DE3311371A1 - Method for the production of inexpensive pure hydrogen gas from residue oils - Google Patents

Abstract

In the processing of crude oil the need for inexpensive and, in particular, pure gaseous hydrogen (H2) has increased considerably in recent years since a general trend in the industrial countries of the world from heavier products to lighter ones can be noted. To this extent, the hydrocracking of vacuum distillates is gaining in importance. The considerable amount of gaseous hydrogen required for this cannot be made available in sufficient quantities. Therefore, this need for gaseous hydrogen is conventionally covered from residue oils by direct combustion of the residue oils, with the addition of steam. The disadvantages of the conventional method consist in the fact that, as a result of the process, the H2 gas contains impurities which rapidly destroy the catalysts in the following process (hydrocracking). Furthermore, more than 55 % by weight of residue oils must be made available for the production of heat, so that the yield of H2 gas is low. These disadvantages are avoided by the method of the invention since injurious substances can be kept away or be removed beforehand by indirect heating and the method requires only 13 % by weight of the residue oil for the production of heat, since the remaining heat required is covered from the CO gas which is produced as a result of the process. In accordance with the method of the invention, the yield of H2 gas is substantially greater than in the conventional methods. Furthermore, the purity satisfies ... Original abstract incomplete.

Description

Λ.L. Alkali-Hydrid GmbH GiselastraPe 41 3

5600 V / unnertal 1

the 28th of March 19B3

Process for the production of inexpensive, pure hydrogen gas from residual oils

Inventor: Dipl.Ing. Albert LICHTE 5600 V / unnertal 1

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The invention relates to a method for producing inexpensive, pure hydrogen gas (H ₂ ) from. Residue oils by mixing the residual oil with an alkali hydroxide melt, preferably with a sodium hydroxide (NaOH) melt between 360 and 4-00 C in the stoichiometric ratio to the carbon (C) content in the residual oil and by heating the mixture to 830 to 95O ⁰ C without pressure or up to a pressure of 10 to 15 bar and by passing the mixture over

a pipeline into a reactor (5) »whereby through

ι
slight relaxation if necessary by a few bar

Gas mixture of carbon monoxide (CO) and sodium hydride (NaH) is generated, the CC gas is freed from the NaH component

Ύ ' becomes and with the liberated NaH component through touch

with V / water 'a very pure hydrogen gas (Ho) is generated.

It is well known that petroleum is a mixture of numerous carbonaceous substances with boiling ranges that continuously merge into one another. By fractional distillation, it is first at atmospheric or slightly above horizontal air into so-called cuts, fractions, disassembled, "ü'ie eg heating gas, LPG, light gasoline at 40-12C ⁰ C, light naphtha at 100-15O ⁰ C, heavy naphtha at 140- 180 (20O) ⁰ C, luminous oil, petroleum at 2C0-250 ° C, gas oil - at 250-38O ⁰ C, spindle oil above 30O ⁰ C, distillation - (^ residue above 35O ° C.

Different cuts are also known as straight-run products are possible.

If more distillate products are desired, the must. Distillation residue (heating oil S, long residue, also Bunker called C-'il) by vacuum distillation further decomposed.

Especially when the crude oil base is used for the production of lubricating oils or for catalytic cracking suitable is.

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The vacuum residue (short residue), if it is not to be processed otherwise, is used for various special purposes, e.g. bitumen for roads, for insulating compounds, roofing felt etc. Catalytic cracking, which ^{takes place at 470 to 500 0} C, is mainly used to in addition to produce gasoline and light gas oil. With this processing there is a risk of inactivating the catalyst too quickly. Cracking residues can be heating oil, usable by visbreaking or coking as petroleum coke for the production of electrodes, carbon brushes etc.

Hydrocracking of vacuum distillates has recently become more important. Although pressures of over 100 bar are necessary, the process is advancing more and more. The need ¹ · of hydrogen gas is substantial and can not always be provided in sufficient lüengen v / ground.

Attempts are currently being made to meet the increased demand for hydrogen gas by burning residual oils and blowing steam into the directly heated residual oil to cover (also through the smoldering process). However, will this not only generates hydrogen gas, but also contains hydrogen sulfide in the gas mixture, Sulfur dioxide, nitrogen, carbon dioxide and, for example, nickel and vanadium etc. The latter destroy the catalysts in the procedures previously described. The sulfur compounds can, for example, by the Claus process removed / grounded. After this procedure, a considerable effort must be made in order to obtain the hydrogen gas to get rid of its by-products.

The inventive idea now consists in the Residual oils through inexpensive and pure hydrogen gas production Better to use with the least amount of energy. It has been found that the inventive device proposed method only a third of the

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annoying accompanying components carried along with the CO-G-as is, is in the palladium separation vessel? freed from CC gas. The dietary fiber is drawn off in the first circulatory system (Fig-3), so that no damaging Influences in the subsequent catalytic process can be v / effectively v / ground.

The result of the method according to the invention shows that from 25 t residual oil approx. 64,444 m ^ hydrogen gas (K2) are recoverable in the normal state.

