A method of producing acetylene and synthesis gas

 

(57) Abstract:

The invention relates to a method for production of acetylene and synthesis gas. Describes two variants of the method. The first option is a method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, characterized in that the gaseous reagents previously separately heated, mixed to homogeneity in the mixing zone, introducing into interaction after passing through the combustion unit and quickly cooled aqueous medium for rapid cooling after the reaction. Provided by recirculation of the water environment for the abrupt cooling in a closed system. The second option is a method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, characterized in that the gaseous reagents previously separately heated, mixed to homogeneity in the mixing zone, introducing into interaction after passing through the combustion unit and quickly cooled aqueous medium for rapid cooling after the reaction. The ratio between the gaseous reactants are chosen so that acetylene and soot formed during the reaction are in a weight ratio of 50-500. The technical result consists in removing nedostatecna relates to a method for production of acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, which is characterized by the fact that gaseous reagents previously separately heated intensively mixed in a mixing zone, introducing into interaction after passing through the combustion unit and quickly cooled aqueous medium for rapid cooling after the reaction.

Production of acetylene and synthesis gas by partial oxidation of hydrocarbons is well known. Partial oxidation of methane (natural gas) to produce acetylene and synthesis gas found large-scale application in the world. While the production of synthesis gas from natural gas by partial oxidation is technically simple process, a process for production of synthesis gas associated with obtaining acetylene, is limited to the exact conditions of space, time and quantities. Usually natural gas and oxygen as the reactants previously separately heated to temperatures up to 700oC, intensively mixed in a mixing zone (cone) and enter into interaction after passing through the combustion unit.

The combustion unit typically includes a number of channels of a special form, in which the rate of the reaction mixture of oxygen/natural gas is much more than the propagation velocity of the flame is inoe mixture.

Reaction chamber adjacent to the combustion unit, characterized by a special volume, allowing the hot gaseous products out of the reaction chamber within a few milliseconds, so the length of stay in it acetylaspartic reaction gas is very short. Extremely short duration of stay in combination with low pressure leads to partial oxidation of the hydrocarbon to acetylene and synthesis gas, because for a short period of time complete conversion of the reactants in the synthesis gas is impossible. After this period of time for which the reaction equilibrium, the corresponding temperature level 1500-2000oC, cannot be attained, the reaction products almost immediately or cooled rapidly to a temperature below 300oC, using as a medium for the abrupt cooling water or residual oils. Sharp cooling prevents the decomposition of the produced acetylene carbon and hydrogen or to avoid interaction of water released during the reaction (process water), with acetylene with the formation of carbon monoxide and hydrogen. Usually such processes are carried out under atmospheric pressure or not is to be used all gaseous or easily vaporized hydrocarbons. While the production of synthesis gas from natural gas by partial oxidation is technically simple process, during the conduct of which is not formed almost no by-products, the process of obtaining synthesis gas associated with obtaining acetylene, depending on specifically to be used as the reactant hydrocarbon always leads to the formation of smaller or larger amounts of soot. In contrast to partial oxidation of methane to synthesis gas, in which soot can be suppressed by high pressure and a relatively large length of stay, in the process of partial oxidation of hydrocarbons to acetylene and synthesis gas low pressure and very short stay, a gap of only a few milliseconds, rise to the formation of acetylene, i.e., incomplete conversion of the reactants in the synthesis gas. Therefore, soot cannot be avoided.

Moreover, the concentration of major components of the reacted or recerving gas depends on the ratio of oxygen/hydrocarbon raw materials. By increasing the oxygen concentration of acetylene increases until, until it passes through a maximum. Usually for DOS is malinich temperature and pressure) should not exceed approximately 0.6.

Rapid cooling recerving gas not only leads to the dissipation of heat from the gas mixture, but also to the removal of soot from the reaction products.

In accordance with the state of the art in this field quenching can be performed by two methods, namely, respectively, by the method of rapid cooling by water and by the method of rapid cooling oils (see Ullmann''s Encyclopedia of Industrial Chemistry, edition 5, volume A1, pages 97-144).

