EP0318903A2 - Process for the hydrogenation of liquid carbon-containing feedstocks - Google Patents
Process for the hydrogenation of liquid carbon-containing feedstocks Download PDFInfo
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- EP0318903A2 EP0318903A2 EP88119848A EP88119848A EP0318903A2 EP 0318903 A2 EP0318903 A2 EP 0318903A2 EP 88119848 A EP88119848 A EP 88119848A EP 88119848 A EP88119848 A EP 88119848A EP 0318903 A2 EP0318903 A2 EP 0318903A2
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- hydrogenation
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- heat exchanger
- heat exchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
Definitions
- the invention relates to a process for the hydrogenation of liquid carbonaceous feedstocks such as heavy oils, oil residues, top or vacuum residues, syncrude from oil shale, tar sands, tars and pitches from hard coal or lignite, with hydrogen-containing gases as hydrogenation gas under the conditions of a phase-phase hydrogenation at elevated temperature and increased pressure in the presence of an additive or a catalyst with a downstream hot separator stage with separate heating of a feed stream formed from the feed materials and a partial stream of the hydrogenation gas and a second partial stream of the hydrogenation gas.
- the feedstocks are liquid either at normal temperature or at elevated temperatures.
- Temperatures in the bottom phase reactor of approximately 400 to 500 ° C. are typical, and the process pressure can be selected between 150 to 1200 bar.
- the invention is based on a method as specified above, in which heavy oil is fed as a feed product to a preheater and in which a partial flow of the total amount of hydrogenation gas required in a gas heat exchanger through which the hot separator head product flows precedes the preheated mixture of heavy oil, possibly additive and hydrogenation gas Entry into the bottom phase reactor is added (see. DE 35 23 709 A1).
- the feed products are heated to the temperature required for entry into the reaction system of the bottom phase hydrogenation by means of a heating furnace provided in the feed product stream.
- This heating furnace is one of the most critical components of any sump phase hydrogenation system. This is due in particular to the operating conditions, which are characterized by high hydrogen partial pressure in the tube, high tube wall temperatures and high total pressure, and which set operational limits over the material that can be used.
- tip preheaters are associated with procedural disadvantages which result from high pressure loss in the preheater, poor heat transfer and undefined conditions due to the three-phase system present in the tube.
- the object of the invention is to design the entire heat management of the process by recovering the heat of reaction in such a way that there is no need for the externally heated feed furnace for heating the feed stream.
- DE 26 51 253 A1 it is stated that in a procedure similar to that at the beginning The specified process of the preheater heated by external heat can be considerably reduced or even completely omitted under certain circumstances, but it is intended that a distillate fraction to be returned to the feed product is reheated in a heat exchanger heated by external heat.
- the additional heating of the distillates brings the advantage of the significantly lower tendency to coke compared to the heating of the coal pulp in a preheater.
- the above object is achieved in the method of the type mentioned above in that the hot separator head product emits its heat to the feed streams mentioned in indirect heat exchange and that by further heating the separately conducted part of the hydrogenation gas in a hydrogenation gas heater and then combining it with the indirect heat exchange heated feed stream the necessary inlet temperature is reached in the bottom phase reactor.
- the specified method is suitable for hydrating liquid carbon-containing feedstocks such as heavy oils, oil residues (top and vacuum residues), syncrude from e.g. B. oil shale, tar sands, heavy oils, tars and pitches from hard coal or lignite u. to process.
- liquid carbon-containing feedstocks such as heavy oils, oil residues (top and vacuum residues), syncrude from e.g. B. oil shale, tar sands, heavy oils, tars and pitches from hard coal or lignite u. to process.
- the present process is also advantageous Oils or heavy mineral oil residues
- Mixtures of finely ground coal and the feedstocks provided according to the invention are supplied as so-called foreign oils ("co-processing").
- Such a procedure has the advantage that the recycle streams required for the mashing of the finely ground coal are largely or completely eliminated.
- Weight ratios of coal and foreign oil of 1 to 5 to 4 to 5 are preferred. All types of coal which can be economically hydrogenated, for example, are suitable as the coal to be used.
- the process can be designed by largely recovering the thermal energy of the reaction products so that a hydrogenation gas heater is sufficient for a separate partial flow of the hydrogenation gas in order to apply the start-up temperature of the hydrogenation reaction required when starting up into the hydrogenation reactor in the bottom phase and to compensate for heat losses .
- This result could only be achieved by optimizing the process control of the reaction products and the feed products in countercurrent, and it is surprising that the thermal energy to be supplied can be introduced into the process via a partial stream of the hydrogenation gas without external heating of the liquid or solid-liquid feed products.
