WO2002002719A1 - Hydratation/hydrogenolyse de charbon au moyen de catalyseurs au borane - Google Patents
Hydratation/hydrogenolyse de charbon au moyen de catalyseurs au borane Download PDFInfo
- Publication number
- WO2002002719A1 WO2002002719A1 PCT/EP2001/007589 EP0107589W WO0202719A1 WO 2002002719 A1 WO2002002719 A1 WO 2002002719A1 EP 0107589 W EP0107589 W EP 0107589W WO 0202719 A1 WO0202719 A1 WO 0202719A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coal
- coals
- hydrogen
- mpa
- hydrogenation
- Prior art date
Links
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
- C10G1/08—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
- C10G1/086—Characterised by the catalyst used
Definitions
- the present invention relates to a process in which largely insoluble hard coal is reacted with hydrogen under pressure in the presence of soluble homogeneous borane catalysts to give soluble carbohydrate products.
- any use of the organic rock coal as a source of liquid fuels and chemical raw materials requires the chemical decomposition of the cross-linked coal macromolecules into smaller structural units.
- hydrocracking reactions are used which are very unselective.
- coal is suspended together with a heterogeneous catalyst made of iron oxide and additives in a coal-derived oil and heated with hydrogen under high pressure (> 300 bar) for a few hours until decomposition begins at approx. 450 ° C [F. Bergius, DRP 301 239 from August 9, 1913; Brit. Pat. 18232, August 1, 1914; DRP 304 348 of September 7, 1919; F. Bergius, Angew. Chem. 1921.
- Triorganoboranes R 3 B are a completely different type of homogeneous hydrogenation catalysts than the soluble metal compounds usually used, from which hydrogenboron bonds such as R 2 BH and with hydrogen under pressure at temperatures above 140 ° C. by hydrogenolysis of boron-carbon bonds further hydrogenolysis ultimately borane BH 3 or the dimeric diborane (BH 3 ) 2 are formed [R. Köster, G. Bruno, P. Binger, Liebigs Ann. Chem. 644 (1961) 1; DBP 1 048 586 (1959), vesselsgesellschaft Kohl mbH., founded by R. Köster (Chem. Abstr. 55 (1961) 3433).
- Reactive hydroborane compounds react with diphenylmethane to form primary cleavage products phenylborane and toluene or benzylborane and benzene.
- reactive hydroboranes are regenerated again and again.
- Other diarylalkanes such as 1,2-diphenylethane and di- (1-naphthyl) methane were also cleaved, with naphthalene being hydrogenated to tetralin units in addition to the CC bond hydrogenolysis.
- the diorganohydroboranes R 2 BH or their dimers (R 2 BH) 2 themselves can also be used as catalysts.
- TPDB tetra- ⁇ -propyldiborane
- the partial hydrogenation of the polycyclic aromatics naphthalene, anthracene, phenanthrene, triphenylene, chrysene, pyrene, perylene and corones was successful, with hydroaromatics intact with at least one or more aromatic six-membered rings were formed [R. Köster, W.
- Coal tar could also be hydrogenated using TPDB as a catalyst [M. Yalpani, R. Köster, MW Haenel, oil, coal, natural gas, petrochemicals. 43 (1990) 344], and even hydrogenolysis of C a k yi-C a i ky ] bonds in alkanes has been achieved with such hydroborane catalysts [M. Yalpani, R. Köster, petroleum, coal, natural gas, petrochemicals. 43 (1990) 348].
- German fat coal medium-volatile bituminous coal, mine Westerholt, Flöz Robert, 23.6% fl. B., 89.4% C (waf)
- Pr 2 BI, DPIB catalyst di-n-propyl iodborane
- Elemental iodine reacts with hydrogen to form hydrogen iodine and has a certain catalytic value in the temperature range between 300 and 500 ° C.
- Table 1 Reaction conditions and results of the hydrogenation / hydrogenolysis of hard coal with homogeneous borane catalysts in toluene.
