DE1545433A1 - Process for converting hydrocarbon distillates into heating and synthesis gases - Google Patents

Description

IECHTSANWÄLTE

DR. JUR. DiPL-CHEM. WALTER BEIL

ALFRED HOEPPENER

DR. JUR. DiPL-CHEM. H.-J. WOLFF

DR. JUR. hANS CHR. AX

623 FRANKFURT AM MAlN-HOCHST

AOELONSiSASSE 58

2 AUG. 1969

Our no.12020

Chevron Research Company San Francisco, CaI., V.Öt.A.

Process for the conversion of hydrocarbon distillates in heating and synthesis gases.

The present invention relates to conversion of hydrocarbon distillates into valuable gases. she particularly relates to a multi-stage process including a hydrocracking stage for converting hydrocarbon distillates in heating and synthesis gases. The invention is hereinafter particularly described in connection with the hot gas production described.

The calorific value of a gas is the amount of heat that a certain amount of the gas gives off under precisely defined combustion conditions. This heating value is given in Kcal / m. Natural gases mostly consist of methane and have a high calorific value of around 8900 Kcal / m- ⁵ . Countries without large reserves of natural gas are dependent on artificially produced gas. This gas has a calorific value of around 4450 Kcal / nr. It will be

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fig is referred to as "town gas" and can be understood as composed of three components: a ¹ , low-heating gas, which is mainly hydrogen, a high-heating gas, which consists of a hydrocarbon or a mixture of hydrocarbons, and a ballast or diluent gas, which is consists of inert gases such as nitrogen and carbon dioxide.

PiIr the usefulness of a dtadtga ^ it is however not ^ allei.n, d ^ r. ^ calorific value decisive, but also the Wobbe number W and the flame speed S. How on will be explained below in connection with ^ igur 4 a town gas must be in a certain area of a Chart on which the, fobbe number against the Plam speed is plotted. The Wobbe number will calculated by dividing the calorific value of the gas through the ■ Square root of the specific density of the gas (related on air). The meaning of the tfobbe number is that 3-ases with the same Wobbe number through the same openings exit at the same temperature and under the same pressure and when burned heat with the same Give up speed. The speed of the plam S is the maximum flame speed of a gas in air, expressed as a percentage of the maximum flame speed of hydrogen in air. The importance of the speed of the flame is that it can be used by everyone specific burner precisely matched to the Wobbe number must be so that imperfect burning, blowing away the flame or flashback of the flame into the burner is avoided. Conventional itait gas has a flame speed which lies between that of natural gas and hydrogen. In Fig. 4 are the wobbe numbers and flame speeds different gases and gas mixtures

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specified.

There are many processes for gasifying coal and hydrogen to hydrogen-rich, low-methane gases, those for synthesis purposes and after enrichment with methane, can be used as town gas, and there are many processes for the gasification of hydrocarbons zu'methanreichen Gases that are used to increase the calorific value of town gas. These processes are catalytic or non-catalytic, and who can see catalytically be continuous processes that do not involve catalyst regeneration is made, or discontinuous, in which the catalyst is periodically regenerated. The main hydrocarbon gasification processes are the following:

1. Steam reforming

Steam reforming can take place under strict conditions with the formation of a hydrogen-rich gas (as in the ICI process), or under mild conditions with the formation of a methane-rich gas (as in the CRG process).

2. thermal hydrocracking;

This leads to a methane-rich gas (as in the GRH process) and is either with a coke bed or Catalyst, a fluidized bed coke bed with controlled coke deposition through periodic absorption of the solids, or operated with a hydroforming catalyst, which affects the response; However, this takes place at the low pressures and high temperatures.

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temperatures that are used are much more than thermal because as a catalytic hydro-coating. To regulate the coke deposition on the catalyst Used steam.

Other "gasification processes that can be used in the process of the invention include the partial oxidation processes. In these processes a gaseous or liquid hydrocarbon feed is partially oxidized, with oxygen or air for light feeds and steam for heavy feeds, usually in the presence of one The pressures are from 7 to 210 atmospheres and the temperatures from 980 to 1925 ° C. The product is mainly hydrogen and carbon monoxide, for example 47 to 60 vol. # EL and 38 to 40 vol. 96 CO. The catalyst can Be iron, fetching methods are well known.

In the Dampfrefonnierungsverfahren be hydrocarbons at elevated temperatures, bei'atmosphärischem or higher pressure and in the presence of a catalyst, usually _a: reacted nickel catalyst on a support with steam to a group consisting of hydrogen, oxides of carbon and methane gas, the composition of which depends on, Reaktionsbeaingungen . ■

The steam fremer can be operated under strict conditions, with a maximum hydrogen content of the gas, or under mild conditions, with the methane content ^: assumes a maximum value. Two peculiar features of steam reforming processes have hitherto prevented their wider use, and the elimination of these disadvantages is a major advantage of this process.

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Finding: The steam reforming catalyst is sensitive to sulfur and the feeds may only have a low cichsulfur content, eg below 0.0005 76, preferably below 0.0001 $ . Heretofore, it has been necessary to achieve this low carbonization level with the aid of expensive desulphurization equipment that could not be used for any other purpose. In addition, the steam reformer is and must be limited in the range of hydrocarbon feeds that it can efficiently process the final boiling point will be below about 232, preferably below 204 ° C, or even below 177 ° C.

