EP0301172B1 - Hydrogenation of carbon-containing feedstocks - Google Patents
Hydrogenation of carbon-containing feedstocks Download PDFInfo
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- EP0301172B1 EP0301172B1 EP88105773A EP88105773A EP0301172B1 EP 0301172 B1 EP0301172 B1 EP 0301172B1 EP 88105773 A EP88105773 A EP 88105773A EP 88105773 A EP88105773 A EP 88105773A EP 0301172 B1 EP0301172 B1 EP 0301172B1
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- European Patent Office
- Prior art keywords
- cold
- slop
- hydrogenation
- fed
- upstream
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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
- C10G1/004—Inhibiting of corrosion
Definitions
- the invention relates to the introduction of alkali donors, especially as a sodium compound, and cold slop in the common high-pressure circuit of a bottom phase hydrogenation with integrated gas phase hydrogenation.
- the feedstocks are also supplied with an alkali dispenser, especially as a sodium compound, so that the chlorine is chemically bound from the feedstocks and discharged from the process together with the hydrogenation residue. Otherwise chlorine corrosion and salt formation (eg ammonium chloride) can occur in the condensation path of the oil products.
- salt formation occurs to a greater extent in accordance with the chemical equation NH s + HCL - NH 4 CL (ammonium chloride), since the NH 3 concentration in the circulating gas is increased as a result of the chemical breakdown of the nitrogen in the refined products.
- the sodium is mixed with the liquid carbonaceous feedstocks as Na 2 S in solid form.
- the Na 2 S dissolves well in aromatic oils - especially raw coal oils from the bottom phase hydrogenation. With refined - or low aromatic - feed oils, the solubility for Na 2 S is very low.
- the Na ⁇ S melts above 110 ° C and gradually releases its hydration water when it is heated further in the heating path. In cooler zones, the Na 2 S can then recrystallize and thus block pipes, fittings and containers.
- soda Na z COs
- Soda has the disadvantage compared to Na 2 S that soda has a specifically lower sodium content and the alkalinity compared to Na 2 S is reduced.
- cold slop When operating the bottom phase hydrogenation with integrated gas phase hydrogenation, cold slop also falls - a mixture of partially unrefined product oils and phenolic water - on. This cold slop will not be worked up, as is customary in the bottom phase hydrogenation, in atmospheric distillation, in which the refined oil products and, if appropriate, the refined solvent are separated into boiling fractions.
- Kaltslop contains unrefined oils and phenolic process water, which are not brought into contact with the refined oils in atmospheric distillation. According to the invention, the cold slop is run over the gas phase hydrogenation and refined.
- the object of the invention is to feed the alkali dispenser - especially Na 2 S - into the high-pressure circuit while avoiding precipitation and clogging, and also to carry out cold slop processing without using an additional atmospheric distillation.
- the object of the alkali donor supply is achieved according to the invention in that the alkali donor - specifically Na 2 S - is fed as an aqueous solution into the heating path or upstream of the sump phase reactor or into the sump phase reactor where heating and evaporation of the aqueous Na 2 S solution takes place.
- the Na 2 S is then in finely divided form in the reaction mixture.
- the cold slop workup in the bottom phase hydrogenation with integrated gas phase hydrogenation is achieved according to the invention in that the cold slot is fed into the heating path or upstream of the bottom phase reactor or into the bottom phase reactor.
- the cold slop is expediently added to the hot separator head product. In this way, the addition of cold slops also supports the temperature setting in the gas phase reactor.
- FIG 1 shows an example of use from coal hydrogenation with an integrated refining stage.
- the mash (1) consisting of ground coal, catalyst and oil, is mixed with a partial stream of the hydrogenation gas (2) in the mash heat exchangers (24), (25) by indirect heat exchange with the hot separator head product stream (9) and the gas phase product stream (10), warmed up.
