EP0123161B1 - Procédé d'hydrogénation de charbon - Google Patents
Procédé d'hydrogénation de charbon Download PDFInfo
- Publication number
- EP0123161B1 EP0123161B1 EP84103345A EP84103345A EP0123161B1 EP 0123161 B1 EP0123161 B1 EP 0123161B1 EP 84103345 A EP84103345 A EP 84103345A EP 84103345 A EP84103345 A EP 84103345A EP 0123161 B1 EP0123161 B1 EP 0123161B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- coal
- degrees
- via line
- pasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
-
- 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
-
- 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
Definitions
- Document DE-A-2 715 625 describes a process for the hydrogenation of coal with solvent and hydrogen at elevated temperatures and pressures in the presence of a catalyst in order to obtain a liquid product. Gases and solids are separated from the liquids. The liquid product is then distilled. Aromatic hydrocarbon mixtures are used as solvents that are foreign to the process, such as. B. anthracene oil. It is also possible to use process oil, but it is not clear what percentage of the process oil is used as grating oil or whether the products boil above 200 ° C.
- Document DE-B-2 040 764 describes a process for liquefying coal, in which coal is pulverized with a naphthenic aromatic solvent under pressure and at high temperature.
- the document DE-A-3 209143 describes a process for the multi-stage hydrogenation of coal, in which finely ground coal is rubbed with only oils of process origin and preferably at pressures of 100 to 400 bar, preferably 250 to 350 bar and temperatures of 400 to 520 ° C 440 to 490 ° C, optionally hydrogenated with hydrogen in a bottom phase in the presence of catalysts, from the gaseous hydrogenation product after separation of the phase containing solids at the reaction temperature using the pressure given by the bottom phase by means of fractional condensation by heat exchange with feed products the hydrogenation stages at least 3 liquid phases are obtained, of which at least one is further hydrogenated in a gas phase in the presence of catalysts using the pressure given by the bottom phase.
- the fractions used for the gas phase hydrogenation should have a boiling range from 180 to 450 ° C., preferably from 200 to 350 ° C., while the fractions of the bottom phase product boiling at temperatures of more than 250 ° C., preferably more than 350 ° C., at least partly after relaxation be recycled as rubbing oil.
- the temperature data for boiling ranges relate to the values obtained at atmospheric pressure (1 bar).
- the proportion of non-process hydrocarbon mixtures in the grinding oil is more than 30% by weight, preferably more than 50% by weight, and can increase up to 95% by weight.
- particularly suitable hydrocarbon mixtures such as heavy, very low-paraffin oils, it is even possible to use them alone as a grinding oil.
- the hydrocarbon mixture used as grinding oil should have an initial boiling point above 200 ° C., preferably above 300 ° C.
- the process-derived oils returned as grinding oil should also have an initial boiling point of more than 200 ° C., preferably more than 300 ° C.
- the amount of process-derived oil used as the grinding component can therefore be reduced, depending on the nature of the non-process hydrocarbon mixture. It is thus possible to obtain hydrogenation product from the bottom phase or gas phase which is otherwise attributed to the grinding process as a valuable product and to replace it with less valuable products in the grinding process. In extreme cases, the total amount of rubbing oil can be provided by non-process oils that are in the. Hydrogenation levels to high quality. Products are processed.
- the process according to the invention is optimized in terms of reaction technology by the direct transfer of the gaseous bottom phase product into the gas phase without intermediate relaxation: in addition to the energetic advantages, undesirable reactions of the thermally unstable and reactive oil-like products of the bottom phase hydrogenation during atmospheric distillation are avoided.
- fractional condensation of the gaseous sump or gas phase product allows the adaptation of the oils used as grinding oils amount and quality of oil to the amount and type of non-process rubbing oils.
- the oil which is obtained in the thickening of the bottom phase products which are solid or liquid at the reaction temperature and pressure or at somewhat lower temperatures and, as mentioned above , are separated before the gas phase hydrogenation or the fractional condensation of the gaseous bottom phase product.
- the thickening is carried out in the usual way, for example by vacuum distillation, smoldering or coking.
