DE2011075A1 - Process for purifying hydrocarbon-containing hydrogen - Google Patents

Description

SHELL INTEBMA3? IOSA1B IiESEAHCH MAAl'SCHAPPIJ The Hague, Netherlands

"Process for. Purifying Hydrocarbon Containing Hydrogen"

Priority: 10. Mrs. 1969? Great Britain, No. 12 383/69

The invention relates to a method of cleaning sum hydrocarbonaceous em hydrogen, which is removed at dex hydrogenated processing of hydrocarbon £> tofföl <~ l ^'l raktionen.

The term "hydrogenative processing" refers here to catalytic Keforiaierverfahren, the hydrocracking, the hydrogenative JSntsulphurisation _s the so-called "hydrofinishing" (with hydrogenating refining without cleavage) and hydrogenation processes such as the hydrogenation of kerosene to improve its soot point or the hydrogenation of Pyrolysis is also used to remove unsaturated aliphatic hydrocarbons. In the case of the catalytic conversion processes, hydrogen is supplied, in the other processes mentioned above, it is consumed.

Hydro cracking produces methane and athane as by-products and higher coals. These hydrocarbons are found the calibration under dön in these processes

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the gas phase. These gases therefore act as contaminants of the hydrogen produced or circulating in these processes. Such an impurity is particularly then undesirable if the hydrogen is recycled into the process. In such a case the quantity of gaseous substances increases After a certain time, hydrocarbons rise to such an extent that the backflowing hydrogen gas has too low a hydrogen content has and must be regarded as exhaust gas.

In hydrogen-consuming processes, such as hydrated desulphurisation and hydrofinishing, a liquid feed is used treated with excess hydrogen under pressure in the presence of a catalyst. The product obtained is in a high-pressure separation device into a gas phase and a separated liquid phase. The gas phase, which is mainly hydrogen and contains a smaller proportion of gaseous hydrocarbons, can, as mentioned, be recycled liquid phase, which has a low V.'ass first of fanteil and a contains a high proportion of C ^, - hydrocarbons, are then the gaseous components are separated off in a low-pressure separating device, a gas stream being obtained which contains hydrogen and relatively high proportions of C-j, hydrocarbons shows "Such a gas flow has too low a hydrogen concentration, in order to be used in the hydrogenation processing of a coal water oil fraction and is therefore regarded as exhaust gas

The object of the invention is to provide a new process but cleaning the aforementioned exhaust gas hydrogen streams are available «u ettl-

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The invention therefore relates to a method for cleaning of hydrocarbonaceous hydrogen, which is characterized is that one withdrawn in the hydrogenative processing of hydrocarbon-BI fractions, hydrocarbon ~ Substantive hydrogen stream in a combustion device, which has a reactor for the partial combustion of a mineral oil fraction with the reactor gases of the combustion device mixed.

The method of the invention offers an economical and for

of hydrogen the industrial scale suitable method for cleaning / of gaseous hydrocarbons and has the advantage that. the gaseous hydrocarbons at least partly in hydrogen being transformed.

The process of the invention is carried out at the temperatures of the reactor gases. Any non-catalytic combustion process is suitable according to the invention, since the temperature of the reaction gases in such a device is always above 1200 ^° C. and is thus sufficiently high for the process of the invention »

The non-catalytic partial combustion of mineral oil fractions is a known process. _{Gaseous fractions p} liquid distillate fractions and residues can be used as feed for the partial incineration under normal conditions. Examples of residues are sop residues and residues obtained from hydrocarbon st off conversion processes. The top residues can be removed by distillation of crude oil in one or more stages, including a distillation under reduced

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* Print can be included, win ». The residues of

Hydrocarbon processes can be prepared according to various

Viscosity breaking methods are obtained as by / ( ⁿ visDreaking "} cracking or thermal reforming" The residue can also be obtained by deasphalting a top residue or a residue obtained by a conversion process in one or more stages, e.g. using propane.