- Most of the hydrogenation gas consisting of cycle gas (15) and fresh hydrogen (17), is heated as stream (5) in the gas heat exchangers (26), (28), (29) and the heating furnace (30) and together with the preheated one Mash fed to the bottom phase reactor (31).
- the aqueous Na 2 S solution is passed alone or together with the cold slop as stream (18) by means of a high-pressure pump (37) into the bottom phase reactor.
- the heating or evaporation of aqueous Na 2 S solution and cold slop in the bottom phase reactor (31) also serves to partially dissipate the heat of reaction and thus reduces the amount of quenching gas (16) required for setting the temperature in the bottom phase reactor.
- the aqueous Na 2 S solution can also be fed in with the cold slop as stream (19) upstream of the bottom phase reactor (31) or as stream (20) between the mash heat exchangers (24) and (25). If the amount of cold slop differs in time, the oven (30) maintains a constant temperature of the Reactor insert (7) set.
- the cold slop - alone or together with vacuum gas oil - is fed into the hot separator top product stream (9) by means of a high-pressure pump (38).
- a high-pressure pump (38) Different feed rates as material flow (21) before or as material flow (22) after the mash heat exchanger (25) make it possible to compensate for different heat transfer rates of the heat exchanger (25). This facilitates a constant temperature setting in the gas phase reactor (33).
- the chlorine is largely bound in the blowdown (8). This prevents salt formation in the material flow (10) and in the gas heat exchanger (28). Water injection to avoid salt formation or to dissolve salts is not necessary in normal operation. Preventive injection of demineralized water (23) behind the intermediate separator (34) into the material flow (12) can be useful if the dosage of the Na 2 S solution is not matched to fluctuations in the chlorine content due to time-related lag. VE water injection also supports the leaching of ammonia in the cycle gas, which has a desirable effect on the salt formation balance in the suppressive direction. Density differences then separate cold oil (13) and water (14) in the cold separator (35) in a manner known per se.
Description
Die Erfindung betrifft die Einbringung von Alkalispendern, speziell als Natriumverbindung, und Kaltslop in den gemeinsamen Hochdruckkreislauf einer Sumpfphasehydrierung mit integrierter Gasphasehydrierung.The invention relates to the introduction of alkali donors, especially as a sodium compound, and cold slop in the common high-pressure circuit of a bottom phase hydrogenation with integrated gas phase hydrogenation.
Bei der Hydrierung von kohlenstoffhaltigen Einsatzstoffen - Kohle, Teeren, schwersiedenden Ölen - wird den Einsatzstoffen außer einem Katalysator auch ein Alkalispender, speziell als Natriumverbindung zugeführt, damit das Chlor aus den Einsatzstoffen chemisch gebunden und gemeinsam mit dem Hydrierrückstand aus dem Prozeß herausgeschleust wird. Anderenfalls können im Kondensationspfad der Ölprodukte Chlorkorrosion und Salzbildung (z.B. Ammoniumchlorid) auftreten. Bei der Sumpfhphasehydrierung mit nachgeschalteter Gasphasehydrierung tritt entsprechend der chemischen Gleichung NHs + HCL--NH4CL (Ammoniumchlorid) die Salzbildung verstärkt auf, da infolge des chemischen Abbaus des Stickstoffs der raffinierten Produkte die NH3-Konzentration im Kreislaufgas erhöht ist.In the hydrogenation of carbonaceous feedstocks - coal, tars, high-boiling oils - in addition to a catalyst, the feedstocks are also supplied with an alkali dispenser, especially as a sodium compound, so that the chlorine is chemically bound from the feedstocks and discharged from the process together with the hydrogenation residue. Otherwise chlorine corrosion and salt formation (eg ammonium chloride) can occur in the condensation path of the oil products. In the bottoms phase hydrogenation with downstream gas phase hydrogenation, salt formation occurs to a greater extent in accordance with the chemical equation NH s + HCL - NH 4 CL (ammonium chloride), since the NH 3 concentration in the circulating gas is increased as a result of the chemical breakdown of the nitrogen in the refined products.