- the oil obtained during the thickening can also be used alone as part of the grinding oil of process origin.
- Fig. 1 Two embodiments of the method according to the invention are described below with reference to the flow diagrams Fig. 1 and 2.
- Fig. 1 the procedure is shown in which only a part of the bottom phase product is subjected to hydrogenation in the gas phase.
- Finely ground and dried coal is fed via line 1, possibly with the addition of a catalyst via line 2, with a non-process-derived liquid hydrocarbon mixture in tank 4, possibly with the addition of one or more process-derived oils from line 5 a mixture of coal and liquid hydrocarbons.
- Process oil can be used as a thickener of the bottom product of the hot separator 6, e.g. B. by vacuum distillation 7, vacuum gas oil fraction obtained via line 8 or as a condensed in the separator 9 01 via line 10, optionally after separating light components in an atmospheric distillation 28 via line 11.
- the slurry is fed via line 12 to the pump 13, brought to a pressure of 300 to 700 bar there and via line 14 through the heat exchangers 15, 16 and, after addition of hydrogen via line 18, through the heat exchanger 17 and after heating in the preheater 19 pumped into the bottom phase hydrogenation 20, which usually consists of several reactors connected in series.
- reaction products leave the reaction part via line 21 and are separated in the hot separator 6.
- the bottom product of the hot separator which is composed of unreacted coal, possibly catalysts, asphaltenes and high-boiling oils, leaves the hot separator via line 22 in order to suitably, for. B. by vacuum distillation (7) or coke processes (7) to be worked up to high-boiling oils and a residual product.
- the oil-like product is either fed via lines 8 and 5 into the grinding container 4 or via lines 23 and 53 and intermediate compression with pump 25 to the pressure of the gas phase hydrogenation of the gas phase hydrogenation 24.
- Compressed product after pump 25 can be heated via line 57 in preheater 26 and introduced via lines 44 and 53 into the gas phase hydrogenation.
- oil-like product can be removed from the process via line 27.
- the residual product of the hot separator sump processing leaves the process via line 29.
- the products present in gaseous form in the hot separator 6 leave it after passing through the heat exchanger 31 via line 30 and are partially condensed by heat exchange with the fresh mash in the heat exchangers 17, 16 and 15 at the pressure predetermined by the phase-phase hydrogenation.
- the resulting liquid fraction is fed to the mashing tank 4 after condensation and a discharge of the gases released via lines 10 and 5, which is not shown in the flow diagram. If necessary, this fraction can reach an atmospheric distillation 28 via line 32, in which further light fractions are distilled off and removed from the process via line 33. The heavy fractions remaining in atmospheric distillation 28 are fed via lines 11 and 5 to the mashing container 4 or leave the process via line 34.
- the fraction remaining in gaseous form in the separator 9 is fed to the separator 36 via line 35 by further heat exchange with the fresh mash in the heat exchanger 16.
- the resulting liquid fraction is via line 37, after adding hydrogen via line 38 and after heat exchange with products of the bottom and gas phase in the heat exchangers 39 and 31, via lines 58, 44 and 53, or after a possibly necessary Heating in the preheater 26 via lines 56, 44 and 53, into the gas phase hydrogenation 24.
- the process pressure given by the bottom phase hydrogenation is used for the gas phase hydrogenation.
- the reaction products leave the gas phase reactor 24 and are supplied via the heat exchanger 39 and line 40 after expansion of the distillation 41.
- the resulting heavy products leave the process via line 42.
- the gaseous products obtained in the distillation 41 are removed from the process via line 45, the lighter liquid products via line 46.
- the gaseous products obtained in the separator 36 are fed to the separator 48 via line 47 and heat exchange with the fresh mash in the heat exchanger 15.
- the resulting liquid products leave the process via line 49.
- the gaseous products obtained in the separator 48 leave the process via line 50 and are released into a gas processing unit.
- the separators 9 and 36 are designed to improve the separation effect as amplifier columns with return 51, 52.
- Fig. 2 shows the procedure in which the entire gaseous bottom phase product is further hydrogenated in the gas phase.