The partial incineration is expedient after that in the British 78G 120, and preferably by the method outlined in British Patent 851,542. Air or air enriched with oxygen can be used However, essentially pure oxygen is preferably used to ensure the presence of more essential Nitrogen particles in the withdrawing current are avoided of nitrogen in the purified 'hydrogen is undesirable'. JSs can also be carrier gases such as' .vas ™ steam and / or carbon dioxide can be used <>

Since the stream withdrawn from a partial combustion process contains not only hydrogen, but also components such as Kuss , Co, H ^ S, CCS, or Op, which in most cases, especially when using the oxygen in one stage of a process for hydrogenation processing, undesirable impurities, these components are preferably removed at least in a high proportion from the stream withdrawn from the incinerator. For this purpose, known methods can be used, such as washing the withdrawing utxoma with. Water and / or OJ for soot removal, as .in eggs British Patent HT, 09? K-OCJirieben is, in this procedure will

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the rubs optionally separated from the ash liquid, for example by pelletization with a hydrocarbon oil, and expediently used as fuel and / or returned by mixing with the charge for the partial combustion device. After the aforementioned scrubbing, the CO contained in the washed gas can be catalytically converted into CO ₂ "the carbon oxysulphide into CO" and HpS and. of oxygen are converted into water ,, The conversion products can at least partially light "Z ₀ B ₀ by treatment with a AbsorptionsflüsBigkeit be separated ₀ are suitable as absorption liquids, liquids" in which carbon dioxide and, if present, sulfur compounds are physically absorbed such as tetramethylene sulfone or N -Methylpyrrolidone-containing liquid, or liquids in which the aforementioned compounds are chemically absorbed, such as a liquid containing an amine, Liquids which contain an alkanolamine and a physically acting absorbent such as tetramethylene sulfone or N-methylpyrrolidone are preferred The aforementioned treatment gives a gas which essentially consists of pure hydrogen. Any hydrogen sulfide separated off in the aforementioned manner can be worked up to sulfur by suitable conventional processes

In the process of the invention, the contaminated hydrogen is expediently in contact with the heating gases for at least 1 second brought · a contact time of more than 10 seconds is generally not required, but can also be used «Preference is given to contact times of 2 to 5 seconds« The contaminated hydrogen can be

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_p mixed by feeding it to the reactor, the partial combustion device ir ». At least part of the hydrocarbon-containing hydrogen stream can also be combined with the charge to the reactor of the combustion device. The hydrogen stream is preferably mixed with the reactor exhaust gases. Can a combustion device be used for the method of the invention? which has a reactor and an exhaust gas boiler «. Such a device is described in British Patent 351,542. In the latter case, the exhaust gas hydrogen can with the. Reactor exhaust gases fed into the aforementioned exhaust gas boiler are mixed. When the Wasserst off sir om with the reactor exhaust gas is mixed, a carburetor is suitably used, for "ß _0. lined with bricks and no installations having Direction reactor" This comparison

Behind
gas is the reactor and, if one is available,

the oasis

in front of the exhaust gas boiler to increase the dwell time / before it cools down switched into this boiler. The advantage of this preferred method of mixing the contaminated hydrogen stream with the reactor exhaust is based on its ease of implementation O

Since according to the method of the invention, a gas with an increased Hydrogen content is to be produced, the exhaust gas becomes hydrogen Purposefully cleaned by being in a combustion-beneficial manner is burned,

Direction is fed in, in which a fuel i / u »a gas mixture (synthesis gas) SU which already has a relatively high quantitative ratio of hydrogen / carbon monoxide is received.

