DE1000551B - Method and device for processing petroleum - Google Patents

Description

Method and device for processing petroleum Addition to patent application A218461Va / 12g The subject of the main patent application A 2I846 IVa / I2g is a process for carrying out endothermic chemical reactions, especially cracking reactions, in which the flow of the input material is tangential to the wall of a cyclone-shaped one Reaction space along the centrally also propagating in whirl) motion Flow of a suitable heat transfer gas and, if necessary, is evaporated and preheated and with the heat carrier gas in the reversal point or in its vicinity is mixed, whereupon the endothermic reaction takes place until due to the heat loss caused by it and the heat dissipation for evaporation or Heating of the preheated or non-preheated feed, the reaction mixture quenched and the reaction is brought to a standstill.

The subject of the invention is a further development of this method in application to petroleum processing. The procedure is characterized by that a fresh oil, which can be suitably pre-cleaned, with superheated steam from about 50 to 15,000, preferably 12,000, reacted in a cyclone is (reaction stage) and that the reaction mixture is then distilled and Separation stations is passed (distillation stage) while at the same time its heat content, down to a temperature of about 200 to 2500, to the direct Distillation of further crude oil and / or for indirect superheating of further steam exploits. In this case, return gas can optionally be fed in together with the fresh oil that comes from previous operations of the same type.

To obtain the superheated water vapor at the high temperatures mentioned it is appropriate to at least part of the same from an oxyhydrogen reaction of To win hydrogen and oxygen, optionally also from the reaction stage accruing methane can be added. This oxyhydrogen reaction is useful carried out in another upstream cyclone. The desired temperature of the superheated water vapor is fed into the Cyclone and by adjusting the ratio between the secondary steam supplied and water vapor obtained from the oxyhydrogen reaction. Hydrogen and oxygen are introduced at the top of the cyclone, which enters additional secondary steam tangentially from the base into the burner so that it cools its wall while he heats himself up.

The superheated steam generated in this way, which depends on the requirements the intended reaction can have a temperature of 800 to 15000 fed to the immediately upstream reaction chamber, which is expediently is also designed as a cyclone, as described in more detail in the main patent.

This reaction or cracking cyclone is left in the center of the tip to the base with the superheated steam generated in the burner cyclone flowing through, while the crude oil to be processed is fed tangentially in countercurrent. Possibly becomes return gas from previous similar operations together with the oil added.

Instead of fresh crude oil, a pre-distillation can also be used if necessary 01 already freed from certain constituents is fed into the reaction chamber will. This pretreatment of the crude oil can be carried out under the current process as described below.

The duration of the reaction and the course of the reaction can be changed by varying the flow rate controlled by the superheated steam and the choice of the dimensions of the crack cyclone will.

A mixture of fission gases emerges from the reaction or cracking cyclone and steaming, steaming unreacted oil and superheated water vapor with a Temperature from about 500 to goo0 or higher.

The process sequence described so far is used as a reaction stage because with it the reaction, d. H. cracking, the raw material is essentially complete.

The reaction mixture coming from the reaction stage is immediately for distillation and separating stations (distillation stage), at the same time its heat content, down to a temperature of about 200 up to 2500, for direct distillation of further crude oil and / or for indirect practice ditzung further water vapor is used.

The reaction mixture is expediently activated as soon as it emerges quickly quenched from the reaction cyclone by injecting fresh crude oil to the point where d. H. lowered in temperature that the cracking reaction does not proceed. It will For example, worked so that the distillation stage in the first vessel for the expediently also a cyclone is chosen, the temperature of the gaseous Olefins, gasoline vapors, medium and heavy oils and superheated steam existing mixture is brought to about 6000.

That in this phase in the hot stream of crack gas and water vapor injected crude oil is brought to distillation by direct heat exchange. If the distillation vessel is designed as a cyclone and care is taken that the fresh oil is distributed in a thin layer on the inner wall of the cyclone the following significant advantages: The non-distillable portion of the Crude oil (residue, asphalt) can be easily poured into the cyclone tip discharge a collecting vessel without any significant changes in cross-section occur in the apparatus; due to the distribution of the oil in a thin layer an extremely gentle thin-layer evaporation is brought about on the cyclone wall; as a result of the presence of cracked gas and water vapor, the distillation goes at very high low partial pressure before stitch, so that expenses for vacuum generation like them would be required in the case of separate distillation of the crude oil, are omitted.

For example, a heavy crude oil that is used in bubble distillation in vacuo gives a residue of 8% when working according to the invention be distilled with only 200/0 residue.