- finely ground and dried coal via line 1 possibly with the addition of a catalyst via line 2
- a non-process-derived liquid hydrocarbon mixture supplied via line 3 and in container 4 possibly with the addition of a thickened bottom product the hot separator 6, e.g. B. by means of vacuum distillation 7, obtained oil via line 5, to a mixture of coal and liquid hydrocarbons.
- the mixture has a solids content of 5-50% by weight.
- the slurry passes via line 12 to the pump 13, which brings it to a pressure of 300-700 bar and via line 14 through the heat exchangers 15, 16 and 17 and after heating in the preheater 19 into the bottom phase hydrogenation 20, which generally pumps out there are several reactors connected in series. Hydrogen is added to the slurry in line 14 via line 18. The reaction products leave the reaction part via line 21 and are separated in the hot separator 6.
- the bottom product of the hot separator consists of unreacted coal, possibly catalysts, asphaltenes and high-boiling oils. It comes via line 22 to a workup 7, z. B. a vacuum distillation or a coker to be worked up in a suitable manner to high-boiling oils and a residual product.
- the oil-like product is fed via line 5 into the grinding container 4 or via lines 23 and 53 and intermediate compression with pump 25 to the pressure of the gas phase hydrogenation of the gas phase hydrogenation 24. If necessary, compressed product after the pump 25 can be brought via line 57 to the preheater 26, heated there and fed via lines 44 and 53 into the gas phase hydrogenation 24. Oil-like product can also be removed from the process via line 27.
- the products present in gaseous form under the conditions prevailing in the hot separator leave the hot separator 6 and are conveyed via lines 43, 44 and 53 using the pressure and heat content given by the phase-phase hydrogenation, if necessary after heating in the preheater 26 via lines 56, 44 and 53, the gas phase hydrogenation 24 fed.
- the products of the gas phase hydrogenation 24 are partially condensed via line 55 by heat exchange with the fresh mash in the heat exchangers 15, 16 and 17 under the pressure given by the gas phase hydrogenation.
- the liquid fraction obtained preferably a fraction of the medium oil and vacuum gas oil boiling range, is led out of the process via line 59.
- the fraction remaining in gaseous form in the separator 9 is fed to the separator 36 via line 35 and further heat exchange with the fresh mash in the heat exchanger 16.
- the resulting liquid fraction preferably a fraction of the naphthase boiling range, is removed from the process via line 54.
- Gaseous product obtained in the separator 36 is fed to the separator 48 via line 47 and heat exchanger 15, condensed portions leave the process via line 49, gaseous products obtained in separator 48 are led out of the process via line 50 and into gas processing. given.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Working-Up Tar And Pitch (AREA)
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3311552 | 1983-03-30 | ||
DE19833311552 DE3311552A1 (de) | 1983-03-30 | 1983-03-30 | Verfahren zur hydrierung von kohle |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0123161A1 EP0123161A1 (fr) | 1984-10-31 |
EP0123161B1 true EP0123161B1 (fr) | 1987-03-04 |
Family
ID=6195065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84103345A Expired EP0123161B1 (fr) | 1983-03-30 | 1984-03-27 | Procédé d'hydrogénation de charbon |
Country Status (5)
Country | Link |
---|---|
US (1) | US4944866A (fr) |
EP (1) | EP0123161B1 (fr) |
CA (1) | CA1231657A (fr) |
DD (1) | DD224863A5 (fr) |
