DE1017724B - Process for the hydrogenative refining of hydrocarbons or hydrocarbon fractions with hydrogen-containing gases and in the presence of sulfur-resistant catalysts - Google Patents

Description

Those involved in coking, smoldering or gasification of hard coal, lignite, oil shale or the like. Fuels or the hydrocarbons or hydrocarbon fractions obtained during petroleum processing have already been refined hydrogenating on sulfur-resistant catalysts, whereby the Hydrogen required for the hydrogenation of hydrogen-containing, in particular hydrogen-rich Gases was delivered. In addition to hydrogen, coal gas, coke oven gas, carbonization gas, A ¥ water gas or similar gases are used. In catalytic refining, the organic Sulfur compounds in the starting materials and optionally in the hydrogen used contained gas are converted into hydrogen sulfide. This hydrogen sulfide is found for the most part in the refined hydrocarbons or hydrocarbon fractions. It is made from it by washing, e.g. B. with water or alkaline solutions removed.

It has now been found that in the refined hydrocarbons or hydrocarbon fractions contained hydrogen sulfide much cheaper and without the expenditure more expensive Caustic soda or with a much smaller amount of caustic soda by means of stripping of a gas can be removed. In this expulsion, which is expedient by gassing the raffinate with part of the residual gas of the hydrogenating refining takes place, most of the hydrogen sulfide is removed from the products of the refining process without introducing substantial quantities of these products into the Pass over residual gas. The treatment of the raffinate containing hydrogen sulfide is carried out according to the invention under a pressure which is lower than that of the hydrogen refining. The rest of the Hydrogen sulfide can then be removed by washing in a known manner, and it has It has been shown that the amounts of hydrogen sulfide remaining in the refined products are so small are that you can get by with very small amounts of detergent. In addition, most of the Hydrogen sulfide in concentrated form and for sulfur production or for its further utilization well-suited shape obtained, or it can be after compression of the residual gas used for fumigation be returned to the procedure. In this case, they are due to the gassing of the raffinate caused losses of raffinate are particularly low.

It can with the same success instead of the residual gas the fresh gas that of the catalytic hydrogenating Refining supplies the necessary hydrogen or part of it to drive out the procedure

for hydrogen refining

of hydrocarbons or

Hydrocarbon fractions

with gases containing hydrogen

and in the presence of sulfur-solid

Catalysts

Applicant:

Metallgesellschaft Aktiengesellschaft,
Frankfurt / M., Bockenheimer Anlage 45

Dr. Heinz Eisenlohr, Frankfurt / M.,

Dr. Oskar Dorschner, Bad Homburg v. d, height,

and Dr. Wilhelm Herbert, Frankfurt / M.,

have been named as inventors

Hydrogen sulfide can be used, especially if this has been treated according to patent 958,496.

The method is explained using a scheme, for example. Line 1 becomes the compressor 2 sucked in the gas available for the hydrogenating refining and to the working pressure of z. B. brought about 35 atm. For refining of 11 gasoline or benzene are z. B. 200 to 500 Ncbm fresh gas, for example in the form of luminous gas or pressurized gasification gas. The compressed gas flows through line 3, the heat exchanger 4 and the line 5 in the evaporator 6 of known design, which can be heated at 7.

The substances to be refined are from the line 8 by means of the pump 9 via the line 10 in the Evaporator 6 brought. At 11, a non-evaporated portion of the substances to be refined can be removed from the Evaporator 6 can be withdrawn.

Gas and vaporized substances to be refined flow from the top of the vaporizer and pass through the Line 12, the heat exchanger 13 and the line 14 into the reactor 15, which is filled with the catalyst 16. The catalyst is on the floor 17 arranged. It can have a composition known for catalytic hydrogen refining.

The vapors of the refined substances leave the reactor 15 together with the gas through the pipe

709 756/385

device 18 and give their heat in the heat exchangers 13 and 4, which are connected by line 19 to the gases and vapors to be heated. The gases and vapors of the refined substances occur from the heat exchanger 4 through the line 20. In the condenser 21 the condensable Hydrocarbon vapors, e.g. B. gasoline vapors, liquefied. Condensate and gases get through the line 22 into the separator 23, where the condensate and gases separate.