The amount of crude oil used in this stage of the process to deter of the reaction mixture and fed to its own distillation is in each Case to be chosen so that the heat consumption for heating and evaporation of the crude oil is high enough to keep the temperature of the reaction mixture fed from the cracking cyclone to lower it so far (about 200 to 6000). that the resulting residue is off the injected crude oil still remains liquid at the distillation temperature and can be discharged from the quenching cyclone in this form.

If the heat content of the reaction mixture leaving the cracking cyclone is to be used exclusively for the distillation of injected crude oil, approximately four to five times the amount of crude oil must be injected and distilled, how distillate is required for the actual cracking reaction. It's hot Processes are always possible, in addition to gaseous olefins also gasoline and diesel oil as fuel and high-boiling fractions as raw material for to use the cracking reaction.

The new process for cracking petroleum is so far unconventional and peculiar than a high one with regard to the reaction level Excess of petroleum prevailed and only the smaller part of it in the reaction stage is subjected to cracking, while for the purpose of highest thermal economic utilization the majority is practically only distilled and deasphalted. Only by This trick succeeds in reducing the high heat content of the process from the Reaction zone exiting vapors and gases with a particularly high efficiency to take advantage of.

With this method of operation it is possible to use a pre-distilled cracking To supply oil and in this way to achieve higher yields of desired products.

Apart from the particularly favorable heat balance, the process offers the advantage, apart from the gaseous olefins that are usually obtained during cracking to produce substantial amounts of valuable cracked gasoline, diesel and gas oil, and it also delivers due to the considerable reduction in the crude oil partial pressure the steam and gas used as a heat transfer medium also contain bitumen as a residue, which has a high commercial value because of its high softening point.

Since with this forced distillation always also a little To the extent that cracking takes place, the gasoline yield will be higher and so will be Obtain higher octane numbers than with normal vacuum distillation.

If fuel production is not desired, it is expediently, the heat content of the reaction mixture emerging from the craclicyclone to use only part of the distillation of injected crude oil and to use it in the the rest by indirect heat exchange to the secondary to be introduced into the burner To give off water vapor and to overheat it. When using heat exchangers usual design, e.g. B.

Tubular heat exchangers, there is the disadvantage that this often have to be cleaned because of the partial condensation of heavy oil components Contamination occurs, which leads to disruptive cross-sectional constrictions. One uses therefore it is advisable to have a battery of several series-connected batteries in this distillation stage. cyclones equipped with heating jackets. This results in trouble-free work, because of the fission gas, fUl and water vapors flowing on the inside of the cyclones existing mixture condensing out high-boiling components without interference the cyclone tip can be discharged and collected in collection containers. A Another decisive advantage of using such a Zyklonbattleril. consists in it, d'ass, thanks to the peculiarity of the cyclonic flows in regular operation, heat transfer coefficients can be achieved, which are far cheaper than the previously known methods.

The amount of water vapor to be added through the heating jackets to the cyclones is determined on the one hand by the total surface of the cyclone shells and on the other hand according to the more or less large amount of that injected into the quenching cyclone Crude oil and the heat withdrawn from the reaction mixture by this. In any case must be the amount of countercurrent through the heating jackets of the cyclones of the distillation stage The introduced water vapor collects with the amount that is injected into the quenching cyclone Crude oil be so large that the temperature of the incoming reaction mixture in the quenching cyclone is reduced with certainty to such an extent that the cracking reaction does not continue so that no undesired secondary reactions can occur.

The more water vapor in the countercurrent flow through the heating jackets The distillation stage is supplied, the less steam needed in the Reaction cyclone upstream burner cyclone generated via the oxyhydrogen reaction will. For example, you can work with good success, if only about the eighth part of the superheated steam required for the cracking reaction of the petroleum is obtained from the molecular conversion of the oxyhydrogen reaction while seven Eighth of the water vapor can be covered from another water vapor source.

Since the cracking is carried out essentially under normal pressure, may well be the specific heat of condensation, but not the heat of condensation as a heat transfer medium serving steam of steam superheating can be made usable. To that too not inconsiderable heat of condensation of the water vapor, which, however, is only can be gained at a low temperature level, not to be lost, can this amount of heat still be used in the operation of an absorption refrigeration system, which generates the cold required in the gas separation system.

There is at least one apparatus suitable for carrying out the process from a combination of a burner cyclone for the generation of superheated steam by the molecular conversion of hydrogen and oxygen, where appropriate methane gas obtained from the reaction stage can also be added and also a feed line for the introduction of water vapor to the other source is, with an adjoining reaction or cracking cyclone and a this downstream quenching cyclone. Either a Fractionation column and one as a separation vessel for the separation of the cracked gas and the Connect the discharge of the liquid formed condenser, or the quenching cyclone comes with a number of other cyclones, each equipped with a heating jacket and are connected to a collecting vessel, to a still added.