Bei der konventionellen Hydrierung - speziell Kohlehydrierung - wird das Natr:um als Na2S in fester Form den flüssigen kohlenstoffhaltigen Einsatzstoffen zugemischt Das Na2S löst sich in aromatenreichen Einsatzölen - speziell rohen Kohle- ölen aus der Sumpfphasehydrierung - gut auf. Bei raffinierten - bzw. aromatenarmen - Einsatzölen ist die Lösefähigkeit für Na2S sehr gering. Oberhalb 110 °C schmilzt das NaεS und gibt bei weiterer Erwärmung im Aufheizpfad stufenweise sein Hydrationswasser ab. In kühleren Zonen kann es dann zu Rekristallisation des Na2S und somit zu Verstopfungen von Rohrleitungen, Armaturen und Behältern kommen.In conventional hydrogenation - especially coal hydrogenation - the sodium is mixed with the liquid carbonaceous feedstocks as Na 2 S in solid form. The Na 2 S dissolves well in aromatic oils - especially raw coal oils from the bottom phase hydrogenation. With refined - or low aromatic - feed oils, the solubility for Na 2 S is very low. The NaεS melts above 110 ° C and gradually releases its hydration water when it is heated further in the heating path. In cooler zones, the Na 2 S can then recrystallize and thus block pipes, fittings and containers.
Als Alkalispender wird außer Na2S auch Soda (NazCOs) verwendet. Soda hat jedoch gegenüber Na2S den Nachteil, daß Soda einen spezifisch geringeren Natrium-Anteil hat und die Alkalität gegenüber Na2S reduziert ist.In addition to Na 2 S, soda (Na z COs) is also used as an alkali dispenser. Soda has the disadvantage compared to Na 2 S that soda has a specifically lower sodium content and the alkalinity compared to Na 2 S is reduced.
Durch Alkalieinspeisung als wässerige Na2S-Lösung wird Chlor gebunden und Salzbildung (Ammoniumchlorid) in den Gaswärmeaustauschern verhindert.
- Na2S in fester oder geschmolzener Form hat eine schlechte Lösefähigkeit in raffiniertem Lösungsmittel. Es entstehen Verstopfungen im Bereich der Anmaischung. Wird NaεS in wässriger Lösung in den Aufheizpfad oder in den Sumpfphasereaktor eingespeist, treten diese Schwierigkeiten nicht auf.
- Na 2 S in solid or molten form has poor solubility in refined solvent. There are blockages in the area of mashing. If NaεS in aqueous solution is fed into the heating path or into the bottom phase reactor, these difficulties do not arise.
Bei dem Betrieb der Sumpfphasehydrierung mit integrierter Gasphasehydrierung fällt auch Kaltslop - ein Gemisch aus z.T. nichtraffinierten Produktölen und phenolhaltigem Wasser - an. Dieser Kaltslop wird nicht - wie sonst üblich bei der Sumpfphasehydrierung - in der atmosphärischen Destillation, in welcher die raffinierten Olprodukte und ggf. das raffinierte Lösungsmittel in Siedefraktionen aufgetrennt werden, aufgearbeitet werden.When operating the bottom phase hydrogenation with integrated gas phase hydrogenation, cold slop also falls - a mixture of partially unrefined product oils and phenolic water - on. This cold slop will not be worked up, as is customary in the bottom phase hydrogenation, in atmospheric distillation, in which the refined oil products and, if appropriate, the refined solvent are separated into boiling fractions.
D. h. Kaltslop enthält unraffinierte Öle und phenolhaltiges Prozeßwasser, welche in der atmosphärischen Destillation nicht mit den raffinierten Ölen in Berührung gebracht werden. Nach der Erfindung wird der Kaltslop über die Gasphsehydrierung gefahren und raffiniert.I.e. Kaltslop contains unrefined oils and phenolic process water, which are not brought into contact with the refined oils in atmospheric distillation. According to the invention, the cold slop is run over the gas phase hydrogenation and refined.