- elemental halogens, hydrogen halides and element-halogen compounds such as nitrogen-halogen compounds, phosphorus halides, antimony halides or else boron trihalides can be used as halogenating reagents.
- the present invention therefore also relates to the use of catalyst systems which consist of mixtures of triorganoboranes R 3 B or organohydroboranes (R 2 BH) 2 or (RBH 2 ) 2 or diborane (BH 3 ) 2 and a suitable halogenating reagent such as, for. B.
- the molar ratio of boron compound to halogenating reagent is generally between 0.1 and 100, preferably between 0.5 and 5.
- DPIB di-rc-propyliodborane
- TPDB tetra-rc-propyldiborane
- TiX Cl, Br, I
- the hydrogen halide HX formed here can convert organoborane compounds into further halogen borane compounds [R. Köster, in Methods of Organic Chemistry (Houben-Weyl), 4th ed., Vol. XITJ73a, p. 382, Thieme, Stuttgart 1982]:
- the molar ratio of metal borate to halogenating reagent is generally between 0.1 and 100, preferably between 0.5 and 5.
- an equimolar mixture of sodium tetrahydroborate NaBH 4 and iodine could be used as a catalyst for the hydrogenation of the fatty carbon in a particularly simple manner (Table 1 , Entries 10 and 11). After 12 hours of reaction in toluene at 280 ° C with hydrogen under pressure (15 MPa pressure at room temperature), the carbohydrate product was 87% soluble in pyridine and showed a ratio of aromatic to aliphatic carbon atoms (C a JC a ⁇ ) of 65:35. From the comparison with the experiment No 4 in Tab.
- catalytically active dihydroiodoborane can be formed from NaBE and iodine under the reaction conditions as follows: NaBH 4 + l 2 * - Nal + H 2 BI + H 2
- the invention includes a significant advance with the surprising and unpredictable finding that very high-carbonized hard coal such as eating coal and lean coal (steam coals, low-volatile bituminous coals, semi-anthracites) and even anthracites in the presence of homogeneous borane catalysts Hydrogen can be reacted.
- very high-carbonized hard coal such as eating coal and lean coal (steam coals, low-volatile bituminous coals, semi-anthracites) and even anthracites in the presence of homogeneous borane catalysts Hydrogen can be reacted.
- German coal low-volatile bituminous coal
- Friedrich der civile mine Flöz Mausegatt 2, 15.0% fl. B., 93.4% C (waf)] was suspended as a suspension in toluene in the presence of the catalyst from NaBEU and iodine Reaction with hydrogen under pressure for 12 hours (15 MPa pressure at room temperature, approx. 25 MPa total pressure at 280 ° C) to give a solid carbohydrate product.
- the hydrogenation increased the solubility in pyridine from ⁇ 1% in the feed coal to 46% in the product and the proportion of aliphatic carbon atoms from 14% to 38% (Table 1, entries 12 and 14).
- Anthracites represent the end of the coaling series and have of all types of coal due to their chemical structure (highest carbon content, lowest hydrogen and oxygen content, high proportion of very large polycyclic aromatics, lowest proportion of aliphatic structures) and physical structure (highest density, very low porosity) ) the lowest chemical reactivity.
- chemical structure highest carbon content, lowest hydrogen and oxygen content, high proportion of very large polycyclic aromatics, lowest proportion of aliphatic structures
- physical structure highest density, very low porosity
- hydroboration of olefins it is known that it can be catalyzed by transition metal and rare earth metal compounds [cf. z. B .: D. Switzerland Switzerland Switzerland Switzerland, Angew. Chem. 97 (1985) 854; Angew. Chem., Int. Ed. Engl. 1-10 (1985) 878; K. Burgess, MJ Ohlmeyer, Chem. Rev. 91 (1991), 1179; KN Harrison, T. Marks, J. Am. Chem. Soc. 114: 6671 (1992); DA Evans, AR Muci, R. Sm, J. Org.