In the process of rapid cooling with water the resulting gas is cooled to approximately 80-90oC cooling water environment. Part of the soot formed during the reaction, the resulting gaseous mixture is removed due to a sharp cooling. The resulting gas mixture is optionally purified and cooled by flushing circulating water in a cooling column, which removes additional amounts of carbon black. In conclusion, the gas mixture is passed through an electrical filter, which remove and wash water additional amount of soot. Thus, the water drains from the system to sudden cooling of the cooling column, and an electric filter are deleted washing soot. However, this water is not stable dispersion or enter the data with the accumulation of water contained in the soot, this last need of water to remove. For this reason, such integrated water drains continue to serve in the decanter for soot. This decanter (basin decanter) due to residual gas, which is associated with soot particles, these last float. The top of the particulate layer, depending on the source material contains 4-8 wt.% of carbon. This soot "Scherbaum" from the water surface and in the future Tegaserod in tanks with stirring, resulting in a gain particulate sludge with a water content of more than 90%. This particulate sludge is burnt in special devices for burning. After that United water runoff from a basin of decantation sent to the tower in which they are cooled, and then return to the step of rapid cooling, a cooling column and an electric filter.

The process of rapid cooling by water leads to significant energy losses at cooling water in the cooling towers and associated with problems of emissions and the problems arising out of the discharge odor. When containing soot foam floats in the open basin decantation, it is a significant source selection aromatics, especially benzene. In cooling towers can also pressostat in their sharp cooling oils, for example, residual oils or high-boiling aromatic heavy oils. When using these oils for rapid cooling or cooling the formed soot suspendered in oil. The resulting gas out of the combustion unit at a temperature of 200-250oC. the Heat absorbed by the medium for rapid cooling, you can pass water with the receiving water vapor by passing the oil through heat recovery steam generators, and then her return to the stage of rapid cooling. Thus, energy losses in the implementation of such a method is less than in the process of rapid cooling with water. The residual heat of the obtained gas is directed to a closed system refrigerators. Thereby preventing emissions. The cooled oil is returned to the combustion unit.

While in the process of rapid cooling water should be replenished loss of water in the decanter and the tower, in the process of rapid cooling oil must add substantial quantities of oil. The reason for this lies in the fact that the sharp cooling in contact with the reaction gas, the temperature reaches 2000oC, part of the oil Criciuma. Exposed, thus cracking the oil decomposes and vstupaetsya as a result of interaction with gases and cracking oil, used for rapid cooling, suspendered in oil. Because the ability of the oil to absorb carbon or soot and products of cracking oils limited, a part containing soot oil to regenerate, so it should be separated from the soot. This is achieved, for example, by distillation of the oil, resulting in carbon is produced in the form of small pellets. The disadvantage of the process of rapid cooling oil is technically expensive regeneration containing soot and oil in the need to add large quantities of heavy oils. Moreover, with collect substantial amounts of soot or coke and lighter products of decomposition of heavy oils, the so-called pyrolysis oils. The advantage of the method of rapid cooling oils is that its implementation does not involve emissions and is accompanied by only a small loss of process heat (see Ullmann''s Encyclopedia of Industrial Chemistry, edition 5, volume A1, pages 106-115).

Of the prior art the closest analogue of the present invention is a method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, including preliminary separate heating of the gaseous reagents, tx2">

The task underlying the present invention is to eliminate the disadvantages of the method of rapid cooling with water and method of rapid cooling oils.

In accordance with one implementation of the present invention, in the method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, in the exercise of which gaseous reagents previously separately heated, thoroughly mixed in a mixing zone, introducing into interaction after passing through the combustion unit and is rapidly cooled, the aqueous medium after the reaction, according to the invention additionally provides for recirculation of the water environment for the abrupt cooling in a closed system.

It was found that the amount of soot generated upon receipt of acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, can be greatly reduced.

It was found that with an increase in the ratio between oxygen and hydrocarbon in the gaseous reagents, the amount of soot formed in crakereanda gas, can be reduced to a much greater extent than the amount of acetylene. Thus, the regulation of the ratio of the quantity of generated oxygen acetylene decreases only slightly.