DE (2) | DE3311552A1 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3532480A1 (de) * | 1984-09-13 | 1986-03-20 | Ruhrkohle Ag, 4300 Essen | Verfahren zur prozesseinstellung und waermerueckgewinnung fuer die sumpfphasehydrierung von kohlen mit integrierter gasphasehydrierung |
DE3585485D1 (de) * | 1984-09-13 | 1992-04-09 | Ruhrkohle Ag | Verfahren zur prozesseinstellung mit waermerueckgewinnung fuer die sumpfphasehydrierung mit integrierter gasphasehydrierung. |
DE3519830A1 (de) * | 1985-06-03 | 1986-12-18 | Ruhrkohle Ag, 4300 Essen | Verfahren zur kohlehydrierung mit integrierten raffinationsstufen |
DE3543240A1 (de) * | 1985-12-06 | 1987-06-11 | Rheinische Braunkohlenw Ag | Verbessertes verfahren zur hydrierenden behandlung von kohle/mineraloel-gemischen |
US5445659A (en) * | 1993-10-04 | 1995-08-29 | Texaco Inc. | Partial oxidation of products of liquefaction of plastic materials |
US9994778B2 (en) | 2015-05-24 | 2018-06-12 | Accelergy Corporation | Direct coal liquefaction process and system |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1986593A (en) * | 1931-05-14 | 1935-01-01 | Universal Oil Prod Co | Treatment of hydrocarbon oils and coal |
US3598718A (en) * | 1969-08-18 | 1971-08-10 | Universal Oil Prod Co | Solvent extraction of coal |
US3700584A (en) * | 1971-02-24 | 1972-10-24 | Hydrocarbon Research Inc | Hydrogenation of low rank coal |
US3755137A (en) * | 1971-03-24 | 1973-08-28 | Hydrocarbon Research Inc | Multi-stage ebullated bed coal-oil hydrogenation and hydrocracking process |
US3870621A (en) * | 1973-07-30 | 1975-03-11 | Exxon Research Engineering Co | Residuum processing |
GB1481690A (en) * | 1973-11-27 | 1977-08-03 | Coal Ind | Hydrogenative treatment of coal |
JPS51122104A (en) * | 1975-04-16 | 1976-10-26 | Mitsui Cokes Kogyo Kk | Process for liquefying coals |
US4054504A (en) * | 1975-10-02 | 1977-10-18 | Hydrocarbon Research, Inc. | Catalytic hydrogenation of blended coal and residual oil feeds |
US4081361A (en) * | 1976-07-26 | 1978-03-28 | Gulf Research & Development Company | Process for the conversion of carbonaceous materials |
GB1604230A (en) * | 1978-05-31 | 1981-12-02 | Mobil Oil Corp | Hydroprocessing coal liquids |
JPS5411903A (en) * | 1977-06-29 | 1979-01-29 | Agency Of Ind Science & Technol | Liquefaction of coal with aromatic and aliphatic oils together |
CA1142113A (fr) * | 1979-09-05 | 1983-03-01 | Osamu Hiroya | Melange de charbon et de petrole |
US4316792A (en) * | 1979-12-21 | 1982-02-23 | The Lummus Company | Hydroliquefaction of coal |
US4300996A (en) * | 1979-12-26 | 1981-11-17 | Chevron Research Company | Three-stage coal liquefaction process |
DE3033075C2 (de) * | 1980-09-03 | 1982-11-18 | Rütgerswerke AG, 6000 Frankfurt | Verfahren zur Herstellung von hochwertigen Kohlenstoffbindemitteln |
DE3105030A1 (de) * | 1981-02-12 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen herstellung von kohlenwasserstoffoelen aus kohle durch druckhydrierung in zwei stufen |
US4405437A (en) * | 1982-01-11 | 1983-09-20 | Electric Power Research Institute | Process for coal liquefaction employing a superior coal liquefaction process solvent |
-
1983
- 1983-03-30 DE DE19833311552 patent/DE3311552A1/de not_active Withdrawn
-
1984
- 1984-03-19 CA CA000449889A patent/CA1231657A/fr not_active Expired
- 1984-03-27 EP EP84103345A patent/EP0123161B1/fr not_active Expired
- 1984-03-27 DE DE8484103345T patent/DE3462520D1/de not_active Expired
- 1984-03-29 DD DD84261389A patent/DD224863A5/de not_active IP Right Cessation
-
1986
- 1986-04-15 US US06/852,391 patent/US4944866A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DD224863A5 (de) | 1985-07-17 |
EP0123161A1 (fr) | 1984-10-31 |
DE3311552A1 (de) | 1984-10-04 |
CA1231657A (fr) | 1988-01-19 |
US4944866A (en) | 1990-07-31 |
DE3462520D1 (en) | 1987-04-09 |
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