- Circulation furnaces come as hydrogenation gas heaters, hereinafter also referred to as hydrogenation gas furnaces, but preferably also radiation ovens, in which heating to a temperature of 300 to 650 ° C., preferably 490 to 550 ° C. takes place.
- stream (9) in the downstream direction comes into heat exchange relationship with the feed stream (3) in the heat exchanger (20) and the partial stream of the hydrogenation gas (5) in the heat exchanger (23) and passes through a reactor (27) for hydrogenation in the gas phase at a fixed bed contact .
- the product stream refined in reactor (27) passes as stream (10) heat exchanger (19) and heat exchanger (22) in heat exchange relationship with stream (3) or stream (5) and an intermediate separator (28) with separation of a hot oil fraction (11).
- the residual stream (12) drawn off by the separator (28) gives the rest of the heat exchangers (18) and (21) for heating the Use products utilizable heat to electricity (3) and electricity (5) and is fed to a cold separator (29), in which a separation of waste water and exhaust gas as well as the recovery of a cold oil fraction (13) and recycling of the cycle hydrogenation gas as stream (15) via compressor (30) done in the process.
- part of the circulating gas stream (16) is advantageously kept available as a quench gas stream and fed in if necessary.
- a gas scrubber can be provided in the usual way for working up the circulating hydrogen gas fraction. Such a work-up ensures a sufficient hydrogen partial pressure in the hydrogenation gas system by removing the C1 to C4 components which are soluble in the gas scrubbing by means of washing liquid.
- the separate partial stream from the total amount of hydrogenation gas to be used can make up 20 to 95, preferably 40 to 80% of the total amount of hydrogenation gas required.
- the stream of feedstocks (1) consisting of a suspension with the additive or catalyst is mixed with a partial stream of the hydrogenation gas (2) composed of circulating hydrogenation gas, stream (15), via compressor (30) while feeding in fresh hydrogen, stream (17). combined to form stream (3) and preheated to the conditions of stream (4) by means of indirect heat exchange in the apparatuses (18), (19) and (20).
- the separate hydrogenation gas stream (5) is also preheated in indirect heat exchange in the apparatuses (21), (22) and (23) and heated to the necessary temperature in hydrogenation gas heater (24), so that the mixture with the material stream (4) required reactor inlet temperature in reactor (25) for stream (7) is reached.
- the desired products are obtained in the reactor (25) or a cascade of reactors connected in series, which are separated in the hot separator (26) into a residue stream (8) and into a top stream (9).
- the top stream (9) is used for preheating in countercurrent to the feed stream (3) and hydrogenation gas stream (5) in the aforementioned apparatuses (18), (19), (20), (21), (22) and (23).
- the circuit shown in the figure provides an integrated gas phase reactor (27) for the purpose of refining and further removal, in particular of the O, S and N-containing heteroatom components.
- Gas phase reactor (27) is advantageously connected between apparatus (23) and apparatus (19).
- the products condensed in the heat exchangers due to the removal of heat are collected in intermediate separators (28) and in cold separators (29).
- the condensates are discharged from the high-pressure circuit as hot oil (11) and cold oil (13). After the hot oil has been drawn off, water can be injected in order to avoid salinization of the downstream heat exchangers.
- the water of reaction formed in the hydrogenation process is optionally separated together with the injection water in the cold separator (29) and discharged as stream (14) from the high-pressure circuit. It contains u. a. the heteroatom compounds removed by refining in the form of the simple hydrogen compounds H2S and in particular NH3 dissolved in the waste water.
- the temperature in the intermediate separator can be freely selected within a certain range.
- the residual gas going overhead in the cold separator (29) is returned with a circuit compressor (30), if necessary after a certain proportion has been discharged.
- the return gas is cold gas as a stream for temperature control of the reactors and the hot separator (16) taken.
- the fresh hydrogen required for the reaction is added as stream (17). Provision can also be made to add stream (2) as a fresh hydrogen stream.
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Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Hydrierung flüssiger kohlenstoffhaltiger Einsatzstoffe wie schwere Öle, Ölrückstände, Top- oder Vakuumrückstände, Syncrude aus Ölschiefer, Teersanden, Teeren und Pechen aus Steinkohle oder Braunkohle, mit wasserstoffhaltigen Gasen als Hydriergas unter den Bedingungen einer Sumpfphasenhydrierung bei erhöhter Temperatur und erhöhtem Druck in Anwesenheit eines Additivs oder auch eines Katalysators mit nachgeschalteter Heißabscheiderstufe unter getrennter Aufheizung eines aus den Einsatzstoffen und einem Teilstrom des Hydriergases gebildeten Einsatzstroms und eines zweiten Teilstroms des Hydriergases. Die Einsatzstoffe sind entweder bei Normaltemperatur oder bei erhöhten Temperaturen flüssig.The invention relates to a process for the hydrogenation of liquid carbonaceous feedstocks such as heavy oils, oil residues, top or vacuum residues, syncrude from oil shale, tar sands, tars and pitches from hard coal or lignite, with hydrogen-containing gases as hydrogenation gas under the conditions of a phase-phase hydrogenation at elevated temperature and increased pressure in the presence of an additive or a catalyst with a downstream hot separator stage with separate heating of a feed stream formed from the feed materials and a partial stream of the hydrogenation gas and a second partial stream of the hydrogenation gas. The feedstocks are liquid either at normal temperature or at elevated temperatures.