Lowering the concentration of acetylene in crakereanda gas to half its maximum level, i.e., when using half the capacity of the combustion unit for acetylene (example 2), the amount of soot formed is only approximately 7% from the amount of soot, which is formed in the case of the operation of the combustion unit to full capacity by acetylene (comparative example 1) and with achievement thus maximum yield of acetylene.

When the ratio of oxygen to hydrocarbon increases to such an extent that the performance of the unit combustion by acetylene is reduced to one-third of its maximum (example 3), the soot formation is reduced to approximately 2% from the amount of soot, which is formed at the maximum performance acetylene block combustion (comparative example 1).

A significant reduction in soot formation in comparison with the formation of acetylene in accordance with the present invention allows to modify the above method of rapid cooling with water so that this can be provided by a closed water recirculation systems for rapid cooling and cooling water. In the implementation of the act is to smash through the respective cooling systems for example, air or plate coolers, which can also be used in combination with cooling towers. This way you can avoid removal of soot in the open basin decantation and necessary heat to the cooling towers. Thus it is possible to eliminate the problems associated with odor and emissions, which would otherwise develop into environmental problems. Soot formed during the reaction, it is preferable to capture water for rapid cooling or cooling and to the left in the water. This allows, therefore, to eliminate the destruction and burning of large quantities of particulate sludge or particulate foam. Soot is preferably removed from the recirculating water for rapid cooling and cooling water only in such quantities that correspond to the amounts of process water generated in the reaction, which must be removed from circulation. Thanks to the removal of relatively small amounts of soot water can be separated by any means.

In accordance with another variant of implementation of the present invention, the aqueous medium for rapid cooling, preferably at least an amount corresponding to at least the quantities and not necessarily replace the fresh water environment. This provides the possibility of regulating the amount of soot to be removed from circulation, and the amount remaining in circulation.

Therefore, the method in accordance with the present invention combines the advantages of the method of rapid cooling with the use of oil, primarily recirculated in a closed system, with the advantages of water method of rapid cooling, in which rapid cooling using low cost environment, not consumed in the process, so there is no need for continuous addition. The disadvantages of both of the known methods of rapid cooling are eliminated primarily such as open basin decanter and the tower in the implementation of water method of rapid cooling, such as technologically advanced regeneration containing soot oils and the need for continuous addition of heavy oils in the implementation of the method of rapid cooling oils.

Hydrocarbons that can be used in accordance with the present invention can be any hydrocarbon, which are quite volatile. These hydrocarbons may include hydrocarbons of only one type, but can also be a CME is hydrocarbon use natural gas. You can apply natural gas of any composition. In accordance with one implementation of the present invention, a natural gas contains at least 98 vol.% methane.

In accordance with the present invention during implementation of the proposed method can be used all lower hydrocarbons, especially paraffins, such as methane, ethane, propane and butane, either individually or as mixtures thereof.

In accordance with another variant implementation of the invention, gas in addition to hydrocarbons may include other gases, such as nitrogen, carbon dioxide, noble gases.

In accordance with one implementation of the present invention is used, the gas may be a pure butane.

The ratio between the oxygen atoms of the oxygen and carbon atoms in the hydrocarbon can be adjusted in accordance with the target weight ratio between acetylene and soot or target performance on acetylene. If you want high performance acetylene, the ratio between the oxygen atoms in the oxygen and carbon atoms in the hydrocarbon can be reduced, while for the reduced performance acetylene capacity of soot on this ratio may be higher. In accordance with the present invention depending on the target of the reaction products of the process conditions can be varied.

When implementing the method in accordance with the present invention, the preferred atomic ratio of oxygen atoms in the oxygen and carbon atoms in the hydrocarbon is at least of 1.05, preferably of 1.05 to 1.6, more preferably of 1.15 to 1.4.

In accordance with one embodiment of the present invention in a hydrocarbon used in natural gas, the volume ratio under normal conditions between the oxygen and natural gas than 0.6, preferably is 0.61-0,78, more preferably of 0.625-0,7.

In accordance with another variant of implementation of the present invention, the ratio between the gaseous reactants is chosen so that acetylene and soot formed during the reaction are in a weight ratio of 50-500, preferably 50-150.