Steam reforming processes under strict conditions were developed by the ICI and are described in the following patents: USA patents 3-103,423 and 3,063-936, as well as Belgian patents 632,913 and 643,039. The ICI steam reforming process under strict conditions produces a hydrogen-rich (ras with a calorific value of about 2670 to 3115 Kcal / nr. JBs uses a nickel catalyst on a carrier, e.g. nickel on alumina The strict reform conditions include a relatively high steam: hydrocarbon distillate ratio, which is sufficient to prevent the formation of carbon at the relatively high temperatures, eg a ratio of 2 to 6 kg steam / kg distillate, a relatively low pressure , for example 0 to 28 atu and a relatively high starting temperature, for example 700 to 900 C. A typical product composition is as follows: 9-14 vol. # CH ₄ , 11-16 vol. # CO, 14-16 vol. # CO ₂ and 61-63 vol. * H ₂ .

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Steam reforming processes under mild bents to obtain ineth'ira'eich-m gas are used by the British G-as Council in the development of strong heating; _: ap method (Catalytic Rich (in ^ = CRj-trocess) amre wenüet. This is described for example in Belgian ta tent 64 5.2 '^ y to in British patent 981.72b. The CRij- / erfanren produced under mild conditions from a Hydrocarbon distillate with a final boiling point of less than about 252 G is a methane-rich gas with a calorific value of about 5350 Dia 7120 Kcal / cm. It uses a Mckel catalyst on a carrier, eg nickel on alumina low steam: carbon hydrogen distillate ratio, which is sufficient to prevent the formation of carbon at relatively low temperatures used, e.g. a ratio of 1 to 5 kg steam / kg distillate, a relatively high pressure, e.g. 9.8 to 35 atm and a relatively low starting temperature, for example 500 to 600 C. A typical product composition is as follows: 59-62 Vol .% CH ₄ , 20-24 Io GO ₂ , 0.7-2 Vol. # GO and 13-16 "

It is also known that : internal hydrocracking processes or hydrocracking processes without catalysts generate large amounts of methane and are therefore used to produce heating gas.

Conventional thermal hydrocracking processes can be used to convert hydrocarbon feedstocks that boil in a wide boiling range. They can be more common at temperatures of 400 to 900 ° C

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440 to 51ü ° C and for bridges from 56 to 24 5 atu at strongly em ·. -hydrogen consumption, e.g. 35.6 to 267 m / hl liquid hydrocarbon feed carried out •will. ■

The aforementioned GRiI process was successful for the conversion of light petroleum distillates in rivable products and widely used in Find heating gas production applied. This process is a thermal hydrocracking process and is used in high temperatures of 425 to 900 C and low pressures of 3.5 to 52 atm in the presence of a hydrogenation gas or "lean gas" carried out. The hydrogenation gas reacts with the distillate in an exothermic reaction, whereby gaseous hydrocarbons, mainly ftethane and ethane are formed. These Gas products are formed from: a) Paraffins in the petroleum distillate, and b) Äeitiketten of aromatics in the Distillate; the aromatic core remains unaffected. The aromatics are separated from the gas product and high quality crude benzene can be obtained. Such methods are described, e.g. in ßriti see patents 830,960 and 899,574, as well Belgian patent 635-755.

. Purely the purification of the gases to reduce theirs There are many conventional methods for the GO and COp content. Usually one or more of these processes is used to purify gases from gasification processes, and especially required from steam reforming processes. A reduction in the CO content is necessary if the end gas consists of largely pure hydrogen should exist, as is the case with synthesis gas for the

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Ainonia production, with lean gases with high flame speed and high Wobbe number, in gas feeds to the hydrocracking zone and in other uses of pure hydrogen is the pail.

GOp must, because it is an inert gas, in general always removed from the gases of a gasification process regardless of the purpose for which the grass is to be used, This applies to ammonia synthesis gases, Methanol synthesis gas and hydrocrack feeder). Man-made heating gases can have a certain, albeit low, CO ^ content.

Various methods are used to remove COp, such as monoethanolamine absorption and the conventional Vetrocoke process, which uses arsenic-activated potassium carbonate solution, which can reduce the COp content from less than 0.1 $> in a single step. The CO can be reacted with HpO at low temperatures of 232 to 260 C, which favor the formation of hydrogen, in the presence of a suitable catalyst, such as an iron oxide catalyst, to form COp and Hp. The equilibrium reaction that takes place is the water gas shift equilibrium or catalytic water gas reaction, often referred to as "shift conversion" or "CO shift conversion", indicating that the equilibrium is shifted from CO to COp. In the conventional reactions, the oil content can be reduced to 0 ^ 3 ° h in a single step

will.

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Ib Ab

The CO content of gas from gasification processes can also be converted into i-ethane by the

Conventional methanation reaction CO + 3 H ₂ > CiL +

HpO be reduced. Can likewise the cop content by the real tion CO ₂ + 4 H ₂ -> GH ₄ + 2 H ₃ O in the presence of a conventional hethanisierungskatalysa tors, such nichtsulfidiertein nickel, platinum, or Pal la diuiu be reduced to Einein not cracked carrier.

Gases from a gasification reaction that have undergone one of the above-mentioned purification stages can, if desired, be subjected to a final purification to remove traces of CO or 00 _? be subjected. This cleaning can consist of a physical removal of CO and CO. or consist in a conversion to products that do not adversely affect the subsequent synthesis or other catalysis. Such a cleaning can accordingly be a conventional copper liquid washing, a methanation or a washing with liquid nitrogen.