Such a synthesis gas can be produced by blowing in Wa ** - steam is produced in the reactor of the incinerator

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COPY

BAD OFHGINAL

be taking daa yoriiaiideiie carbon monoxide while taking Formation of V hydrogen according to the equation

ώ ^ 2 2
is oxidized to Kohlendioxy.d "To perform such conversion can be in the burner of the aforementioned reactor water vapor in excess of _P based on the optionally already introduced water vapor ₅ blow, preferably the water vapor, however, eingeblasenf at the outlet of the reactor in this or the reactor -Exhaust gases added =. This combination of the steam3 with the reactor exhaust gases or the corresponding introduction into the reactor at its outlet opening are preferably used because the temperature at the outlet opening is greater than the temperature at the reactor's burner.

aicsors ¹ IaIQ. da oei cien iierz? sc.2c _ ^ .. L3n uZesrceraTursii 2121 all the more

Isiuscnosydmengs is needed the higher the tifrapc-rs-ture.

The water vapor is also used to promote the conversion of the methane contained in the exhaust gas hydrogen to CO and H _0. Furthermore, the conversion of GOS to CO ₂ and H ₂ S is effected by water vapor.

The purified hydrogen finally obtained by the process of the invention can be used in any process in which highly pure hydrogen is required. If 3.B. the method of uem the contaminated hydrogen originates _a% W, - aserstoff-providing method, may represent purified jtoff ini ^J J ^ sverfahren advantage in processing; hydrogenated be estimated at ₉ aenen hydrogen consumed relatively ur.a

00983S / 1932

COPY BAD ORIGINAL

we need pure hydrogen

The method of the invention is particularly suitable for Heinigen hydrocarbonaceous hydrogen _f obtained at a hydrogenating processing in which a boiling above the applicable for gasoline temperature range Kohlenwasserst is off oil-Fralcti on used as feed, "The in the hydrogenating process as quake products Gaseous hydrocarbons that are formed and contaminate the hydrogen that is recycled into hydrogen-consuming processes are relatively easy to develop in cracking reactions. Such cracking reactions can occur when hydrocarbon oil fractions boiling above the gasoline temperature range undergo hydrogenation

in particular
processed, / z, Bo by hydro-cracking or hydrogenating desulphurisation,

The process of the invention is therefore particularly applicable in combination with hydrogenation processing processes in which feeds boiling above the temperature range applicable for gasoline are hydrogen cracked or desulphurised.The hydrocarbon oil fraction subjected to the hydrocracking or the hydrogen desulphurisation is preferably a deasphalted one in these processes 01, which was obtained by separating a residual oil by treatment with a deasphalting solvent into this deasphalted oil and asphalt compounds. The solvent used in such a practical EntaephaltiorunkSverfahren contains at least one low-boiling paraffinic hydrocarbon having 3 or more carbon atoms, the solvent may further comprise at least one alcohol Z ₀ B, the British in the

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Particularly suitable are low-boiling paraffin carbons with 4 or more carbon atoms, such as heptane, hexane and especially pentane, since these hydrocarbons are capable of converting the oil into essentially oil-free asphaltenes on the one hand and deasphalted on the other hand Separating oil with a very high yield “The use of the method of the invention for the purification of hydrogen obtained in the hydrogenative processing of deasphaited oil fractions has the advantage that the asphaltic compounds obtained in the linted asphalting stage are mixed with the mineral oil reactions subjected to partial incineration In this way, the aforementioned asphaltic compounds, which are otherwise only suitable as power or fuels, deliver hydrogen which is used in the respective hydrogenation processing process or in any other process in which Wa hydrogen is required, can be used _o

As mentioned, the method of the invention is very suitable for the purification of hydrocarbon contaminated hydrogen emitted from an apparatus for hydrogenative processing is withdrawn, in which a deasphalted oil obtained by separating the asphaltic compounds from a residual oil oil is processed, as in this case both the asphaltic connections and the residue fraction, (or the recycle oil) of the hydrogenative processing process can be partially burned in the same incinerator can, which is used to separate the gaseous hydrocarbons rom exhaust gas hydrogen. The finally received

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tene purified hydrogen can at least partially in the device be recycled for hydrogenation processing.