In accordance with one embodiment of the present invention, the concentration of soot in the aquatic environment for rapid cooling does not exceed 1 wt. %, preferably 0.1-1 wt.%, and more preferably 0.2 to 0.4 wt. %. In predpochte between the oxygen atoms in the oxygen and carbon atoms in the hydrocarbons is approximately 1.3, due to which the weight ratio between the produced acetylene and soot is approximately 100.

Other distinctive features and advantages of the invention are described in more detail in the following examples.

Experiments in these examples was performed using the same device, as described in Ullmann''s Encyclopedia of Industrial Chemistry, edition 5, volume 1, 1985, page 107. Gaseous reagents served as natural gas and oxygen. Natural gas contained at least 98 vol.% methane.

However, in accordance with the present invention can be used with natural gas or gas mixture of any composition.

Gaseous reagents separately heated to 600oC, was mixed to homogeneity in the mixing zone of the combustion unit and introduced into the interaction after passing through the diffuser and the combustion unit. After a few milliseconds of reaction time containing acetylene gaseous cracking products was rapidly cooled with water to a temperature of 80oC. the resulting acetylene and synthesis gas was provided as usual by the fractional absorption and subsequent desorption using an appropriate solvent. Formed as a by-product of sacii water for rapid cooling or cooling water. In the process in accordance with comparative examples soot was removed from the water for rapid cooling and cooling water according to the method of decanting, which is described above.

Specific experimental conditions and results of experiments are presented in table 1, provided at the end of the description.

From the above examples you can see that in the process in accordance with comparative example 1 in the case of removal of soot together with process water resulting concentration of soot in the process water is 2.1%. In this process due to the high concentration of soot to remove it from the water for rapid cooling and cooling water must be applied adverse and hazardous method desantirovaniya. Furthermore, it is necessary cooling water in the cooling towers. The same applies to comparative example 2, which is achieved by the soot concentration of 1.65%. This concentration of soot is too high for the recirculation of the cooling medium. In accordance with examples 1 and 3 the concentration of soot reduce respectively to 0.36 and less than 0.07 per cent. In a closed system soot in such concentration does not create any problems for the recycling of water for rapid cooling and cooling water. Remove Ncentratio soot, which does not impede water circulation for rapid cooling and cooling water. Thus, for water circulation for rapid cooling and cooling water in examples 1 and 3 it is possible to use a closed system. You must remove approximately 3 m3per hour containing soot process water. To remove soot this exhaust water can, for example, to filter or can be routed to the effluent treatment plant. Example 1 performance acetylene is three quarters of this performance in comparative example 1. However, performance on soot reduced from 75 to 10 kg/h, i.e., hence, by a factor of about 8 (performance silicas in accordance with example 1 is approximately 1/8 from performance silicas in accordance with comparative example 1).

In example 2, the performance of acetylene reduced to 1/2 of this performance in comparative example 1. However, performance on soot is reduced by a factor of 15, up to 5 kg/h, compared to comparative example 1.

Examples 4 and 5 demonstrate the results in the case of an even greater correlation between the oxygen and natural gas. The concentration of soot in recirculatio 10 and 6 tons per day. At the same time, the ratio between acetylene and soot increases accordingly up to 347 and 417. Thus, if, in accordance with one embodiment of the invention, to permit a reduced yield of acetylene, the performance soot can be reduced to very small amounts, reaching in this way a very high weight ratio between acetylene and soot. In accordance with one embodiment of the invention, used the ratio of oxygen to natural gas may, therefore, depend on the target amounts and types of reaction products, as well as the required reduction of soot formed during the reaction.

The composition of gaseous hydrocarbons can be varied. The following example (example 6) hydrocarbons were characterized by the following composition: 86 about. % methane, 0,5% vol. ethane, 2,7% vol. propane, 9,6% vol. butane, 0,1% vol. of pentane, and the rest is nitrogen, carbon dioxide and helium. The number of carbon atoms in the hydrocarbon mixture was 1,3428 Nm3C/Nm3of the mixture. Obtained results are given in table. 2 (see the end of the description).