Catalytic hydrocracking is well known and has found extensive use in recent years. It has been described many times, for example in U.S. Patent 2,944-.006. The hydrocracking catalyst used contains a hydrogenating-dehydrogenating component, which is either based on a strongly acidic crack component, how silica / alumina is precipitated or otherwise intimately connected with it, or on is not applied to a carrier, or on a weakly acidic cracking component compared to silica / alumina, is dejected. The strongly acidic crack composition

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I ü H -J

nerite can be made from silica / alumina, silica / alumina / zirconium oxide, Alumina / ßoroxyden, fluorinated Ko: * - component and p.acid-treated clays exist. The preferred Crack components for jtjs according to the invention Processes are silica / clays with a silica ability from 30 to 99 wt .- ^. The hydrogenating-dehydrogenation line Component can be made from one or more metals from Group VI and VII ues Periodic Table or of which oxides, sulphides and sele ^ ides consist, which are used alone or with activators or stabilizers. Examples are the oxides and sulfides and selenides of nickel, '', '- :. tj? i Lt, Pl'ttin, Palla diuiü, Called molybdenum and tungsten. A:; -. R -) niers preferred The catalyst is nicicel sulfide on a silica / alumina Cr '- .ck component.

Can be the Kohlenwasserstoffbeschickumjen, lie in the conventional hydrocracking process converted any, boiling between about 35 and 593 grams of distillates, or about 260 ⁰ C siedenue jerk may be stands. However, distillates boiling between 35 and 454 G, preferably 93 and 343 ° C., are preferred as hydrocracking feed for the combination process according to the invention. Since the hydrocracking catalysts are generally stick-off sensitive, and since nitrogen compounds tend to accumulate in the higher-boiling fractions and residues, if the final boiling point is not far above 343 G, the feed is in most cases sufficiently free of nitrogen in order to allow the hydrocrackers to operate satisfactorily without prior hydrofining of the feed. The charges can

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Mender * contains sulfur from 0.0005 to 0.03%. Most contain hydrocarbon pollutants Sulfur in this amount, and it is one of the advantages of the process of the invention that the hydrocracking catalyst not only hydrocracked the feed, but also largely desulfurized it.

This desulfurization effectiveness of the hydrocracking catalyst enables, under the reaction conditions mentioned, a reduction in the sulfur content from 0.0005 to 0.3 % to below 0.0005 # with simultaneous hydrocracking of the feed. This combination of hydrocracking and desulphurisation is an important feature of the process of the invention because it allows hydrocarbon feeds which are unsuitable as steam reforming feeds due to their excessive sulfur content and / or too high final boiling point to be largely converted into a steam reforming feed by hydrocracking, which has a sufficiently low sulfur content and final boiling point.

This catalytic hydrocracking is for the he- The reason why the inventive method is so particularly important because it involves the conversion of hydrocarbon feedstocks in substantial amounts of lower boiling material with extremely little simultaneous formation light hydrocarbon gases, especially methane and ethane permitted. Because the formation of such easier Gases under hydrogen consumption is going on, the hydrogen requirement is lower here than when light Gases in this zone are generated in large quantities.

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In addition, the partial pressure of hydrogen in the Hydrocracking zone and thus lower operating costs being held.

In the drawings, Figure 1 is a flow diagram for carrying out an embodiment of the invention Process in which one or more hydrocracking stages in conjunction with a first, under strict reform conditions, and a second, under mild reforming conditions working steam reforming stage is driven. Figure 2 shows a flow diagram for one form of exercise, in which one or more hydrocracking stages in conjunction with one under severe Reformierungsbe conditions operated steam reforming stage and a thermal hydrocracking stage, in particular a gas, return hydrogenator is operated. Figure 3 is a graph showing typical gas equilibrium composition en in the hydrocarbon / steam reaction in the presence of a nickel catalyst at constant pressure, different temperatures and two different Shows steam / distillate ratios. Figure 4 is a graph in which the Wobbe number W is plotted against the flame speed S, and in which the various locations of hydrocarbon gases, hydrogen, inert gas and gas mixtures are shown.

In its broadest framework, the pre-. lying invention one or more hydrocracking stages with at least one subsequent gasification stage producing valuable gases. In particular, there is

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the invention in a method of self-generation more valuable Gases from a hydrocarbon distillate, and this process consists of this distillate hydrocracked in at least one hydrocracking zone and at least part of the product stream in a gasification zone is gasified from the hydrocracking zone.

According to another embodiment of the invention this distillate becomes fractions in a hydrocracking zone separated, including at least a first fraction and a second fraction with significant amounts of hydrocarbons with a higher molecular weight than the hydrocarbons in the first fraction, then at least a substantial part of this first fraction converted into a methane-rich gas in a gasification zone and the second fraction in a sub-strict one Reforming conditions operated steam reforming zone steam reformed to a hydrogen-rich gas.

According to a further embodiment of the invention, the distillate is hydroge cracked in a hydrocracking zone, the product stream from this hydrocracking zone is separated into fractions, including at least a first one Fraction and a second fraction with significant amounts of higher molecular weight hydrocarbons than the hydrocarbons in the first fraction, then the first fraction is in a first steam reforming zone steam reformed under mild reforming conditions to a methane-rich gas and the second Fraction in a second steam recovery zone steam reformed to a hydrogen-rich gas under strict conditions.

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According to another embodiment of the invention a hydrocarbon distillate is hydrocracked in a hydrocracking zone, the product stream from this Zone divided into at least a first and a second fraction, the second of which is substantial amounts of Hydrocarbons with a higher molecular weight than which has hydrocarbons in the first fraction, then a substantial part of the first fraction will be in a gasification zone to a gas rich in xethane, the second fraction in a steam reforming process. «- zone reformed under severe conditions to a hydrogen-rich gas dsjnpf and at least part of this hydrogen-rich gas passed into the hydrocracking zone after purification, with this purification from a shift conversion, COp removal and final purification, namely methanation for conversion of traces of CO in COp, or a liquid wash to remove residual CO and COpι.