Der Erfindung liegt die Aufgabe zugrunde, den Alkalispender - speziell Na2S - unter Vermeidung einer Ausfällung und Verstopfung in den Hochdruckkreislauf einzuspeisen und weiterhin die Kaltslopaufarbeitung ohne Verwendung einer zusätzlichen atmosphärischen Destillation durchzuführen.The object of the invention is to feed the alkali dispenser - especially Na 2 S - into the high-pressure circuit while avoiding precipitation and clogging, and also to carry out cold slop processing without using an additional atmospheric distillation.
Die Aufgabe der Alkalispenderzufuhr wird erfindungsgemäß dadurch gelöst, daß der Alkalispender - speziell Na2S - als wässerige Lösung in den Aufheizpfad oder vor dem Sumpfphasereaktor oder in den Sumpfphasereaktor eingespeist wird, wo eine Aufheizung und Verdampfung der wässerigen Na2S-Lösung stattfindet. Das Na2S liegt dann in fein verteilter Form im Reaktionsgemisch vor.The object of the alkali donor supply is achieved according to the invention in that the alkali donor - specifically Na 2 S - is fed as an aqueous solution into the heating path or upstream of the sump phase reactor or into the sump phase reactor where heating and evaporation of the aqueous Na 2 S solution takes place. The Na 2 S is then in finely divided form in the reaction mixture.
Die Kaltslopaufarbeitung bei der Sumpfphasehydrierung mit integrierter Gasphasehydrierung wird erfindungsgemäß dadurch gelöst, daß der Kaltslop in den Aufheizpfad oder vor dem Sumpfphasereaktor oder in den Sumpfphasereaktor eingespeist wird.The cold slop workup in the bottom phase hydrogenation with integrated gas phase hydrogenation is achieved according to the invention in that the cold slot is fed into the heating path or upstream of the bottom phase reactor or into the bottom phase reactor.
Zweckmäßig erfolgt eine gemeinsame Einspeisung von wässeriger Na2S-Lösung und Kaltslop in den Prozeß, um zusätzliche Hochdruckeinspeisepumpen einzusparen.It is advisable to jointly feed aqueous Na 2 S solution and cold slop into the process in order to save additional high-pressure feed pumps.
Soll der Kaltslop getrennt von der Na2S-Lösung in den Hochdruck-Kreislauf eingespeist werden, so erfolgt die Kaltslopzugabe zweckmäßig in das Heißabscheiderkopfprodukt. Auf diese Weise unterstützt die Kaltslopzugabe gleichzeitig die Temperatureinstellung im Gasphasereaktor.If the cold slop is to be fed into the high-pressure circuit separately from the Na 2 S solution, the cold slop is expediently added to the hot separator head product. In this way, the addition of cold slops also supports the temperature setting in the gas phase reactor.
In Fig. 1 wird ein Anwendungsbeispiel aus der Kohlehydrierung mit integrierter Raffinationsstufe dargestellt.1 shows an example of use from coal hydrogenation with an integrated refining stage.