This example shows that, in accordance with the present invention the composition is used in which imeneniya closed water recirculation systems for rapid cooling and cooling water.

Example 7

This example used the pure butane.

Source butane, Nm3/h: - 1930 (5000 kg)

The source of oxygen, Nm3/h: - 4200

The volumetric ratio of oxygen/butane: - 2,176

The ratio O/C: - 1,088

Acetylene in vol.%: - 6,85

Performance acetylene, tons per day: - 31,5

In examples 3-6 presents additional experimental results, showing that with an increase in the ratio between oxygen and natural gas, the quantity of generated soot decreases much faster than the performance of the acetylene.

The results of the experiments show that, in accordance with the present invention, the amount of soot formed in the process of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen can be reduced so that the possible recirculation of the water environment for rapid cooling, used in the course of conducting this process in a closed system.

1. A method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, characterized in that the gaseous reagents previously separately heated, thoroughly mixed in a mixing zone, introducing into interaction after about the different topics as provided for recirculation of the water environment for the abrupt cooling in a closed system.

2. The method according to p. 1, characterized in that after the abrupt cooling water environment is subjected to sudden cooling indirect cooling, in particular coolers, plate coolers or other cooling means.

3. The method according to p. 1, characterized in that after the abrupt cooling of the aquatic environment for rapid cooling, preferably in an amount corresponding at least to the amount of process water generated during the oxidation reaction, are removed from circulation and not necessarily replace the fresh water environment.

4. The method according to p. 3, characterized in that the soot formed during the reaction and contained in the aquatic environment for rapid cooling, after the abrupt cooling allocate part of the aquatic environment for rapid cooling, removed from circulation.

5. The method according to p. 1, characterized in that the gaseous reagents atomic ratio of oxygen atoms in the oxygen and carbon atoms in the hydrocarbon is at least 1,05.

6. The method according to p. 5, characterized in that the atomic ratio of 1.05 to 1.60, predovoi natural gas, and volume ratio in normal conditions between the oxygen and natural gas exceeds 0.6.

8. The method according to p. 7, characterized in that the volume ratio in normal conditions is 0.61 - 0,78, preferably of 0.625 - 0,70.

9. The method according to p. 1, characterized in that the concentration of soot in the aquatic environment for rapid cooling does not exceed 1 wt.%, preferably 0.1 - 1 wt.%, more preferably 0.2 to 0.4 wt.%.

10. A method of producing acetylene and synthesis gas by partial oxidation of hydrocarbons with oxygen, characterized in that the gaseous reagents previously separately heated, thoroughly mixed in a mixing zone, introducing into interaction after passing through the combustion unit and quickly cooled aqueous medium for rapid cooling after the reaction, characterized in that the ratio between the gaseous reactants are chosen so that acetylene and soot formed during the reaction are in a weight ratio of from 50 to 500.

11. The method according to p. 10, characterized in that the acetylene and soot formed during the reaction are in a weight ratio of 50 to 150.

12. The method according to p. 10, characterized in that the gaseous reagents atomic ratio between the ptx2">

13. The method according to p. 12, characterized in that the atomic ratio of 1.05 to 1.60, preferably 1,15 - 1,40.

14. The method according to p. 12, characterized in that the hydrocarbons are natural gas and the volumetric ratio under normal conditions between the oxygen and natural gas exceeds 0.6.

15. The method according to p. 14, characterized in that the volume ratio in normal conditions is 0.61 - 0,78, preferably of 0.625 - 0,70.

16. The method according to p. 10, characterized in that provided for recirculation of the water environment for the abrupt cooling in a closed system.

17. The method according to p. 10, characterized in that environment for rapid cooling is subjected to indirect cooling, in particular, coolers, plate coolers or other cooling means.

18. The method according to p. 16, characterized in that the circulation will remove the water in an amount corresponding to the amount of water formed during the oxidation reaction.

19. The method according to p. 16, characterized in that the soot formed during the reaction and contained in the aquatic environment for rapid cooling, after the abrupt cooling allocate part of the aquatic environment for rapid cooling, remote from the circus is to be placed does not exceed 1 wt.%, preferably 0.1 - 1 wt.%, more preferably 0.2 to 0.4 wt.%.