In Fi _G 1 represents a üusübungsform aer present invention is shown, used in the one or more hydrocracking steps in connection with two steam reformers, one of which is under severe reforming conditions, and the other is operated under mild reforming conditions. In the form of exercise shown, great adaptability is achieved with regard to the formation of different products in varying amounts and compositions. The products include synthesis gases, high-purity hydrogen and heating gases with different heating values and other properties.

According to Fig. 1, a hydrocarbon feed, preferably a carbon boiling between 10 and 343 C

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Hydrogen distillate is passed through line 1 into hydrocracking zone 2, which can consist of one or more hydrocracking stages. Those skilled in the art know that when more than one hydrocracking stage is used, valuable hydrocracked products can be withdrawn from each stage for any purpose. Each stage in hydrocracking zone 2 is operated with the hydrocracking catalysts and conditions described above. The hydrocracking zone 2 is supplied with circulating hydrogen through line 3 and with fresh hydrogen through line 4 as required. The effluent from hydrocracking zone 2, if this zone consists of one stage, or from the last stage if it comprises several stages, consists of materials the average molecular weight of which is substantially lower than the average molecular weight of the feed and it contains H _? S, in which substantially all of the sulfur originally contained in the feed to the final stage in zone 2 is bound. This effluent is passed from zone 2 through line 5 into separation zone 10. From the separation zone 10, C ₁ and Cp hydrocarbon gases and HpS are removed through line 11.

For a more detailed explanation of FIG. 1 and also FIG. 2, the normal boiling points are given below paraffinic hydrocarbons from Cc to C-, ρ, which are higher than those of the corresponding isomers.

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link ■ ⁰ C 2 link 0
C. 8th CH ₁₂ 36, O C ₉ H ₂₀ 150 ^C 6 ^H 14 69 4th C ₁₀ H ₂₂ 174 8th ^C 7 ^H 16 98 ,8th ^G 11 ^H 24 195 5 ^C 8 ^H 18 125 ^C 12 ^H 26 214,

The terms used in the description ¹¹ Cz "," C ^ "," Cc ", etc. are to both the normal and the isomeric hydrocarbon compounds include the specified carbon content. From zone 10 a between C ₅ and 232 C is boiling Stream, as shown, passed into the first steam reformer 12 and reacted there under strict steam reforming conditions with steam supplied through line 18. This first steam reformer can expediently be a reformer according to the ICI process Preferably below, as discussed above in connection with steam reforming processes, this stream has the low sulfur content required for steam reformer feeds because it is a hydrocracked product from which sulfur has been removed by the hydrocracking reaction.

All of the flow from zone 10 to the first steam reformer 12 may include all or some of the flows in lines 13, 14, 15 and 16, as shown. All parts of the C ₁₁ -232 ° C materials in line 16 that

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not directed into zone 12, can by conduction 17.

Zone 10 becomes a boiling point in the C - ^ - Cy area Current, as shown, passed to the second steam reformer 23 and there under mild steam reforming conditions reacted with steam supplied through line 24. This second steam reformer can expediently be a CRG process reforiner. All of that passed from zone 10 to the second steam reformer 23 Electricity can include all or part of the materials coming from zone 10 through lines 25 »26, 13 or 14 can be deducted.

If desired, a C-z product can be added by conduction 27 can be deducted. A Cc »Cg product that because of the previous Hydrocraekreaktion a desulphurized Product is, 'can be withdrawn through line 28 if desired will. A C ^ stream or an FPG stream (liquefied, petroleum gas consisting of Ο * »and G.) can be passed through line 29 and withdrawn as product through line 30 or from line 29 to line 31 as fuel gas enrichment material as described below.

The first steam reformer 12 becomes a hydrogen-rich stream which can contain 61-63 vol.? £ H ₂ , 14-16 vol. # CO ₂ , 11-16 vol. 96 CO and 9-12 vol. £ CH ₄ , as has already been described in connection with strict steam reforming and as will be explained below in connection with FIG

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goes. On the other hand, some of this can also be routed in line 5'o and some in line 37. Gases flowing through line 36 can be fed into the air reformer 38 and treated there in order to reduce their methane content to below 1% by volume. The gases flowing out of the air reformer 38 are guided through line 39 and from there through line 40 to the cleaning system 41 or through line 40 to the cleaning system or through line 40 to the cleaning system 41 or through line 45 to the COp removal zone 46. On the other hand, some of these gases in line 39 can be passed through line 40, and another part through line 45. The cleaning plant 41, in which gases from line 41 are cleaned, preferably consists of a shift converter zone 50, a COp removal zone 51 and a final cleaning zone 52, which can be operated by any conventional method, e.g. a kethanization process to remove traces to remove or convert CO and COp. A detailed description of the zones that can be contained in the cleaning system 41 and their mode of operation has already been given above. A high-purity hydrogen stream, which can have a hydrogen concentration of about 97% by volume, is passed from the cleaning system 41 through line 53, from which part can be passed through lines 3 and 1 to the hydrocracking zone 2. A portion of the high-purity hydrogen stream in line 53 can be withdrawn through line 54 in order to be used as an independent product or for the synthesis of iunmoniaks.

Gases with low methane and CO ₂ content, however

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A significant amount of H ₂ and CO can be obtained from the G0 ^ ~ removal zone 46 for use in the synthesis of methanol.