Hierbei sind Temperaturen im Sumpfphasereaktor von etwa 400 bis 500 °C typisch, und der Verfahrensdruck kann zwischen 150 bis 1200 bar gewählt werden.Temperatures in the bottom phase reactor of approximately 400 to 500 ° C. are typical, and the process pressure can be selected between 150 to 1200 bar.
Die Erfindung geht aus von einem Verfahren wie oben angegeben, bei dem Schweröl als Einsatzprodukt einem Vorheizer zugeführt wird und bei welchem ein in einem von dem Heißabscheiderkopfprodukt durchströmten Gaswärmetauscher aufgeheizter Teilstrom der insgesamt erforderlichen Hydriergasmenge dem vorgewärmten Gemisch von Schweröl, ggf. Additiv und Hydriergas vor Eintritt in den Sumpfphasereaktor zugegeben wird (vgl. DE 35 23 709 A1).The invention is based on a method as specified above, in which heavy oil is fed as a feed product to a preheater and in which a partial flow of the total amount of hydrogenation gas required in a gas heat exchanger through which the hot separator head product flows precedes the preheated mixture of heavy oil, possibly additive and hydrogenation gas Entry into the bottom phase reactor is added (see. DE 35 23 709 A1).
Bei den bekannten Verfahren der eingangs angegebenen Art erfolgt die Aufheizung der Einsatzprodukte auf die für den Eintritt in das Reaktionssystem der Sumpfphasenhydrierung erforderliche Temperatur mittels eines im Einsatzproduktstrom vorgesehenen Aufheizofens. Dieser Aufheizofen ist eines der kritischsten Bauteile jeder Sumpfphasehydrieranlage. Dies liegt insbesondere an den, durch hohen Wasserstoffpartialdruck im Rohr, hohe Rohrwandtemperaturen und hohen Gesamtdruck gekennzeichneten, Betriebsbedingungen, die über den einsetzbaren Werkstoff betriebstechnische Grenzen setzen.In the known processes of the type specified at the outset, the feed products are heated to the temperature required for entry into the reaction system of the bottom phase hydrogenation by means of a heating furnace provided in the feed product stream. This heating furnace is one of the most critical components of any sump phase hydrogenation system. This is due in particular to the operating conditions, which are characterized by high hydrogen partial pressure in the tube, high tube wall temperatures and high total pressure, and which set operational limits over the material that can be used.
Nach "Die katalytische Druckhydrierung von Kohlen, Teeren und Mineralölen", Springer-Verlag, Berlin/Göttingen/Heidelberg 1950, Seite 232, erfolgte grundsätzlich die Aufheizung der Reaktionsteilnehmer in Wärmetauschern und im Spitzenvorheizer. Als Wärmeaustauscher wurden generell "Bündel"-Regeneratoren verwendet, und für die Spitzenvorheizung mittels des extern beheizten Aufheizofens wurden haarnadelförmige Druckrohre von 90 bzw. 110 mm lichtem Durchmesser und etwa 30 000 mm Gesamtlänge eingesetzt, wobei der Produkteinsatzstrom innerhalb der mittels Wälzgasbeheizung geheizten Rohre geführt wurde.According to "The catalytic pressure hydrogenation of coal, tars and mineral oils", Springer-Verlag, Berlin / Göttingen / Heidelberg 1950, page 232, the reaction participants were basically heated in heat exchangers and in the tip preheater. "Bundle" regenerators were generally used as the heat exchanger, and hairpin-shaped pressure tubes of 90 or 110 mm in diameter and approximately 30,000 mm in total length were used for the tip preheating by means of the externally heated heating furnace, the product feed stream being conducted within the tubes which were heated by means of roller gas heating .
Die durch eine Mehrphasenströmung von Gasen und Dämpfen, Flüssigkeit sowie Feststoff im Rohr gekennzeichneten Verfahrensbedingungen ziehen erhebliche Unsicherheiten bei der Auslegung des Aufheizofens sowohl bei der Berechnung des Druckverlustes als auch des Wärmetransportes nach sich.The process conditions, which are characterized by a multi-phase flow of gases and vapors, liquid and solid in the tube, result in considerable uncertainties in the design of the heating furnace, both when calculating the pressure loss and the heat transfer.