- the molar ratio of the added transition metal or rare earth metal compounds to the Borane catalysts are generally between 0.01 and 100
- the catalysts of the invention can be used in a process for the hydrogenation / hydrogenolysis of hard coal, which is characterized in that the ground hard coal as a suspension in liquid hydrocarbons in the presence of these catalysts with hydrogen at a pressure between 1 and 100 MPa, preferably between 10 and 30 MPa and at temperatures between 140 and 500 ° C, preferably between 200 to 400 ° C, preferably in particular between 220 and 350 ° C to carbohydrate products be implemented.
- Aliphatic, aromatic or hydroaromatic hydrocarbons or their mixtures preferably aromatic hydrocarbons such as, for example, benzene, toluene, xylenes, trimethylbenzenes, alkyl-, dialkyl-, trialkylbenzenes or their mixtures, can be used to suspend the hard coal and catalyst components and as a solvent for the catalysts.
- aromatic hydrocarbons such as, for example, benzene, toluene, xylenes, trimethylbenzenes, alkyl-, dialkyl-, trialkylbenzenes or their mixtures
- hard coal in the coaling range from gas flame and gas coal (caking coals, high-volatile bituminous coals) to eating coal and lean coal (steam coals, low-volatile bituminous coals, semi-anthracites) and Anthracites, preferably hard coal in the coaling area from fat or coking coals (coking coals, medium-volatile bituminous coals) to eating and lean coal (steam coals, low-volatile bituminous coals, semi-anthracites) and anthracites.
- the process of the present invention can also be used to produce hydrogenation products from very high-carbonized hard coal such as table coal, lean coal and anthracite which are inert in Bergius coal liquefaction.
- very high-carbonized hard coal such as table coal, lean coal and anthracite which are inert in Bergius coal liquefaction.
- the ratios of aromatic to aliphatic carbon atoms (C a i / C a i) and of carbon to hydrogen (CH) in the hydrogenation products of the high-carbon hard coal correspond to those of low-carbon hard coal.
- the hydrogenation products of the highly-coaled hard coal like lignite and low-coal coal such as gas flame and gas coal (lignites, sub-bituminous coals, caking coals, high-volatile bituminous coals) can be further processed into coal oils using the Bergius technical coal liquefaction processes.
- the process of the present invention with Bergius coal liquefaction processes to form a multi-stage or integrated process process, the very high-carbonized hard coal is also accessible for direct coal liquefaction.
- macromolecular fossil raw materials such as heavy oils, petroleum distillation residues, tar sands or oil shale as well as coal products such as tars or pitches and finally also macromolecular plastics can also be processed hydrogenating or hydrogenolytically to hydrogenation products with the method of the present invention.
- macromolecular fossil raw materials such as heavy oils, petroleum distillation residues, tar sands or oil shale as well as coal products such as tars or pitches
- macromolecular plastics can also be processed hydrogenating or hydrogenolytically to hydrogenation products with the method of the present invention.
- Fat coal Westerholt mine, Flöz Robert: 23.6% fl. B., 89.4% C, 4.72%
- the pre-broken hard coal was mixed with dry ice for embrittlement and as a protective gas with an impact pin and a ring sieve mill on ground (average grain 60 microns), dried at 10 "3 Torr 3 d under argon.
- Tetra-n-propyldiborane [( n Pr BH) 2 , TPDB] was prepared as a mixture of low and highly propylated diboranes and tri-n-propylborane according to a literature procedure [R. Köster, P. Binger, Inorg. Synth. 15 (1974) 141; R. Köster, in Methods of Organic Chemistry (Houben-Weyl), 4th edition, Vol. Xm / 3a, p. 333, Thieme, Stuttgart 1982].
- the TBDB used here had a hydride content of 1.73%.
- Di-n-propyliodoborane [Pr 2 BI, DPIB] was prepared by reacting TPDB and iodine according to ( n Pr 2 BH) 2 + I 2 ⁇ 2 n Pr 2 BI + H 2 according to a literature procedure [R. Köster, MA Grassberger, Liebigs Ann. Chem. 719 (1968) 169]. According to elemental analysis [C 25.26%, H 4.84%, B 5.31%, I 63.89%] and ⁇ B-NMR spectrum, the DPIB used here was a (2: 1) mixture of di-n-propyl iodborane and diiodo-n-propylborane.