The preferred embodiment of the method of the invention is therefore in the purification of a hydrocarbon-containing hydrogen stream, which comes from a device for the hydrogenation Processing is withdrawn, in which a hydrocarbon oil fraction with consumption of hydrogen to at least one hydrogenation product and at least one residue fraction is processed, wherein a hydrocarbon-containing hydrogen stream is deducted. The processed hydrocarbon oil fraction is a deasphalted oil fraction that is produced by separation of a residual oil by means of a deasphalting

solvent into a deasphalted oil and asphaltisohe Connections was obtained, at least part of this asphaltic Compound and at least a part of the residue fraction obtained from the apparatus for hydrogenative processing are fed into a combustion device for partial combustion. The obtained exhaust gas hydrogen is mixed with the reactor gases of the combustion device, and soot / carbon oxides and sulfur compounds, as described above, are removed from at least a portion of the incinerator withdrawing stream separated. The purified hydrogen is put into the apparatus for hydrogenative processing returned.

The invention will now be explained in greater detail by means of the flow themes shown in FIGS. 1, 2 and 3. In these figures, the same numbers always indicate the same facilities.

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FIG. 1 illustrates an embodiment of the method of FIG Invention, in which contaminated hydrogen withdrawn from an apparatus for hydrogenative processing in an incinerator, in which one mineral oil fraction is non-catalytic is partially burned, freed from methane, ethane and the higher hydrocarbons »

Figure 2 illustrates another embodiment of the process of the invention in which the contaminated hydrogen is mixed with the reactor off-gases the combustion device is mixed before these exhaust gases are fed into the exhaust gas boiler, and at the the purified hydrogen is at least partially returned to the device for hydrogenative processing.

Figure 3 illustrates the cleaning of one of a device hydrogen streams obtained for catalytic reforming.

In Figure 1, a hydrocarbon oil fraction is via line 2 fed into a device for hydrogenation processing 1. The product formed in this device is drawn off via line 4 and the residue via line 3. Possibly If this residue is wholly or partially recirculated into the device 1 via line 5, it contains hydrocarbons Hydrogen is withdrawn via line 7 and can partially be returned to device 1 via line 6, in which fresh hydrogen can be fed in via line 6a. The hydrocarbonaceous hydrogen is put into an incinerator 8 fed in, which is fed via line 9 with a mineral oil fraction. The mineral oil fraction

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is partially burned in the device 8 in the combustion device 8, the contaminated hydrogen is obtained with that obtained after the partial combustion of the aforementioned oil fraction Reactor gases mixed «The entire liia conversion mixture is withdrawn via line 10 and can be freed from undesired impurities by conventional methods.

In FIG. 2, a residual oil fraction is fed via line 14 into a deasphalting device 13, which is fed with a deasphalting solvent via line 15 Hydrogen is processed with consumption of the hydrogen fed in via line 6a “The hydrogenated product is removed via line 4”, the residue is drawn off via line 3 “The residue is partly returned via line 5 to device 1 for further processing. Hydrogen is withdrawn from device 1 via line 7 and partly returned via line 6. Via line 16 from the device 13 Sntasphaltierungs abgezo gene iiückstand zuminuest is partially fed into line 16 where it is mixed with the coming via line 3a from the apparatus residue. The residue coming from the device 13 can be drawn off via line 17. The combined residues from line 18 can be mixed with a mineral oil fraction by being fed into line 9, via which such fraction is fed into the reactor 8a of the incinerator 8 . The exhaust gases from the reactor 8a are transferred to the exhaust gas boiler 8b via line 8c.