Der Einsatz derartiger Spitzenvorheizer ist mit verfahrenstechnischen Nachteilen behaftet, die sich aufgrund hohen Druckverlustes in dem Vorheizer, schlechter Wärmeübertragung sowie undefinierter Zustände wegen des im Rohr vorhandenen Dreiphasensystems ergeben.The use of such tip preheaters is associated with procedural disadvantages which result from high pressure loss in the preheater, poor heat transfer and undefined conditions due to the three-phase system present in the tube.
Betriebstechnische Nachteile resultieren aus der Neigung zur Verkrustung der Innenseite der Ofenrohre und aus Verkokungsreaktionen des Produktes in den Rohren. Damit verbunden sind eine Laufzeitbegrenzung der Hydrieranlage insgesamt sowie auch sicherheitstechnische Probleme wie das Auftreten von sogenannten "hot spots", die zu Rohrreißern führen können.Operational disadvantages result from the tendency to incrust the inside of the stove pipes and from coking reactions of the product in the pipes. Associated with this are a limitation of the runtime of the hydrogenation plant as a whole and also safety-related problems such as the occurrence of so-called "hot spots" which can lead to pipe tears.
Demgemäß besteht die Erfindungsaufgabe darin, die gesamte Wärmeführung des Prozesses unter Rückgewinnung der Reaktionswärme verfahrenstechnisch so zu gestalten, daß auf den extern zu beheizenden Einsatzproduktofen zur Aufheizung des Einsatzstromes verzichtet werden kann. In der Druckschrift DE 26 51 253 A1 ist zwar angegeben, daß bei einer Verfahrensweise ähnlich wie bei dem eingangs angegebenen Verfahren der durch Fremdwärme beheizte Vorerhitzer erheblich verkleinert oder unter Umständen sogar ganz weggelassen werden könne, dafür ist aber vorgesehen, daß eine in das Einsatzprodukt zurückzuführende Destillatfraktion in einem durch Fremdwärme beheizten Wärmetauscher erneut aufgeheizt wird. Die zusätzliche Aufheizung der Destillate bringe gegenüber der Aufheizung des Kohlebreis in einem Vorerhitzer den Vorteil der wesentlich geringeren Verkokungsneigung.Accordingly, the object of the invention is to design the entire heat management of the process by recovering the heat of reaction in such a way that there is no need for the externally heated feed furnace for heating the feed stream. In the
Gemäß der Erfindung wird die genannte Aufgabe bei dem Verfahren der eingangs angegebenen Art dadurch gelöst, daß das Heißabscheiderkopfprodukt im indirekten Wärmetausch seine Wärme an die genannten Einsatzströme abgibt und daß durch weitere Aufheizung des separat geführten Teiles des Hydriergases in einem Hydriergasaufheizer und anschließende Vereinigung mit dem durch indirekten Wärmetausch aufgeheizten Einsatzstrom die notwendige Eintrittstemperatur in den Sumpfphasereaktor erreicht wird.According to the invention, the above object is achieved in the method of the type mentioned above in that the hot separator head product emits its heat to the feed streams mentioned in indirect heat exchange and that by further heating the separately conducted part of the hydrogenation gas in a hydrogenation gas heater and then combining it with the indirect heat exchange heated feed stream the necessary inlet temperature is reached in the bottom phase reactor.
Das angegebene Verfahren ist geeignet, hydrierbare flüssige kohlenstoffhaltige Einsatzstoffe wie schwere Öle, Ölrückstände (Top- und Vakuumrückstand), Syncrude aus z. B. Ölschiefer, Teersanden, Schwerölen, Teeren und Pechen aus Steinkohle bzw. Braunkohle u. dgl. zu verarbeiten.The specified method is suitable for hydrating liquid carbon-containing feedstocks such as heavy oils, oil residues (top and vacuum residues), syncrude from e.g. B. oil shale, tar sands, heavy oils, tars and pitches from hard coal or lignite u. to process.