Die Maische (1), bestehend aus gemahlener Kohle, Katalysator und ÖI, wird mit einem Teilstrom des Hydriergases (2) in den Maischewärmeaustauschern (24), (25) durch indirekten Wärmeaustausch mit dem Heißabscheiderkopfproduktstrom (9) und dem Gasphaseproduktstrom (10), aufgewärmt. Der größte Teil des Hydriergases, bestehend aus Kreislaufgas (15) und Frischwasserstoff (17), wird als Strom (5) in den Gaswärmeaustauschern (26), (28), (29) und dem Aufheizofen (30) aufgeheizt und gemeinsam mit der vorgewärmten Maische dem Sumpfphasereaktor (31) zugeführt. Die wässerige Na2S-Lösung wird allein oder gemeinsam mit dem Kaltslop als Strom (18) mittels Hochdruckpumpe (37) in den Sumpfphasereaktor geleitet. Die Aufheizung bzw. Verdampfung von wässeriger Na2S-Lösung und Kaltslop im Sumpfphasereaktor (31) dient gleichzeitig zur teilweisen Abführung der Reaktionswärme und reduziert somit die benötigte Quenchgasmenge (16) zur Temperatureinstellung im Sumpfphasereaktor.The mash (1), consisting of ground coal, catalyst and oil, is mixed with a partial stream of the hydrogenation gas (2) in the mash heat exchangers (24), (25) by indirect heat exchange with the hot separator head product stream (9) and the gas phase product stream (10), warmed up. Most of the hydrogenation gas, consisting of cycle gas (15) and fresh hydrogen (17), is heated as stream (5) in the gas heat exchangers (26), (28), (29) and the heating furnace (30) and together with the preheated one Mash fed to the bottom phase reactor (31). The aqueous Na 2 S solution is passed alone or together with the cold slop as stream (18) by means of a high-pressure pump (37) into the bottom phase reactor. The heating or evaporation of aqueous Na 2 S solution and cold slop in the bottom phase reactor (31) also serves to partially dissipate the heat of reaction and thus reduces the amount of quenching gas (16) required for setting the temperature in the bottom phase reactor.
Die wässerige Na2S-Lösung kann auch mit dem Kaltslop als Strom (19) vor den Sumpfphasereaktor (31) oder als Strom (20) zwischen den Maischewärmeaustauschern (24) und (25) eingespeist werden. Bei zeitlich unterschiedlichen Kaltslopmengen wird mit dem Ofen (30) eine konstante Temperatur des Reaktoreinsatzes (7) eingestellt.The aqueous Na 2 S solution can also be fed in with the cold slop as stream (19) upstream of the bottom phase reactor (31) or as stream (20) between the mash heat exchangers (24) and (25). If the amount of cold slop differs in time, the oven (30) maintains a constant temperature of the Reactor insert (7) set.
Alternativ wird der Kaltslop - allein oder gemeinsam mit Vakuumgasöl mittels Hochdruckpumpe (38) in den Heißabscheiderkopfproduktstrom (9) eingespeist. Durch unterschiedliche Einspeisungen als Stoffstrom (21) vor oder als Stoffstrom (22) nach dem Maischewärmeaustauscher (25) können unterschiedliche Wärmeübertragungsleistungen des Wärmeaustauschers (25) kompensiert werden. Hierdurch wird eine konstante Temperatureinstellung im Gasphasereaktor (33) erleichtert.Alternatively, the cold slop - alone or together with vacuum gas oil - is fed into the hot separator top product stream (9) by means of a high-pressure pump (38). Different feed rates as material flow (21) before or as material flow (22) after the mash heat exchanger (25) make it possible to compensate for different heat transfer rates of the heat exchanger (25). This facilitates a constant temperature setting in the gas phase reactor (33).