In this case, the heating jacket becomes the last cyclone of the battery Connected to a supply line for fresh steam, the heating jackets all Cyclones interconnected by pipes and from the heating jacket of the first Cyclones overheated from a feed line for the home passage through the heating mantles Steam placed at the base of the burner cyclone for the oxyhydrogen reaction.

In addition, the reaction or cracking cyclone will be close to its base provided with a supply line for fresh oil and return gas and also receives one of line for the reaction mixture giving its base to the base of the quenching cyclone, into which, in turn, an injection line for the crude oil to be fed in is connected. It is advisable to use the supply line described for water vapor from the last cyclone the distillation stage up to the burner cyclone a branch equipped with valves switch on, with the help of which this steam supply line is short-circuited can, to individual or all cyclones of the Desti llationsstufe from the steam passage by turning off their heating mantles.

Of course, both the process and the apparatus can be varied within wide limits, depending on in which direction the processing of crude oil should be directed.

Figs. I and 2 show two examples of the forms of management of the Apparatus and also explain how the process works.

Fig. J shows an apparatus scheme in which the main emphasis is placed on it is to fractionate the largest possible amount of crude oil and in this way the waste heat to exploit the actual cracking reaction.

The essential parts of the apparatus are the burner cyclone 1 for the implementation of the combustion of hydrogen and oxygen to superheated steam, the reaction or cracking cyclone 2, the quenching cyclone 3, the downstream one Fractionation column 4 and at the same time as a separation vessel for the separation of cracked gas and liquid discharge formed condenser 5.

Hydrogen and oxygen enter the burner cyclone I via the Lines 6 and 7 separated at the top, while setting the desired one Secondary steam temperature required by the installed near the base Nozzle 8 is fed tangentially. The one that overheated from the oxyhydrogen combustion Water vapor emerges from the burner cyclone at a temperature of 800 to 15000 and into the top of the cracking cyclone 2. Here i; hm becomes tangential through the nozzle g a mixture of feed oil (e.g. fresh oil + return oil) and return gas (consisting of all gaseous hydrocarbons not converted into the desired end product from the cracked gas). The endothermic cracking reaction takes place in the middle room of the cracking cyclone in front of you, and the reaction mixture of cracked gas, vapors and superheated Water vapor exits the central tube at the base of the cyclone at a temperature from about 500 to 9000 out and into the quench cyclone 3 over, being in the mixture crude oil is injected through pipe and nozzle IO in such an amount that its evaporation at the low partial pressure caused by the high dilution takes place in a thin film on the wall of the quenching cyclone 3.

The oil bowls then emerge together with water vapor and cracked gas the central pipe via line 1 1 at a temperature of about 200 to 5000 and are introduced into the fractionation column 4 at a suitable point. The crude oil constituents that cannot be evaporated under the selected pressure and temperature conditions are thereby formed at the top of the quenching cyclone 3 via the siphon-like Line I6 withdrawn. Depending on the level of crude oil imported at 10 and the This distillation residue withdrawn at 16 can be used at the temperature of the mixture thus produced the consistency of a heating oil or the consistency of a bitumen with a high Have softening point.

In the column 4, the separation into light and heavy distillate components takes place instead of. The product leaving overhead at a temperature of around 80 to 2000 contains the total amount of the cracking in the cracking cyclone during normal operation 2 resulting components, the light gasoline fractions and the water vapor, while heavy oils can be withdrawn from the bottom of column A at 14.

The products discharged in line 12 are in the condenser 5 condensed out. This is designed so that the non-condensable fission gases withdrawn via line I7 and fed to a gas separation system. The liquid products precipitated in the condenser 5 are pumped 19 deducted. Part of it is via line 13 to feed the Column 4 is used, while another part via line 18 is a separating vessel Conventional design is supplied, in which the separation into water and liquid hydrocarbons he follows.

The column shown only sees the separation into two components before. But you can of course the column by creating opportunities to take off side streams so that a multiple separation is carried out can be.

If necessary, the bottom of the column can be carried along via line 15 direct steam.

Dep. 2 shows an apparatus scheme which is used when a distillation of crude oil beyond the level of distillate as a starting material required for cracking is undesirable, d. H. so if the plant is in primarily to serve the production of gaseous olefins. In this case it is necessary that the waste heat from the actual cracking process continues to freeze this same process is made subservient. This is most conveniently done in such a way that the secondary steam supplied from outside the apparatus preheated and overheated as high as humanly possible and consequently the overheating this secondary steam depress the amount of oxyhydrogen to be expended, d. H. the use of elemental hydrogen and oxygen.