Mit Vorteil werden dem vorliegenden Verfahren aber auch neben den als Einsatzstoffe vorgesehenen schweren Ölen oder schweren mineralölhaltigen Rückständen Gemische von feingemahlener Kohle und der erfindungsgemäß vorgesehenen Einsatzstoffe als sogenannte Fremdöle ("Co-processing") zugeführt. Eine solche Arbeitsweise hat den Vorteil, daß die bei der Kohlehydrierung erforderlichen recycle-Ströme zur Anmaischung der feingemahlenen Kohle weitgehend oder ganz entfallen. Bevorzugt werden Gewichtsverhältnisse von Kohle und Fremdöl von 1 zu 5 bis 4 zu 5. Als einzusetzende Kohle kommen alle Sorten in Betracht, die wirtschaftlich hydriert werden können, z. B. typische Gasflammkohlen des Ruhrgebiets.In addition to the heavy materials intended as starting materials, the present process is also advantageous Oils or heavy mineral oil residues Mixtures of finely ground coal and the feedstocks provided according to the invention are supplied as so-called foreign oils ("co-processing"). Such a procedure has the advantage that the recycle streams required for the mashing of the finely ground coal are largely or completely eliminated. Weight ratios of coal and foreign oil of 1 to 5 to 4 to 5 are preferred. All types of coal which can be economically hydrogenated, for example, are suitable as the coal to be used. B. typical gas flame coal of the Ruhr area.
Es wurde gefunden, daß das Verfahren durch weitestgehende Rückgewinnung der Wärmeenergie der Reaktionsprodukte so gestaltet werden kann, daß ein Hydriergasaufheizer für einen separaten Teilstrom des Hydriergases genügt, um die beim Anfahren erforderliche Anspringtemperatur der Hydrierreaktion beim Eintritt in den Hydrierreaktor in der Sumpfphase aufzubringen und Wärmeverluste auszugleichen. Dieses Ergebnis konnte nur durch Optimierung der Verfahrensführung der Reaktionsprodukte und der Einsatzprodukte im Gegenstrom erreicht werden, und es ist überraschend, daß es gelingt, die zuzuführende Wärmeenergie über einen Teilstrom des Hydriergases ohne Fremdbeheizung der flüssigen oder fest-flüssigen Einsatzprodukte in das Verfahren einzubringen.It has been found that the process can be designed by largely recovering the thermal energy of the reaction products so that a hydrogenation gas heater is sufficient for a separate partial flow of the hydrogenation gas in order to apply the start-up temperature of the hydrogenation reaction required when starting up into the hydrogenation reactor in the bottom phase and to compensate for heat losses . This result could only be achieved by optimizing the process control of the reaction products and the feed products in countercurrent, and it is surprising that the thermal energy to be supplied can be introduced into the process via a partial stream of the hydrogenation gas without external heating of the liquid or solid-liquid feed products.
Als Hydriergasaufheizer, nachfolgend auch als Hydriergasöfen bezeichnet, kommen Umwälzöfen, vorzugsweise aber auch Strahlungsöfen, in Betracht, in denen eine Aufheizung auf eine Temperatur von 300 bis 650 °C, vorzugsweise 490 bis 550 °C erfolgt.Circulation furnaces come as hydrogenation gas heaters, hereinafter also referred to as hydrogenation gas furnaces, but preferably also radiation ovens, in which heating to a temperature of 300 to 650 ° C., preferably 490 to 550 ° C. takes place.
In weiterer Ausgestaltung des vorgeschlagenen Verfahrens werden der Einsatzstrom (3) durch drei Wärmetauscher (18, 19, 20) und der separat aufzuheizende Hydriergasstrom (5) vor Eintritt in den Hydriergasofen (24) durch drei Wärmetauscher (21, 22, 23) im Gegenstrom zu dem Heißabscheiderkopfprodukt geführt.In a further embodiment of the proposed method, the feed stream (3) through three heat exchangers (18, 19, 20) and the separately heated hydrogen gas stream (5) before entering the hydrogenation gas furnace (24) through three heat exchangers (21, 22, 23) in countercurrent led to the hot separator head product.
Bei der Aufteilung der Gesamt-Hydriergasmenge auf die beiden Teilströme kann auch so vorgegangen werden, daß für den Einsatzstrom Frischwasserstoff als Feed und für den zweiten Teilstrom des Hydriergases das Kreislaufhydriergas vorgesehen werden.When dividing the total amount of hydrogenation gas between the two partial streams, it is also possible to proceed in such a way that the circulating hydrogenation gas is provided for the feed stream fresh hydrogen as feed and for the second partial stream of the hydrogenation gas.