The gas in line 37 serves as a hydrogen-rich, methane-poor gas, which is mixed with a methane-rich Gas can be enriched in any proportions to produce a heating gas with a moderately high calorific value,

■ z

e.g. to achieve about 4450 Kcal / nr. Accordingly, this can low-heating gas in line 37 by combining with a methane-rich gas from the second steam reformer 23, which flows through lines 60 and 61, are enriched. The gas in line 37 can also by means of C ^ hydrocarbons flowing through line 31 or FPG can be improved. Finally, the gas in line 37 can also be enriched by gas from external sources which can consist of FPG, natural gas, refinery gas or exhaust gas and through lines 62, 63 and be guided. The gas in line 37 can be mixed with one or more of these enrichment gases in any Quantities are blended and the resulting gas mixture can through line 65 to the shift converter zone 66, where a CO content is reduced. A heating gas with a moderately high calorific value is withdrawn from displacement converter zone 66 through line 67. Enrichment gas for the gas in line 37 can be passed through line 68 instead of 61, and through line 69 instead of 64, respectively according to the desired degree of purification of the enrichment gas.

The second steam reformer 23 is converted into a methane

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rich gas passed through line 60 and line 75 to purification plant 76, which is preferably a COg removal zone 77 and a methanation zone 78; the gas is cleaned in this cleaning system and the cleaned gas, which has a high calorific value, E.g. 8900 keal / nr is called hot-strong through line 79 Gas won. The gas in line 75 can, if desired with gases from an external source flowing through lines 62, 63 and 85. Alternatively, the gas from an external source may be conducted through lines 62, 86 and 87 to the gas to be enriched in line 79. From the separation zone 10 can materials that are in the range of about 193 C and the feed boiling to the hydrocracking zone 2, are circulated by line. This material can be 232 C + Materials from Line 95 and C-q-232 C materials Line 24 included. On the other hand, if the intention is to operate hydrocracking zone 2 in a single pass, the materials flowing in lines 24 and 95 can be withdrawn as a product via line 97, which because of the desulphurizing effect to which these materials are subjected in hydrocracking zone 2 is largely sulfur-free.

According to the exercise form shown in FIG Invention, heating gases can not only have different calorific values, but also with different combinations obtained from Wobbe number and flame speed as can be seen from FIG. 4 described below.

In Figure 2, an embodiment of this er-

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Finding shown in which one or more hydrocracking stages in connection with a Dauipreformierungsötufe, -die operated under strict reform conditions and a thermal hydrocracking stage, in particular a gas circulation hydrogenator is used. With the form of exercise shown, there is a great deal of adaptability with regard to the manufacture of different products in varying quantities and compositions achieved. The products include synthesis gases, high-purity hydrogen and heating gases with different calorific values and other characteristics.

According to FIG. 2, a hydrocarbon feed is preferred a hydrocarbon distillate boiling in the range Cu-343 G through line 101 in the hydrocracking zone 102, which may include one or more hydrocracking zones. The skilled person knows that using multiple hydrocracking zones, valuable hydrocracked products from any of the stages for any Uses can be deducted. Every level in the hydrocracking zone 102 is carried out with the catalysts and under the hydrocracking conditions described above were operated. The hydrocracking zone 102 is recirculated with hydrogen through line 103, if necessary and supplied with fresh hydrogen through line 104. The effluent from the hydrocracking zone 102, if any Zone comprises only one stage, or consists of the last stage if this zone contains several stages from materials whose average molecular weight is significantly below the average molecular weight the charge and it contains HgS, in which largely all of the sulfur is bound,

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which was contained in the feed to the last stage in zone 102. This effluent from zone 102 is agitated through line 105 to separation zone 110. From the separation zone 110. G ₁ - and GP carbons>; hydrogen gases and HpS are removed via line 111.

For a better understanding of FIG. 2, reference is made to the boiling point table which was given in connection with FIG. 1 and in which the Gc to G ₁₃ -norinal paraffinic hydrocarbons are mentioned. From the zone 110, a stream boiling in the region of C, - 232 G is passed to the steam reformer 112, which is operated under strict conditions and is supplied with steam from line 113. This steam reformer can expediently be an ICI process reformer. The final boiling point of this current should not exceed 232 ⁰ C and preferably be even lower, as has been said in the context of strict steam reforming. This stream has the low sulfur content required for steam reformer feeds because it is a hydrocracked product from which sulfur has been removed as a result of the hydrocracking reaction.

The total flow from zone 110 to steam reformer 112 may include all or some of the currents in lines 120, 121, and 122. All parts of the 0 - ^ - 232 ° C materials in line 122 that are not directed into zone 112 can be passed through line 123.

Zone 110 becomes one in the range 0 ^ -232 ° C boiling stream to thermal hydrocracker 130

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out, the two-way gas circulation hydrogenator can and will be there under thermal hydrocracking conditions with a hydrogen-rich gas, which expediently one from the steam reformer 112 through Line 131 circulated, purified hydrogen rich Gas can be implemented.

All of the stream that is routed from zone 110 to the thermal hydro cracker 130 can be all or contain a portion of the materials emerging from zone 110 through all or some of lines 132, 133 »120 and 122 can be deducted. The C-z product can, if desired be withdrawn through line 134. A Cu, Cg product, which because of the previous hydrocracking reaction If it is a desulphurised product, it can be used be withdrawn through line 135. A PPG stream may be sent over line 136 if desired Product can be removed. Each part of the flow in line 134 or the flow in line 136 can be used as heating gas Enrichment material for the hydrogen-rich, low-methane gas generated in the steam reformer 112, be used.