Durch die Einspeisung der wässerigen Na2S-Lösung in den Prozeß wird das Chlor weitgehend in den Abschlamm (8) gebunden. Somit wird die Salzbildung im Stoffstrom (10) und im Gaswärmeaustauscher (28) verhindert. Eine Wassereinspritzung zur Vermeidung von Salzbildung oder zur Auflösung von Salzen ist bei Normalbetrieb nicht notwendig. Präventiv kann die Einspritzung von VE-Wasser (23) hinter den Zwischenabscheider (34) in den Stoffstrom (12) dann von Nutzen sein, wenn die Dosierung der Na2S-Lösung auf Schwankungen des Chlorgehaltes durch zeitlich bedingten Nachlauf nicht abgestimmt ist. Außerdem unterstützt die VE-Wassereinspritzung die Auswaschung von Ammoniak im Kreislaufgas, was sich auf das Salzbildungsgleichgewicht in unterdrückender Richtung wünschenswert auswirkt. Mittels Dichteunterschiede erfolgt dann eine Trennung von Kaltöl (13) und Wasser (14) im Kaltabscheider (35) in an sich bekannter Weise.By feeding the aqueous Na 2 S solution into the process, the chlorine is largely bound in the blowdown (8). This prevents salt formation in the material flow (10) and in the gas heat exchanger (28). Water injection to avoid salt formation or to dissolve salts is not necessary in normal operation. Preventive injection of demineralized water (23) behind the intermediate separator (34) into the material flow (12) can be useful if the dosage of the Na 2 S solution is not matched to fluctuations in the chlorine content due to time-related lag. VE water injection also supports the leaching of ammonia in the cycle gas, which has a desirable effect on the salt formation balance in the suppressive direction. Density differences then separate cold oil (13) and water (14) in the cold separator (35) in a manner known per se.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3725367 | 1987-07-31 | ||
| DE3725367A DE3725367C1 (en) | 1987-07-31 | 1987-07-31 | Process for the hydrogenation of carbonaceous feedstocks |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0301172A2 EP0301172A2 (en) | 1989-02-01 |
| EP0301172A3 EP0301172A3 (en) | 1989-07-26 |
| EP0301172B1 true EP0301172B1 (en) | 1990-12-19 |
Family
ID=6332766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88105773A Expired - Lifetime EP0301172B1 (en) | 1987-07-31 | 1988-04-12 | Hydrogenation of carbon-containing feedstocks |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0301172B1 (en) |
| JP (1) | JPS6436686A (en) |
| AU (1) | AU609153B2 (en) |
| BR (1) | BR8803775A (en) |
| DE (2) | DE3725367C1 (en) |
| PL (1) | PL151645B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2573154B1 (en) | 2005-04-29 | 2019-07-24 | Altaca Insaat ve Dis Ticaret A.S. | Apparatus for converting organic material |
| EP1879981B1 (en) | 2005-04-29 | 2014-07-23 | Altaca Insaat ve Dis Ticaret A.S. | Method for converting organic material into hydrocarbon fuels |
| WO2007059783A1 (en) * | 2005-11-24 | 2007-05-31 | Scf Technologies A/S | Method and apparatus for converting organic material using microwave excitation |
| CN104388118B (en) * | 2014-11-24 | 2017-01-04 | 湖南省馨盛能源开发有限责任公司 | The technological process of producing diesel by coal tar |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE692631C (en) * | 1934-09-26 | 1940-06-24 | I G Farbenindustrie Akt Ges | Process for preventing corrosion in the heat treatment of coal, tars, mineral oils and the like like |
| DE3038309A1 (en) * | 1980-10-10 | 1982-05-19 | Ruhrkohle Ag, 4300 Essen | COAL LIQUIDATION |
-
1987
- 1987-07-31 DE DE3725367A patent/DE3725367C1/en not_active Expired
-
1988
- 1988-04-12 EP EP88105773A patent/EP0301172B1/en not_active Expired - Lifetime
- 1988-04-12 DE DE8888105773T patent/DE3861308D1/en not_active Expired - Fee Related
- 1988-07-14 JP JP63173851A patent/JPS6436686A/en active Pending
- 1988-07-15 AU AU19096/88A patent/AU609153B2/en not_active Ceased
- 1988-07-21 PL PL1988273853A patent/PL151645B1/en unknown
- 1988-07-29 BR BR8803775A patent/BR8803775A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL151645B1 (en) | 1990-09-28 |
| EP0301172A2 (en) | 1989-02-01 |
| AU1909688A (en) | 1989-02-02 |
| EP0301172A3 (en) | 1989-07-26 |
| PL273853A1 (en) | 1989-04-03 |
| BR8803775A (en) | 1989-02-21 |
| JPS6436686A (en) | 1989-02-07 |
| AU609153B2 (en) | 1991-04-26 |
| DE3725367C1 (en) | 1988-09-22 |
| DE3861308D1 (en) | 1991-01-31 |
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