Via the line 24 a part of the gases, for. B. 1000 to 3000 Ncbm per ton of substances to be refined and hour, fed back into the process via the cycle gas compressor 25 and line 26. A other part, e.g. B. 100 to 400 Ncbm per ton of materials to be refined and hour, is used as residual gas withdrawn via lines 27 and 28, relaxed by means of reducing valve 29 and discharged via line 30, z. B. before the gas cleaning of the gas generation plant, the catalytic hydrogen refining supplied with the required hydrogen-containing gas.

From the separator 23 water is withdrawn at the bottom at 31, the z. B. can come from a direct irrigation of the capacitor 21. The raffinate still contains dissolved hydrogen sulfide, e.g. B. in an amount of 2 to 3 g H ₂ S / l with a sulfur content of 0.5 to 0.6 percent by weight in the substances to be refined. The raffinate is discharged through line 32 and, after expansion from 35 atmospheres to 1 atmospheres, by means of valve 33 through line 34 to the z. B. given tower 35 filled with Raschig rings. About 15 Ncbm of gas per ton and hour are withdrawn from the line 28 by means of the line 36. B. 1.2 atü, be relaxed.

This gas is introduced into the lower part of the tower 35 via the line 38.

It contains about 6 to 10 g of H ₂ S / Ncbm. At the bottom of the tower 35, the raffinate is withdrawn through line 39, expanded to normal pressure by means of valve 40 and sent via line 41 with a content of about 0.1 g H ₂ S / l to a plant in which the remaining hydrogen sulfide from the raffinate in a known manner, e.g. B. by caustic washing, is removed. So over 95%> of the hydrogen sulphide dissolved in the raffinate can be expelled with the residual gas containing hydrogen sulphide or similar other gases. As a result of this measure according to the invention, the caustic consumption drops from about 10 kg of NaOH (100%) to less than 0.5 kg of NaOH per ton of raffinate. The alkali saving in kg NaOH per ton of raffinate increases even further with raw products with higher sulfur contents.

The gas enriched with hydrogen sulfide can be discharged from the tower 35 via the lines 42, 43, the pressure reducing valve 44 and the line 45 are discharged into the residual gas, or it is wholly or partially, if necessary after a reduction in its pressure, the fresh gas via lines 42 and 46 forwarded. In this case, losses of raffinate are avoided or reduced.

If the hydrogen sulfide is blown out of the raffinate with the help of fresh gas, this z. B. optionally taken after compression from line 3 by means of line 47 and optionally after a pressure reduction by means of valve 48 via the lines 49 and 38 into the tower 35. In particular In the case of fresh gases containing oxygen, pretreatment of the fresh gas is recommended according to patent 958 496 to avoid the formation of elemental sulfur in the raffinate.

This pretreatment is preferably carried out in such a way that the fresh gas is released at normal or elevated pressure and elevated temperature of about 50 ° C up to the temperatures of the subsequent catalytic refining with hydrogenating contacts in contact is brought, the z. B. Metals of VI. Group of the periodic table in oxidic and / or sulfidic form, in particular molybdenum, tungsten, vanadium, and other metals, in particular the VIII. Group of the Periodic Table, such as cobalt, nickel, iron, and / or optionally Can contain carriers.

Claims (5)

Claim Et 1. Process for the catalytic refining of hydrocarbons or hydrocarbon fractions in the presence of hydrogen or hydrogen-containing gases on sulfur-resistant catalysts, characterized in that the · hydrogen sulfide contained in the refined liquid Products of the process is contained, from it for the most part by blowing means the gases used or produced in the process and the remainder z. B. by washing from the Products is removed. 2. The method according to claim 1, characterized in that the containing hydrogen sulfide Raffinate is blown out with the residual gas at a pressure which is below the pressure of the hydrogenating Refining lies. 3. The method according to claim 1, characterized in that the blowing out of the contained in the raffinate Hydrogen sulfide takes place with fresh gas. 4. The method according to claims 1 and 3, characterized in that the fresh gas before Blowing off the hydrogen sulfide is subjected to a preparation according to patent 958,496. 5. The method according to claims 1 and 4, characterized in that the with hydrogen sulfide enriched gas is fed to the residual gas or optionally the fresh gas. References considered: U.S. Patent No. 2,560,374. 1 sheet of drawings © 709 755/385 10.57