VI-B metal component and a Group VIII metal component. 1. For the purpose of generating the product under the conditions of 1.5 volts- # svavel av en rämaterialcharge av Tung svartolja, vid vilket förfarande (a) rämaterialhargen oce vte bringas att reagera i en första catalyticeaction with avsvavlingsbetingelser för omvand (b) reacting with the reaction of the reactants in the form of a fraction of the reaction and the reaction of the reactants of the effluent fraction, and i en andra catalytic reaction, i vilken även inledes friskt väte för ersättning av väteförluster och-förbrukningen i förfarandet, förvandling av ytterligare gamder svshaltiga föreningar enluren en fracten en frac form of the ocean and the other part this fraction, and (e) the equivalents and other fractions of the form of the fractions of the reaction group, and the brine is used in the form of the fractions of the reaction group, The reaction time is equal to 75% of the total material content, and the reaction is carried out with the reaction of the reactants with the reactants of the reactants with the addition of the active substances.