Is selected from the steam reformer 112, a hydrogen-rich stream which 61-63 ¥ ol. £ H _2, 14-16 VoI $> CO _2, 11-16 VoI 4 "and CO 9-12 VoI # CH may contain _4., As in The context of strict steam reforming, discussed below in connection with FIG. 3, is passed through line 140, from where it is passed into line 141 or 142. On the other hand, part of it can be routed into line 141 and part thereof into line 142. Gases flowing through line 141 can be guided into the air reformer 143 and

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treated there to un- their Hethan content. ter 1 vol.fo to reduce. The gases flowing out of the air reformer 14 3 are passed through line 14.4 and from there through line 14 5 to the cleaning system 14 or through line 147 to the COp removal zone 148. On the other hand, some of the gases can be fed into line 144 through line 14 5 and another part through line 147 -be conducted. The cleaning system 146, in which gases from line 14 5 are cleaned, preferably consists of a shift converter zone 149 »a CCL removal zone 150 and a final cleaning zone 151ι which can be operated according to conventional methods, for example as an ethanization zone To remove or convert traces of CO and CO _2. A detailed description of the zones in the cleaning system 146 and their working groups was given above. A high-purity hydrogen stream, which can have a hydrogen concentration of about 97 % by volume, is passed from the cleaning system 146 through line 152, from where a portion can be passed through lines .103 and 101 to the hyro-cracking zone 102. A. Part of the high-purity hydrogen stream in line 152 can be withdrawn via line 153 as product or for use in ammonia synthesis.

Gases with low methane and CO ₂ content, but significant H ₂ and CO content, can be withdrawn from COp removal zone 154 for use in methanol synthesis.

The gas in line 142 serves as a hydrogen-rich, low-methane gas, which is mixed with a methane

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rich gas enriched in any proportions can be used to achieve a heating gas with a moderately high calorific value, e.g. of around 4450 Kcal / m. This Thus low-heating gas in 142 can be enriched before or after it enters the displacement converter zone was directed. Enrichment can be carried out by means of PPG from line 136 »> net han-rich gas from the thermal hydrocracker 150 or (fas from an external source, e.g. FPG, natural gas, refinery gas or Exhaust gas, or combinations thereof. The enrichment can take place in any ratio of low methane gas can be made to enrichment gas. As shown in the figure, the low methane gas becomes in line 142 to displacement converter zone 160 where the CO content of the gas is reduced. The shift converter zone 160 becomes the low methane Gas passed through line 161 and with an enrichment gas flowing through line 162 to a fuel gas combined with medium-high calorific value, which is taken through line 163. The enrichment gao in line 162 preferably includes that entering line 162 from thermal hydrocracker 130 via line 165 Gas, on the other hand or in addition, can mute the enrichment gas from an external source and enter line 162 through line 164.

The thermal hydrocracker 130 becomes a methane and ethane-rich gas with a significant hydrogen content passed through line 170 to crude benzene removal zone 171, where crude benzene is removed therefrom and used as Product is withdrawn through line 172. That arose

"Z

This gas, which has a calorific value of over 8900 Kcal / m, is extracted from the crude benzene removal zone 171 via

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device 173 as heating gas with a high calorific value, This gas can be used if desired ;; with a gas off an external source flowing through hole 174 versi'tinitten v; ground.

(According to the exercise form shown in Figure 2 can not only use heating gases with different calorific values, but also with any combination of Wobbe number and Flaminenges chwinaiikeit are won, as can be seen from FIG. 4 below.

Figure 3 is a graphical representation of more typical Equilibrium Compounds in the Kohler Hydrogen Vapor Reaction in the presence of a nickel catalyst at a constant pressure of 26 atü, at different temperatures and at two different steam / distillate ratios. As in the Discussed connection with steam reforming under mild conditions or under strict conditions the temperatures are higher with severe steam reforming than with mild steam reforming. For example produces an IGI steam reformer, which is under severe conditions, including an outlet temperature of about 760 C, with a steam-read ill a t ratio of 4.0 kg steam / kg distillate and operated at a pressure of 26 atmospheres, a gas product of a composition as defined by line A in FIG. On the other hand, one produces CRG reformer operating under mild conditions including an exit temperature of about 53b C and at a steam / distillate ratio of 1.6 kg steam / kg distillate, and at a pressure of 26 atmospheres becomes, a gas product with a composition like them

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1545-33

in Fi _t ';u.r'-5 is determined by the line is.

From the previous meeting .eier and from the earlier observations on steam refining it emerges that under the conditions of Koh-1 enwass only off-Dainj: · freak ti on a) a lower temperature and b) a lower steam / hydrocarbon ratio favors the formation of GlL. The CH. Formation is also favored by higher pressures, which are usually less than 35 at'i. One recognises also that the conditions promoting CH also favor CO “storage during production is strongly inhibited by CÖ and Hp.

Conversely, it can be seen that a) higher conditions than those favoring hydrogen formation Temperatures and b) higher steam to hydrocarbon ratio Gc belong. The formation of hydrogen is also "promoted by lower pressures, which however in in all cases in the range below 2ö atü. La ?. recognizes that those favoring the formation of hydrogen Conditions dit Cü-jeroduiction promote and education by Gü “and CH. severely hinder.