 

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8 cl, 1 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining acetylene by Sachsse-Bartholome method by burning natural gas/oxygen mixture in one or several burners with obtaining pyrolysis gas, which is cooled in furnace columns in two or more stages. One or several furnace columns are respectively connected to each burner, with said pyrolysis gas being extinguished at first stage of cooling by means of pyrolysis oil with obtaining low-boiling fraction, containing styrene, indene, benzene, toluene and xylene, from one or several furnace columns, which is cooled by direct cooling with water and is divided in phase-separator into water phase and organic phase, containing styrene, indene, benzene, toluene and xylene, which is supplied into head part of one or several furnace columns as phlegm. Method is characterised by the fact that organic phase, containing styrene, indene, benzene, toluene and xylene,is supplied from phase-separator to selective hydration on catalyst, which contains at least one metal of platinum group on inorganic metal oxide as substrate, containing from 0.05 to 5 wt % of platinum group metal, counted per the total catalyst weight, with said selective hydration being carried out under pressure from 1 to 40 bars and temperature in the range from 25 to 150°C.

EFFECT: application of claimed invention makes it possible to reduce problems, associated with polymer deposits.

10 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of producing acetylene and synthetic gas. Disclosed is method of producing acetylene and synthetic gas by partial oxidation of hydrocarbons with oxygen, wherein initial gases, which enter stream containing hydrocarbon, and flow containing oxygen, first, preliminary heated separately, then mixed in mixing zone, and after flowing via burners cause their reaction in combustion chamber, then quickly cooled. At that, to block of burners surface facing combustion chamber stream of washing gas flow is added. this washing gas is introduced via several holes through burner unit, wherein averaged ratio of effective area of unit of burners surface to number of these holes for gas flushing flow in burners ranges from 5 to 100 cm2, wherein averaged ratio of unit of burners effective surface to number of these holes for gas flushing flow in burners is calculated from ratio of total effective surface of unit of burners to total number of holes for gas flushing and carried out through holes for washing flow to gas distributing devices so that 70-100 vol% of supplied washing gas flow is directed parallel to surface of burners unit side facing combustion chamber.

EFFECT: invention allows to produce synthesis gas and acetylene using improved method of partial oxidation of hydrocarbons, which prevents deposits on surface of unit of burners without using mechanical treatment.

7 cl, 4 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method for producing acetylene and synthesis gas by partial oxidation of hydrocarbons by means of oxygen. The first feed flow containing one or more hydrocarbons and the second feed flow containing oxygen are preheated separately from each other, mixed in a mass flow ratio from the second feed flow and the first feed flow corresponding to the oxygen number λ, less than or equal to 0.35. The oxygen number λ is the ratio of the amount of oxygen actually present in the second feed flow and the stoichiometrically necessary amount of oxygen that is required for the complete combustion of one or more hydrocarbons contained in the first feed flow that are fed to the combustion chamber (F) by means of the burner unit (B), where there is a partial oxidation of hydrocarbons with producing cracked gas, which is subjected to quenching to a temperature from 200 to 250°C after the combustion chamber relative to the flow direction by using the oil injection for quenching. This produces a flow of gaseous products Ig, which is cooled in the distillation column (BK) with additional oil for quenching. Liquid from one or more suitable stages is withdrawn from this distillation column (BK), cooled by indirect heat exchange with water to produce a flow and is again fed to the distillation column (BK), above the stage, from which it was withdrawn, to produce a gaseous stream products IIg, cooled to the temperature of 60°C to 90°C, which is fed to the final cooler (SK), where, as a result of direct heat exchange with water, there is a flow of gaseous products IIIg, cooled to the temperature of 20°C to 50°C, as well as process water flow Iliq. Process water flow Iliq is purified by partial evaporation in a single-stage pressure-relief tank (E). This process water flow Iliq is evaporated in the amount of 0.01 wt % up to 10 wt % in terms of the total weight of the same flow to produce a purified process water flow IIliq, which is utilized with wastewater.

EFFECT: high yield of acetylene while observing existing environmental restrictions.

9 cl, 1 dwg, 1 ex

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