- Solubilities in pyridine were determined by Soxhlet extraction. Charcoal samples (approx. 200 mg or 2 to 3 g) were extracted from glass fiber tubes with hot pyridine for 1-2 days until the pyridine was colorless. The tubes were then extracted with ether for 8 h to remove adhering pyridine and the tubes and the extraction residues were dried for 3 d in a high vacuum. Out the differences in weight of the sleeves before and after the extraction, the solubilities were obtained as an average of 2 determinations in each case.
- Example 1 (entry No 5 in Tab. 1):
- Example 2 (entry No 3 and No 4 in Tab. 1):
- Example 1 40 g of finely ground fat coal with a solution of 4.0 ml (14.8 mmol) of TPDB in 150 ml of anhydrous toluene were placed in a stirred autoclave (500 ml volume) twice for 24 hours at 280 ° C. in the presence of hydrogen under pressure (15 MPa pressure at room temperature) stirred. Only a slight decrease in pressure of approximately 0.2 MPa was observed for both reaction periods. After the autoclave had been completely let down, 120 ml of methanol were added to the dark suspension and the mixture was stirred at 130 ° C. in a closed autoclave for 24 h.
- Example 4 40 g of finely ground fat coal with a solution of 4.0 ml (14.8 mmol) of TPDB and 9.0 g (24.4 mmol) of titanium tetrabromide in 150 ml of anhydrous toluene were placed twice in a stirred autoclave (500 ml volume) twice for 24 h at 280 ° C in the presence of hydrogen under pressure (15 MPa pressure at room temperature). The pressure drop in the first and second 24 h was 1.7 and 0.8 MPa, respectively. After the autoclave had been completely let down, 120 ml of methanol were added to the dark suspension and the mixture was stirred at 130 ° C. in a closed autoclave for 24 h.
- Example 4 20 g of finely ground fat coal with a solution of 1.0 ml (3.7 mmol) of TPDB and 5.0 g (9.0 mmol) of titanium tetraiodide in 150 ml of anhydrous toluene were placed twice in a stirred autoclave (500 ml volume) twice for 24 hours at 280 ° C in the presence of hydrogen under pressure (15 MPa pressure at room temperature). The pressure drop in the first and second 24 h was 1.5 and 0.4 MPa, respectively. After the autoclave had been completely let down, 120 ml of methanol were added to the dark suspension and the mixture was stirred at 130 ° C. in a closed autoclave for 24 h.
- Example 10 (entry No 15 in Tab. 1):
- Example 8 40 g of charcoal, 1.14 g (30 mmol) of sodium borohydride (sodium tetrahydridoborate NaBH 4 ) and 7.61 g (30 mmol) of iodine in 150 ml of toluene were placed twice in a stirred autoclave (500 ml volume) at 280 ° for 24 h C stirred in the presence of hydrogen under pressure (15 MPa pressure at room temperature). The pressure drop in the first and second 24 h was 2.2 and 0.3 MPa, respectively.
- Example 7 According to the detailed description in Example 7, 30 g of hydrogenation product from the charcoal from Example 10 (entry No 15 in Table 1), 0.86 g (22.6 mmol) of sodium borohydride (sodium tetrahydridoborate NaBH 4 ), 5.71 g (22.5 mmol) of iodine and 150 ml of toluene in a stirred autoclave (500 ml volume) at 280 ° C for 12 h in the presence of hydrogen under pressure (15 MPa pressure at room temperature). After cooling, a decrease in pressure of 1.7 MPa was determined.
- Example 12 (entry No 18 in Tab. 1):
- Example 8 40 g of anthracite, 1.14 g (30 mmol) of sodium borohydride (sodium tetrahydridoborate NaBH) and 7.61 g (30 mmol) of iodine in 150 ml of toluene were placed twice in a stirred autoclave (500 ml volume) at 280 ° C. for 24 h stirred in the presence of hydrogen under pressure (15 MPa pressure at room temperature). The pressure drop in the first and second 24 h was 1.9 and 0.3 MPa, respectively.