ά Η <

FIG. 4 is a graph in which the Y / obbe number Vi is plotted against the flame speed S and in which the locations of various hydrocarbons, hydrogen, inert gas and gas mixtures are plotted. The Wobbe index and the Flarmnengesehwindigkeit of gas mixtures can be estimated from the figure, A. A mixture of two individual gases is roughly characterized by a point on the straight line between them

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two gases and according to the quantitative ratio of the two gases contained in the mixture.

From the figure it can be seen that when a burner is set to work properly with a given Gases X is set, a triangle around the · location of gas X indicating the boundaries within which the gas mixture must be if satisfactory results are obtained with this burner should. The three limits of the triangle, namely imperfect burn, blow away and kickback, were made discussed above in connection with heating gas characteristics.

Bei Piel 1;

600 nr / day of a single distilled gasoline from a Middle Eastern crude oil with a density of 0.703, consisting of C ₁ - to C, .- hydrocarbons and containing 0.05 $ sulfur, is hydrocracked on a "Cg-UmIauf" basis , ie all hydrocarbons in the effluent from the hydrocracker which contain more than 5 carbon atoms are returned to the hydrocracker. The hydrocracker is treated with a sulfided catalyst of a silica / alumina cracking component and 6 wt .- # nickel at 77 atmospheres, 89 m ⁵ Hydrogen / hl of fresh feed and an initial temperature of 312 C. The temperature is gradually increased as required in the range from 312 to 427 C in order to achieve a constant conversion of the hydrocracker feed of about $ 60 into Ce oil
achieve.

into Cc hydrocarbons and lighter materials too

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ORIGINAL INSPECTED

The hydrocracker yields of Gu and lighter ones Materials is as follows:

H ₂
H ₂ S

(rew,% in the coal

hydrogen loading kg / day

1685 0.05 213 0.45 14730 0.71 307G 22.56 96500 39.40 168300 39.29 167300

total

102.46

The HpS is removed from the hydrocracker product, a C _c portion of the product stream is reformed in an ICI steam reformer and the remainder of the product stream is reformed in a GRG steam reformer. The composition of the Hydrocraeker product stream is as follows:

To the CRG reformer To the ICI reformer

1685 14730

3023 96400 168200 23900

143700

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From this feed, the CRG reformer produces 35,000 nr / day of a gas product with a specific density of 0.663 »a calorific value of b'730 Kcal / m- ⁵ and the following composition:

GO ₂ 18.5 VoI

CO 0.6 »

H ₂ 15.1

GH ₄ 65.8

The ICI reformer uses this feed to produce 666,100 m / day of a gas product which, after passing through a shift converter zone for converting CO into CO _{2, has} the following composition:

CO ₂ 21.8 VoI 4>

CO 3.7

H ₂ 66.7

CH ₄ 7.8

450,000 nrv days of this ICI reformer product are blended with 55,000 nr / day CRG reformer product to form town gas that has a calorific value of 5000 Kcal / nr and a flame speed of about 29.

The rest of the ICI-reformer product, 216100 m / day sierungszone cleaned successively in a shift converter zone, a cop removal zone and a methane!, Wherein a substantially methane and about 88 VoI 4> is hydrogen gas consisting formed

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will. .This hydrogen-rich gas 'turns' into a hydro cracker led to its hydrogen demand in part to satisfy.

Example 2:

608 no. Of simple distilled petroleum in example 1 become with a single pass, i.e. without return unconverted products in the hydrocracking zone, hydrocraoct. The hydrocracker comes with the same Catalysts and operated under the same conditions as in Example Γ. The yields are like follows :.

H ₂
H ₂ S

Wt. ^ B, based on hydro
crack er hydrocarbon
Besehung kg / tas 920 0.05 214 0.03 10300 0.18 773 6.90 29600 18.18 78150 26.04 113900 20.45 87950 30.20 130000

The HpS is made from the hydrocracker product stream removed, part of the current is in an ICI

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Steam reformers are steam reformed and the remainder of the stream is steam reformed in a CRG steam reformer, such as the table below shows:

To the CRG reformer To the ICI reformer kg / day kg / day

H ₂ 918

C ₁ 10300

C ₂₇₇₄

C ₅ 29615

C ₄ 78150

C ₅ 112000

C ₆ 84000 5898

C ₇ + 130000

550,000 nr / day of the CRG reformer product, which has the composition given in Example 1, are

• 2

those with 450,000 nr / day of the ICI reformer product, which has the composition given in Example 1, to 1000000 nr / day of a town gas that has the same calorific value and the same flame speed as the Town gases of Example 1 has.

The remainder of the ICI reformer product, 167800 m3 / day, becomes hydrogen rich as in Example 1 Gas cleaned, which is sent to the hydrocracker.

Be ispiel

3
574 ar of a simply distilled gasoline

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a Middle Eastern crude that has a specific gravity of 0.753, from CV to G ^ coal water only openly exists and 0.077 contains 96 sulfur is on a C ^ + basis hydrocracked, i.e. all hydrocarbons in the effluent from the hydrocracker with more than 6 carbon atoms returned to the hydrocracker. The hydrocracker is made with the same catalysts and under the same Conditions operated as in Example 1. The yields are as follows:

Weight? *, Based on hydro
cracker hydrocarbon
feed k / T ^H 2 1536 H ₂ S 0.08 344 ^G l 0.07 15230 ^G 2 0.40 1722 ° 3 ■ 15.70 67600 ^G 4 42.20 181900 ^G 5 16.98 73050

The HpS is removed from the Hydro crack er product stream, part of this stream is used in an ICI steam reformer steam reformed and the remainder is steam reformed in a CRGr steam reformer, as from the following Table shows:

To the CRG-Refarmer To the ICI-Reformer kg / day kg / day

H ₂ 1536

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- 34 - Table (port setting)

To the CRG-Refonner · To the ICI-Reformer W day kg / day

G ₁ 15240

G ₂ 1721

C ₃ 67600

C ₄ 181900

G ₅ 37900-77700

G ₆ 73050

550,000 mV day of the CRG ref ormer product, the has the same composition as in Example 1, 450000 mVTag of the ICI reformer product that has the same composition as in Example 1, blended to 1,000,000 nr / day of a town gas, which the same calorific value and the same plamming speed as the town gas of Example 1 has.