Dabei tritt Strom (9) in Abstromrichtung nacheinander mit dem Einsatzstrom (3) in Wärmetauscher (20) und dem Teilstrom des Hydriergases (5) in Wärmetauscher (23) in Wärmetauschbeziehung und durchläuft einen Reaktor (27) zur Hydrierung in der Gasphase an einem Festbettkontakt. Der in Reaktor (27) raffinierte Produktstrom durchläuft als Strom (10) Wärmetauscher (19) und Wärmetauscher (22) in Wärmetauschbeziehung mit Strom (3) bzw. Strom (5) sowie einen Zwischenabscheider (28) mit Abtrennung einer Heißölfraktion (11). Der von Abscheider (28) abgezogene Reststrom (12) gibt in den Wärmetauschern (18) und (21) seine restliche für die Aufheizung der Einsatzprodukte verwertbare Wärme an Strom (3) und Strom (5) ab und wird einem Kaltabscheider (29) zugeführt, in dem eine Abtrennung von Abwasser und Abgas sowie die Gewinnung einer Kaltölfraktion (13) und Rückführung des Kreislaufhydrierungsgasanteils als Strom (15) über Kompressor (30) in den Prozeß erfolgen.In this case, stream (9) in the downstream direction comes into heat exchange relationship with the feed stream (3) in the heat exchanger (20) and the partial stream of the hydrogenation gas (5) in the heat exchanger (23) and passes through a reactor (27) for hydrogenation in the gas phase at a fixed bed contact . The product stream refined in reactor (27) passes as stream (10) heat exchanger (19) and heat exchanger (22) in heat exchange relationship with stream (3) or stream (5) and an intermediate separator (28) with separation of a hot oil fraction (11). The residual stream (12) drawn off by the separator (28) gives the rest of the heat exchangers (18) and (21) for heating the Use products utilizable heat to electricity (3) and electricity (5) and is fed to a cold separator (29), in which a separation of waste water and exhaust gas as well as the recovery of a cold oil fraction (13) and recycling of the cycle hydrogenation gas as stream (15) via compressor (30) done in the process.
Zur Temperaturregelung im Sumpfphasereaktor (25) und im Heißabscheider (26) wird mit Vorteil ein Teil des Kreislaufgasstroms (16) als Quenchgasstrom zur Verfügung gehalten und im Bedarfsfall eingespeist.For temperature control in the bottom phase reactor (25) and in the hot separator (26), part of the circulating gas stream (16) is advantageously kept available as a quench gas stream and fed in if necessary.
Im Anschluß an den Kaltabscheider (29) kann in üblicher Weise eine Gaswäsche zur Aufarbeitung des Kreislaufhydriergasanteiles vorgesehen werden. Durch eine derartige Aufarbeitung wird durch Entfernung der in der Gaswäsche mittels Waschflüssigkeit löslichen C₁- bis C₄-Bestandteile ein ausreichender Wasserstoffpartialdruck in dem Hydriergassystem gewährleistet.Following the cold separator (29), a gas scrubber can be provided in the usual way for working up the circulating hydrogen gas fraction. Such a work-up ensures a sufficient hydrogen partial pressure in the hydrogenation gas system by removing the C₁ to C₄ components which are soluble in the gas scrubbing by means of washing liquid.
Der separate Teilstrom aus der insgesamt einzusetzenden Hydriergasmenge kann 20 bis 95, vorzugsweise 40 bis 80 % der insgesamt erforderlichen Hydriergasmenge ausmachen.The separate partial stream from the total amount of hydrogenation gas to be used can make up 20 to 95, preferably 40 to 80% of the total amount of hydrogenation gas required.
Das vorliegende Verfahren wird nachfolgend anhand des Schemas der Zeichnung mit den angegebenen Bezugszeichen weiter erläutert.The present method is explained in more detail below with the aid of the diagram in the drawing with the specified reference symbols.
Der aus einer Suspension mit dem Additiv bzw. Katalysator bestehende Strom der Einsatzstoffe (1) wird mit einem aus Kreislaufhydriergas, Strom (15), über Kompressor (30) unter Einspeisung von Frischwasserstoff, Strom (17), zusammengesetzten Teilstrom des Hydriergases (2) zu Strom (3) vereinigt und mittels indirektem Wärmeaustausch in den Apparaten (18), (19) und (20) auf die Bedingungen von Strom (4) vorgewärmt.The stream of feedstocks (1) consisting of a suspension with the additive or catalyst is mixed with a partial stream of the hydrogenation gas (2) composed of circulating hydrogenation gas, stream (15), via compressor (30) while feeding in fresh hydrogen, stream (17). combined to form stream (3) and preheated to the conditions of stream (4) by means of indirect heat exchange in the apparatuses (18), (19) and (20).
Der separate Hydriergasstrom (5) wird ebenfalls im indirekten Wärmeaustausch in den Apparaten (21), (22) und (23) vorgewärmt und in Hydriergasaufheizer (24) auf die notwendige Temperatur erhitzt, so daß in der Mischung mit dem Stoffstrom (4) die erforderliche Reaktoreintrittstemperatur in Reaktor (25) für Strom (7) erreicht wird.The separate hydrogenation gas stream (5) is also preheated in indirect heat exchange in the apparatuses (21), (22) and (23) and heated to the necessary temperature in hydrogenation gas heater (24), so that the mixture with the material stream (4) required reactor inlet temperature in reactor (25) for stream (7) is reached.