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leads »The exhaust gases are in line 8c with the over line The supplied hydrogen gas is mixed ο The boiler's exhaust gas 8d is transferred via line 10 to a device 11 intended for a combined treatment, in which the soot is removed, the carbon monoxide is catalytically converted to carbon dioxide and that Carbon dioxide and the sulfur compounds in an absorption liquid be absorbed. Essentially pure hydrogen is withdrawn via line 12 and at least partially over Line 6a fed back into the device 1 o

In Figure 3, a kohlenwasserstoffhalti & er hydrogen stream, the processing of a heavy naphtha catalytically reforming device is obtained 19 and 60 VoI ₀ - contains $ hydrogen, transferred via line 20 to a combustor 8, a petroleum fraction is fed into the through line. 9 The mineral oil fraction is partially burned in the device 8. In the combustion device 8, the hydrogen stream is mixed with the hot reactor gases. The conversion mixture is withdrawn via line 10 and freed from undesired impurities in a device 11 intended for a combined treatment, the Huss being removed, the carbon monoxide being catalytically converted to carbon dioxide and the carbon dioxide and the Sulfur compounds are absorbed in an absorption liquid. Pure hydrogen can be withdrawn via line 12. Via line 21, hydrogen is fed into a hydro-cracking heater 22, in which a mineral oil fraction is catalytically cracked in the presence of hydrogen. Hydrogen contaminated by gaseous hydrocarbons is drawn off via line 23 and

98 39/1 ^ 3 2

if necessary, directly into the combustion process via line 24 Direction fed and / or mixed with the withdrawn via line 20 from the Platfornlng reactor 19 hydrogen stream Some of the contaminated hydrogen can be drawn off via line and used in processes in which no pure hydrogen is required »

The examples illustrate the invention.

example 1

Refinery gas obtained from a platforming reactor is cleaned by mixing it with the reactor exhaust gases from a combustion device in which a bunker C heating oil is partially burned using essentially pure oxygen to produce synthesis gas ο The refinery gas has the following composition (in VoI _n ~%) on;

Hydrogen 60.0

Methane 18.0

Ethane 13.0

Propane 6.0

Butanes 2.5

Pentanes C, 5

The measured molecular weight of the gas mixture is 12.43 o The Bunker G heating oil has the following properties:

Density ^d 15/4 · ° ^'97

Redwood viscosity I, sec. (37.8 ° C) 3000 Coking test according to Conradaon, weight <, - # 10.2

lower calorific value, koal 9840

Aeohe, GeWo- # 0.07 Analysis:

Sulfur, Gewo-? 6 3.50

Hydrogen, wt. - # 11.3o

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Carbon, wt. 5 & 84.6g

Nitrogen, wt. '■ .0.40

^ Oxygen, weight 0.13

Bunker C fuel oil is t in the burner of the combustion apparatus at a rate of 257 / ν fed ₀ The water vapor is t in the reactor at a rate of 128 / ^ Eind the oxygen at a rate of 196 000 Hm / v ^a% total lead . The reactor gases are produced in a proportion of 883 206 Nm / v ^ and have the following composition (in vol .- ^) :

Carbon dioxide '4.74

Carbon monoxide 39.29

Hydrogen 39.97

Hydrogen sulfide 0.68

Carbon oxysulfide 0.03

Methane '. . 0.26

Water 13.77

Nitrogen 0/56

Argon 0.70

The reactor exhaust gases have a temperature of 1400 ⁰ C and a

2 '

Pressure of 30 kg / cm. The exhaust gases are in one called a carburetor acting, lined with bricks

Reactor without internals fed in * The refinery gas is

Tas blown into the carburetor at a speed of 64.25t / ι. The residence time of the gas in the gasifier is 4 seconds. The gas flowing out of the carburetor is cooled in an exhaust gas boiler

That from the carburetor ausstritaenä · = * gas that has a temperature of 1000 C has the following composition (in

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Carbon dioxide 2.31

Carbon monoxide 37.58

Hydrogen 46.64

Hydrogen sulfide 0.55

Carbon oxysulfide 0.03

Methane 3.67

Water 8.20

Nitrogen 0.45

Argon 0.57

The amount of gas flowing out of the carburetor is 095 740 Nm / if ^ From the above composition of this gas is It can be seen that the methane content originally contained in the refinery gas has been significantly reduced and that the higher Hydrocarbons have been completely converted.