The main parts of the apparatus are the burner cyclone I for the oxyhydrogen reaction, the reaction or cracking cyclone 2, the quenching cyclone 3 and those attached to them subsequent distillation cyclones4, 5, 6, all of which are connected to one another by pipelines connected heating jackets. The cyclones 3, X, 5, 6 are collecting and collection vessels 7.

8, 9, IO assigned via lines I7, I9, 2I, 23 with the after peaks of the aforementioned cyclones shown below. The supply line for fresh water vapor is formed by the valve 37 and the pipes 28, 29, 3I, 33, 35, 36 and the intermediate heating jackets of the cyclones 3. 4, 5, 6. This live steam supply line can with the help of valves 2A, 25, 26, 27 and the intermediate pipe sections are short-circuited in such a way that one or more cyclone heating jackets are switched on and the steam is released immediately can be fed tangentially to the base of the burner cyclone I via the line I3.

Of course, the apparatus is not limited to the use of limited to four cyclones in the distillation stage.

Hydrogen and oxygen are supplied to the burner cyclone I through the pipes II and I2 supplied separately. Fresh oil and return oil are passed through the crack cyclone 2 the line 14 is fed, while that intended to quench the reaction mixture Crude oil through line 15 into the transition from cracking cyclone 2 to the quenching cyclone 3 is injected. The cylinders 3, 4, 5, 6 stand through the central connector si and Line sections I6, I8, 20 each in connection with the next cyclone. The gases from the cyclone. 6 are abefii! Rrt through the central connector and line 22.

The apparatus is operated in such a way that, for example, the Temperature from cyclone 3 to the discharge from cyclone 6 from about 6000 to about 250 °, whereby in the collecting containers 7, 8, 9, 10 different fractions, z. B. gasoline, diesel oil, lubricating oil can be obtained.

Depending on the desired heat management, it is also possible to use the or the last cyclones of the battery to drive as an evaporator by instead of water vapor Water is introduced.

Figs. I and 2 v. To a certain extent illustrate the two borderline cases of the method according to the invention. There are a large number of combinations between them or variants that allow all of the different ones that occur in practice To meet needs. For example, you can also use the hot crack gases first let their specific heat be given off to the secondary steam and only afterwards At a lower temperature level, decompose crude oil into distillate and residue and the distillate under gentle conditions in the required amount to the cracking cyclone conduct.

PATENT CLAIM: I. Process for the processing of petroleum after patent application A2ISß6IVa / I2g, characterized in that an appropriately pre-cleaned fresh oil, possibly mixed with return gas obtained from previous operations, in a cyclone with superheated steam of about soo to 15,000 for reaction brought (reaction stage) and the reaction mixture to distillation and separation stations is passed (distillation stage), while at the same time its heat content down to a temperature of about 200 to 2500 for direct distillation more Oil and / or for indirect overheating of other water vapor.

Claims (1)

2. The method according to claim I, characterized in that at least a part of the superheated steam from an expedient in an upstream Another cyclone set in motion oxyhydrogen gas reaction from hydrogen and oxygen is delivered. where methane may also be obtained from the reaction stage can be added. 3. The method according to claim I and 2, characterized in that the gaseous reaction mixture emerging from the cyclone serving as the reaction vessel Olefins, vapors from gasoline, medium and heavy oils and superheated steam is quickly quenched by injecting fresh crude oil to the point where the reaction does not continue to run. 4. The method according to claim I to 3, characterized in that quenching, distilling and separating in a battery of series-connected, cyclones equipped with heating jackets with associated separation or Collection vessels is made. 5. The method according to claim I to X, characterized in that more fresh crude oil is fed to the system in the distillation stage than in the reaction stage is to be enforced. 6. The method according to claim I to 3 and 5, characterized in that that in the Desti.llationsstufe for separation into the liquid desired in each case End products and into an oil suitable for the reaction stage with a distillation cyclone and a downstream fractionation column is operated. 7. Device for performing the method according to claims I to 6, consisting of a burner cyclone, a downstream crack cyclone, a subsequent quenching cyclone and an adjoining one Separation plant for the reaction mixture. 8. Apparatus according to claim 7, characterized in that on the quenching cyclone, one behind the other, another row of heating jackets equipped and each connected to a collecting vessel for fractionated cyclones Connect distillation and separation, the heating jackets of which are parts of a supply line for represent additional water vapor to the Brentier cyclone. Considered publications: German Patent Specifications No. 859444, 879 09I; U.S. Patent Nos. 2,628,890, I 908 001, 1911 476; french Patent Specification No. 10,000,402; British Patent No. 409 875.