Im Reaktor (25) bzw. einer Kaskade hintereinander geschalteter Reaktoren fallen die gewünschten Produkte an, die im Heißabscheider (26) in einen Rückstandsstrom (8) und in einen Kopfstrom (9) aufgetrennt werden.The desired products are obtained in the reactor (25) or a cascade of reactors connected in series, which are separated in the hot separator (26) into a residue stream (8) and into a top stream (9).
Der Kopfstrom (9) wird zur Vorwärmung im Gegenstrom zu Einsatzstrom (3) und Hydriergasstrom (5) in den vorgenannten Apparaten (18), (19), (20), (21), (22) und (23) genutzt. Die in der Figur gezeigte Schaltung sieht einen integrierten Gasphasereaktor (27) zwecks Raffination und weiterer Entfernung insbesondere der O-, S- und N-haltigen Heteroatomanteile vor. Gasphasereaktor (27) ist mit Vorteil zwischen Apparat (23) und Apparat (19) geschaltet.The top stream (9) is used for preheating in countercurrent to the feed stream (3) and hydrogenation gas stream (5) in the aforementioned apparatuses (18), (19), (20), (21), (22) and (23). The circuit shown in the figure provides an integrated gas phase reactor (27) for the purpose of refining and further removal, in particular of the O, S and N-containing heteroatom components. Gas phase reactor (27) is advantageously connected between apparatus (23) and apparatus (19).
Die aufgrund des Wärmeentzuges in den Wärmetauschern kondensierten Produkte werden in Zwischenabscheider (28) und in Kaltabscheider (29) gesammelt. Die Kondensate werden als Heißöl (11) und Kaltöl (13) aus dem Hochdruckkreislauf ausgeschleust. Nach dem Heißölabzug kann Wasser eingespritzt werden, um die Versalzung der nachgeschalteten Wärmeaustauscher zu vermeiden.The products condensed in the heat exchangers due to the removal of heat are collected in intermediate separators (28) and in cold separators (29). The condensates are discharged from the high-pressure circuit as hot oil (11) and cold oil (13). After the hot oil has been drawn off, water can be injected in order to avoid salinization of the downstream heat exchangers.
Das beim Hydrierprozeß gebildete Reaktionswasser wird gegebenenfalls zusammen mit dem Einspritzwasser im Kaltabscheider (29) abgetrennt und als Strom (14) aus dem Hochdruckkreislauf ausgeschleust. Es enthält u. a. die durch Raffination entfernten Heteroatomverbindungen in Form der in dem Abwasser gelösten einfachen Wasserstoffverbindungen H₂S und insbesondere NH₃.The water of reaction formed in the hydrogenation process is optionally separated together with the injection water in the cold separator (29) and discharged as stream (14) from the high-pressure circuit. It contains u. a. the heteroatom compounds removed by refining in the form of the simple hydrogen compounds H₂S and in particular NH₃ dissolved in the waste water.
Je nach Auslegung der Wärmeaustauscher bzw. Anordnung des Zwischenabscheiders kann die Temperatur im Zwischenabscheider innerhalb eines bestimmten Bereiches frei gewählt werden.Depending on the design of the heat exchanger or the arrangement of the intermediate separator, the temperature in the intermediate separator can be freely selected within a certain range.