Example 2

The process of Example 1 is repeated, but the refinery gas is ^{fed into the gasifier at a rate of 45.35 t / V 8} «The gas flowing out of the gasifier has a temperature of 1000 C and has the following composition

setting (in

Carbon dioxide 3.09

Carbon monoxide 37.80

Hydrogen 43.62 hydrogen sulfide 0.60

Carbon oxysulfide 0.02

Methane 3.59

Water 10.18 nitrogen 0.49

Argon 0.61

The proportion of gas flowing out of the carburetor is 106 480 Nm ⁵ / day.

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From the above examples it can be seen that the im The hydrocarbons contained in refinery gas have completely disappeared as a result of mixing with the reactor exhaust gases. the The composition of the gas flowing out of the gasifier also shows that the ratio of hydrogen to Carbon monoxide increased compared to that of the reactor ^ exhaust gases Has..

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Claims (1)

Claims / "■■ 1, a method for purifying hydrocarbon-containing hydrogen, characterized in that one one in the hydrogenative processing of hydrocarbon oil fractions withdrawn, hydrocarbon-containing hydrogen stream in a combustion device that has a reactor for the partial combustion of a mineral oil fraction, mixed with the reactor gases of the combustion device, 2. The method according to claim 1, characterized in that the part «combustion with essentially pure oxygen is carried out. 3ο method according to claim 1 or 2, characterized in that the contact time of the hydrocarbon containing hydrogen stream with the reactor gases 1 to 10 seconds, preferably 2 to 5 seconds. 4. The method according to claim 1 to 3 »thereby ge— P indicates that the hydrocarbon-containing hydrogen stream is mixed with the reactor exhaust gases from the combustion device « 5. The method according to claim 1 to 3 »characterized in that the combustion device with is equipped with an exhaust gas boiler, and that the hydrocarbon-containing Hydrogen flow with the reactor flue gases from the incinerator is misused before they are fed into the exhaust gas boiler " 009839/1932 60 A method according to claim 4 or 5, characterized ge characterizing ζ ei et chn that the hydrocarbon containing hydrogen stream is mixed in a connected behind the carburetor reactor with the reactor exhaust gases, 7β Method according to claim 4 to 6, characterized in that; that the reactor exhaust gases water vapor is added, 8. The method according to claim 1 to 7 »characterized in that at least part of the Combustion device emanating gases by removing the Russee, converting the carbon monoxide into carbon dioxide and then converting it Removal of carbon dioxide is cleaned, 9. The method according to claim 8, characterized in that » that the carbon dioxide by an alkaline wash, preferably by means of an alkanolamine containing Solution, is removed, 10. The method according to claim 1 to 9, characterized in that that at least part of the received purified hydrogen as feed to the process for the hydrating processing of the hydrocarbons and oil fractions is returned, U. The method according to claim 1 to 10, daduroh gekennze I don't think the hydrogenated hydrocarbon Oil fraction one above that for gasoline Temperature range is boiling fraction. 009839/1932 12o A method according to claim 1 to 11 characterized in _F, the class processed hydrogenating hydrocarbon oil fraction, a deasphalted oil is obtained by separation of a residual oil by treatment with a deasphalting solvent in the deasphalted oil and asphaltiBche compounds. 13. The method according to claim 12 _P, characterized in that at least some of the asphaltic compounds obtained when deasphalting the residual oil are partially burned in the combustion device. 14. The method according to claim 1 to 13 »characterized in that at least part of the hydrocarbonaceous hydrogen stream of the feed for the reactor is added to the incinerator, 15. The method according to claim 1 to 14, characterized in that in a device for hydrogenation processing a deasphalted oil fraction obtained by separating the asphaltic compounds by means of a solvent from a residual oil with hydrogen consumption m at least one hydrogenation product and at least one residue fraction with recovery of a contaminated by hydrocarbons Hydrogen stream is processed and that at least part of the asphaltic connections and at least a 'wedge of the residue fraction obtained are partially incinerated in a combustion device. 009839/1932 16. The method according to claim 15 * characterized in that the device for hydrating Processing is a hydro-cracking device » 009839/1932