Fig. 3 gives an example of an installation structure Carrying out the method according to the invention again.

Preheated residual oil of approx. 380 C is fed to a mixing nozzle (3). Line pump (2) conveys the sodium hydroxide melt (NaOH) through the Kisch nozzle (3) from a storage container (1), which is only electrically heated for start-up, while the mixture of residual oil and NaCH is pumped through a Eöhren furnace (4) and is brought to the reaction temperature of 835 to 95O ⁰ C in the process. The system can be operated without pressure, but also at a pressure of 10 to 15 bar, preferably 12 bar. The heated mixture is fed into a reactor (5) via one or more pipelines, where it is brought to a lower pressure by relieving it, whereby the two gas components CO and NaH are formed. These are passed directly into the separating column (8) consisting of ... packing elements. Below the reactor (5), metals such as nickel, vanadium, etc. are separated and deposited from the NaCH melt by a separator (7), while the NaOH melt flows back into the storage container (1).

With the introduction of the gas mixture CO and II3H into the Separating column (8) can be combined according to the invention Effectively earth the Saizschmelz circulatory system (system 1: 17/18/8/10 and system 2: 13/14/15/16).

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System 1 consists of a pump (1 ⁷ ), condenser (1R), separating column (R) and storage tank (10). That is to say, the separating column (R) is sprinkled with an NaCH molten salt ^{cooled to about 5PO 0} C by means of a pump (17). Here, the molten metal absorbs KaH through the rising gas mixture, while the GO-G-as is still separated from the hydrogen gas previously bound in the cooling oil by a palladium separating vessel "(* 9). The CO Gas is fed to a burner in the Höhrenofen (4) as fuel gas, where about 13% by weight of the residual oil is also subjected to combustion.

System 2 also consists of pump (13), cooler (14-), Separating column (15) and the storage container (16). The NaH is enriched by means of a pump (13) KaOH melt for sprinkling the separating column (15) fed. Water is added approximately in the middle of the column by sprinkling or blowing in steam. Here ' NaH reacts with water directly to NaOH, with the formation of very pure hydrogen gas, which the hydrogenation plants etc. can be supplied / grounded. The NaOH recovered from the NaH is recovered from the storage container (16) passed to the beginning of the process in the storage container (1).

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Claims (9)

jpJAC! ·. -. '»■. . Π 1. Process for the production of inexpensive, pure hydrogen gas (H ^) from residual oils by Raschen. of the residue oil ir.with an alkali hydroxide melt, preferably with a sodium hydroxide (NaOH) melt between 360 and 400 ⁰ C in the stoichiometric ratio to the carbon (C) portion in the residue oil and by heating the mixture to 830 to 95O ° C pressureless or up to a pressure of 10 to 15 bar and by introducing the mixture through a pipeline into a reactor (5), whereby a gas mixture of carbon monoxide (CO) and sodium hydride (NaH) is generated by slight expansion, possibly by a few bar, the CO- Gas is freed from the · NaH component and with. the freed NaH component is produced by contact with water a very pure hydrogen gas (H2), characterized in that? the heating takes place indirectly for the course of the reaction. 2. The method according to claim 1, characterized in that about 23 wt .- ^ from the residual oil used pure hydrogen gas (Ho) is produced and about 13 wt .- $ is used to "cover the heat of reaction. 3. The method according to claims 1 and 2, characterized in that that the process-related resulting carbon monoxide (CC) gas covers the entire remaining heat requirement. 4. The method according to claims 1 to 3, characterized in that that the gas mixture formed in the reactor (5) of carbon monoxide (CO) and sodium hydride (NaK) in the two combined molten salt circulation systems. (System 1: 17/18/8/10 and System 2: 13/14/15/16). BAD ORIGSNAL COPY 5. Process according to claims 1 to 4, characterized in that that the sodium hydride (NaII) component in the gas mixture is absorbed by the molten salt in the Kreilauf system 1 (reservoir 2 (1O)). 6. The method according to claims 1 to 5, characterized in that that the sodium hydride (NaH) picked up by the molten salt by contact with V / ater at any temperature, but preferably 380 ⁰ C at ca.ι, is converted in the circulation system again in sodium hydroxide (NaOH) (reservoir 3 (16)) and very pure hydrogen gas (K2) is generated. 7. The method according to claims 1 to 6, characterized in that dai? the recovered sodium hydroxide (NaCH) from the System 2 (reservoir 3 (16)) back into the heater circuit (Reservoir 1 (1)) is supplied. 8. The method according to claims 1 to 7, characterized in that that the accompanying substances in the residual oil as well as previously bound hydrogen gas (H ₂ ) are removed from the combined salt cycle system 1, namely hydrogen gas (H2) through a palladium separating vessel (9)> nickel (Ni), vanadium (V) etc. below the reactor (5) through the separator 1 (7) and sulfur (S) as sodium sulfate (Na ₂ SO ^) or the like below the storage container 2 (10) through the separator 2 (12). 9. The method according to claims 1 to 8, characterized in that that the heat released from 1-reaction sequence 1 and (Cooler (14 and 18)) for steam or electricity generation is used. BATH ORIGINAL