Das in Kaltabscheider (29) über Kopf gehende Restgas wird, ggf. nach Ausschleusung eines gewissen Anteils, mit einem Kreislaufkompressor (30) zurückgeführt. Dem Rückführgas wird zur Temperaturführung der Reaktoren und des Heißabscheiders Kaltgas als Strom (16) entnommen. Der für die Reaktion erforderliche Frischwasserstoff wird als Strom (17) zugegeben. Es kann auch vorgesehen werden, den Strom (2) als Frischwasserstoffstrom zuzugeben.The residual gas going overhead in the cold separator (29) is returned with a circuit compressor (30), if necessary after a certain proportion has been discharged. The return gas is cold gas as a stream for temperature control of the reactors and the hot separator (16) taken. The fresh hydrogen required for the reaction is added as stream (17). Provision can also be made to add stream (2) as a fresh hydrogen stream.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873741105 DE3741105A1 (en) | 1987-12-04 | 1987-12-04 | METHOD FOR HYDROGENATING LIQUID CARBONATED SUBSTANCES |
DE3741105 | 1987-12-04 |
Publications (3)
Publication Number | Publication Date |
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EP0318903A2 true EP0318903A2 (en) | 1989-06-07 |
EP0318903A3 EP0318903A3 (en) | 1990-05-02 |
EP0318903B1 EP0318903B1 (en) | 1992-11-25 |
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Application Number | Title | Priority Date | Filing Date |
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EP88119848A Expired - Lifetime EP0318903B1 (en) | 1987-12-04 | 1988-11-29 | Process for the hydrogenation of liquid carbon-containing feedstocks |
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Country | Link |
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US (1) | US4983279A (en) |
EP (1) | EP0318903B1 (en) |
JP (1) | JPH01207386A (en) |
AU (1) | AU620056B2 (en) |
CA (1) | CA1316862C (en) |
DE (2) | DE3741105A1 (en) |
PL (1) | PL158169B1 (en) |
ZA (1) | ZA889071B (en) |
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US5738779A (en) * | 1996-07-18 | 1998-04-14 | Texaco Inc. | Hydrotreating process with two phase flow splitting and heat recovery |
US8944069B2 (en) * | 2006-09-12 | 2015-02-03 | Vidacare Corporation | Assemblies for coupling intraosseous (IO) devices to powered drivers |
EP2792729A1 (en) | 2013-04-17 | 2014-10-22 | XTLgroup bv | Process for hydroprocessing a liquid feed comprising hydrocarbons into fuel components |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3505553A1 (en) * | 1985-02-18 | 1986-08-21 | Veba Oel Entwicklungs-Gesellschaft mbH, 4650 Gelsenkirchen | METHOD FOR PRETREATING TREATMENT PRODUCTS FOR CARBON HYDROGENATION |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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AU522767B2 (en) * | 1979-08-24 | 1982-06-24 | Gulf Research & Development Company | Coal hydrogenation |
AU522787B2 (en) * | 1979-08-24 | 1982-06-24 | Gulf Research & Development Company | Coal liquefaction |
DE2936008A1 (en) * | 1979-09-06 | 1981-04-02 | Saarbergwerke AG, 6600 Saarbrücken | METHOD FOR HYDROGENATING COAL |
DE3105030A1 (en) * | 1981-02-12 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE CONTINUOUS PRODUCTION OF HYDROCARBON OILS FROM COAL BY PRESSURE HYDROGENATION IN TWO STAGES |
CA1238287A (en) * | 1984-08-04 | 1988-06-21 | Werner Dohler | Process for the production of reformer feed and heating oil or diesel oil from coal |
EP0177676B1 (en) * | 1984-09-13 | 1992-03-04 | Ruhrkohle Aktiengesellschaft | Process carried out by heat recuperation for suspension hydrogenation with integrated gas phase hydrogenation |
DE3523709A1 (en) * | 1985-07-03 | 1987-01-08 | Veba Oel Entwicklungs Gmbh | METHOD FOR PRETREATING THE APPLICATION PRODUCTS FOR HEAVY OIL HYDRATION |
-
1987
- 1987-12-04 DE DE19873741105 patent/DE3741105A1/en active Granted
-
1988
- 1988-11-28 CA CA000584350A patent/CA1316862C/en not_active Expired - Fee Related
- 1988-11-29 EP EP88119848A patent/EP0318903B1/en not_active Expired - Lifetime
- 1988-11-29 DE DE8888119848T patent/DE3876219D1/en not_active Expired - Fee Related
- 1988-12-01 AU AU26458/88A patent/AU620056B2/en not_active Ceased
- 1988-12-02 ZA ZA889071A patent/ZA889071B/en unknown
- 1988-12-02 PL PL1988276160A patent/PL158169B1/en unknown
- 1988-12-02 US US07/279,089 patent/US4983279A/en not_active Expired - Fee Related
- 1988-12-03 JP JP63305173A patent/JPH01207386A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3505553A1 (en) * | 1985-02-18 | 1986-08-21 | Veba Oel Entwicklungs-Gesellschaft mbH, 4650 Gelsenkirchen | METHOD FOR PRETREATING TREATMENT PRODUCTS FOR CARBON HYDROGENATION |
Also Published As
Publication number | Publication date |
---|---|
US4983279A (en) | 1991-01-08 |
EP0318903A3 (en) | 1990-05-02 |
PL276160A1 (en) | 1989-07-24 |
DE3741105C2 (en) | 1990-01-04 |
DE3876219D1 (en) | 1993-01-07 |
JPH01207386A (en) | 1989-08-21 |
AU620056B2 (en) | 1992-02-13 |
DE3741105A1 (en) | 1989-06-15 |
AU2645888A (en) | 1989-06-08 |
ZA889071B (en) | 1989-08-30 |
PL158169B1 (en) | 1992-08-31 |
CA1316862C (en) | 1993-04-27 |
EP0318903B1 (en) | 1992-11-25 |
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