The rest of the ICI reformer product, 245700 m '/ day becomes a hydrogen-rich gas as in Example 1 cleaned, which is sent to the hydrocracker.

In game 4:

572 m · ^{5 of} a simply distilled petroleum feed as in Example 3 are hydrocracked in a single pass, ie without reflux of unconverted products into the hydrocracking zone. The hydrocracker is with the same catalyst and under the

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the same conditions as in Example 1 "operated.

The following yields are obtained:

based on the hydrocracker carbon feed

kg / day

H ₂ 0.08 867 0.05 344 ⁰ I. 0.28 11000 C ₂ 10.99 1184 C, 29.54 47200 η C ₄ + i C ₄ 19.25 126900 ^C 5 11.89 82750 ^C 6 30.09 51050 Grj + 129500

The H ₂ S is removed from the Hydroeracker product stream, part of the stream is steam reformed in an ICI steam reformer and the remainder of the stream is steam reformed in a CE.Gr Bampf reformer, as can be seen in the table below:

To the CRG reformer kg / day

868
10950 1203 47200

126900

To the ICI reformer kg / day

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To the CRG reformer To the ICI reformer kg / day kg / day

C ₅ 82750

C ₆ 42500 8600

550,000 nr / day of the CRG reformer product "it the composition specified ^{in Example 1 are blended with 450000 m 5} / day of the ICI reformer product" it of the composition specified in Example 1 to 1000000 m / day of a town gas that contains the has the same flame speed and the same calorific value as the town gas of Example 1.

The remainder of the ICI-Refoimer product, 176750 vr / day, is purified as in Example 1 to a hydrogen-rich gas which is sent to the hydrocracker.

Be ispiel 5:

635 * a single distilled crude oil consignment made from Middle Eastern crude oil, with a density of 0.744 and a boiling range of 99 to 181 ° C and a sulfur content of 0.05 5% with the catalyst and hydroge cracking under the conditions of Example 1.

The product stream from the hydrocracker is after removal of hydrogen and hydrogen sulfide in a C ^ and a Cc + fraction separated. the The latter fraction is steam refored in an ICI steam reformer.

The product stream from this punch former »der 9O9884 / ÖI02

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contains about 18 » OO is directed to a shift converter zone where CO is converted to CO ₂ . The product stream from the displacement converter zone is a gas with a heat value of 2960 Kcal / m and the following composition:

Mole percent

H ₂ 66

CO 3

CO ₂ 22

CH ₄ 9

This gas with a low calorific value is approx

13 VoI 4 * EPG (C, and 0) from the Hydrocraeker blended into a town gas with a calorific value of 3140 Kcal / nr and a flame speed of about 40.

From this description it will be readily apparent to a person skilled in the art that the various embodiments of the present invention can be carried out in a highly adaptable manner »wherein Heating gas mixtures can be produced that have a wide variety of compositions and that the ge desired Position in the wobbe number / flame speed magram take in.

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Claims (6)

15A5433 claims; 1. Process for the production of gases, in particular heating and synthesis gases from hydrocarbon distillates, characterized in that there is a hydrocarbon distillate catalytically hydrocracked, at least a first part of the product stream from the Hydrocracking zone gasified in a gasification zone, optionally a second part of the product stream, its Hydrocarbons to a significant extent a higher one Molecular weight as the hydrocarbons of the first part of the product stream, in a hydrogen rich Gas converts and from this hydrogen-rich gas optionally a part with that from the first part of the product stream formed from the hydro crack zone blends and / or after cleaning in the hydro crack zone returns. 2. The method according to claim 1, characterized in that one a) hydrocracking a hydrocarbon distillate; b) separating the cracked product into at least two fractions, a substantial part of the hydrocarbons in the second fraction has a higher molecular weight than the hydrocarbons the first fraction; c) the first fraction in a gasification zone gasified to a methane-rich gas, which may be at least partially high-calorie Heating gas is withdrawn; 909884/0802 U O <+ d) the second fraction under severe steam reforming conditions converts to a hydrogen-rich gas, which with that from the methane-rich gas obtained from the first fraction is combined into a fuel gas with a medium calorific value and / or withdrawn for synthesis purposes and / or purified and in a purification stage is returned to the hydrocracking stage. 3. The method according to claim 1 or 2, characterized in that that the gasification zone is a steam reforming zone operated under mild conditions. 4. The method according to claim 1 or 2, characterized in that the gasification zone is a thermal Hydroerackzone 1st. 5. The method according to claim 4, characterized in that that the thermal hydrocracking zone is a gas circulation hydrogenation zone is. 6. The method according to claim 2, characterized in that that the purification stage consists of a Versehiebungskonverterxone and / or a COp Entfer voltage zone and / or a methane! sization zone and / or 809884/0802 BAD ORIQJNAt. a liquid washing zone to remove traces of CO and GO ₂ . Pur Chevron Research Company As Dr.W.Befl Lawyer 908884/0802 Leersette