- Example 8 According to the detailed description in Example 8, 30 g of hydrogenation product of the anthracite from Example 12 (entry No 18 in Table 1), 0.86 g (22.6 mmol) of sodium borohydride (sodium tetrahydridoborate NaBHi), 5.71 g (22.5 mmol) iodine in 150 ml of toluene was stirred twice for 24 h at 280 ° C. in the presence of hydrogen under pressure (15 MPa pressure at room temperature). The pressure drop in the first and second 24 h was 1.2 and 0 MPa, respectively.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
La présente invention concerne un procédé permettant l'hydratation / l'hydrogénation de matières premières fossiles macromoléculaires et de matières synthétiques macromoléculaires, notamment de charbons, par utilisation d'hydrogène sous pression en présence de catalyseurs au borane. Les catalyseurs actifs sont des composés organobore-halogène et l'halogène hydroborane R2BX ou RBX2 (R = H, organyle; X = F, Cl, Br, I) qui sont soit utilisés tels quels, soit préparés à partir de composés borane R3B ou de borates métalliques M<+>[R4B]<-> (R = H, organyle) et de réactifs d'halogénation appropriés dans les conditions réactionnelles in-situ. Contrairement aux procédés de fluidification de charbon selon Bergius, les charbons même hautement carbonisés tels que les charbons E beta et maigres (houilles maigres, houilles bitumineuses à faible teneur en matières volatiles, semi-anthracites) et les anthracites sont mis en réaction avec de l'hydrogène.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001285793A AU2001285793A1 (en) | 2000-07-04 | 2001-07-03 | Hydrogenation / hydrogenolysis of hard coal, using borane catalysts |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10032316.2 | 2000-07-04 | ||
DE2000132316 DE10032316A1 (de) | 2000-07-04 | 2000-07-04 | Hydrierung/Hydrogenolyse von Steinkohle mit Boran-Katalysatoren |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002002719A1 true WO2002002719A1 (fr) | 2002-01-10 |
Family
ID=7647635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/007589 WO2002002719A1 (fr) | 2000-07-04 | 2001-07-03 | Hydratation/hydrogenolyse de charbon au moyen de catalyseurs au borane |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU2001285793A1 (fr) |
DE (1) | DE10032316A1 (fr) |
WO (1) | WO2002002719A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006041870A1 (de) * | 2006-09-06 | 2008-03-27 | Studiengesellschaft Kohle Mbh | Lösungsmittelfreie Hydrierung / Hydrogenolyse von hochinkohlten Steinkohlen mit Boran- und Iod-Katalysatoren |
DE102013107865A1 (de) | 2012-07-26 | 2014-01-30 | Studiengesellschaft Kohle Mbh | Verfahren zur direkten Kohleverflüssigung |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB277974A (en) * | 1926-09-23 | 1928-12-06 | Adolf Ludwig Heinrich Spilker | A process for hydrogenating and splitting hydrocarbons, the distillation products ofvarious coals and their constituents, as also the coals themselves |
GB2270085A (en) * | 1992-08-04 | 1994-03-02 | Exxon Research Engineering Co | Coal depolymerisation and hydroprocessing |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3741104A1 (de) * | 1987-12-04 | 1989-06-15 | Ruhrkohle Ag | Verfahren zur hydrierung fester kohlenstoffhaltiger einsatzstoffe |
-
2000
- 2000-07-04 DE DE2000132316 patent/DE10032316A1/de not_active Withdrawn
-
2001
- 2001-07-03 AU AU2001285793A patent/AU2001285793A1/en not_active Withdrawn
- 2001-07-03 WO PCT/EP2001/007589 patent/WO2002002719A1/fr active Search and Examination
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB277974A (en) * | 1926-09-23 | 1928-12-06 | Adolf Ludwig Heinrich Spilker | A process for hydrogenating and splitting hydrocarbons, the distillation products ofvarious coals and their constituents, as also the coals themselves |
GB2270085A (en) * | 1992-08-04 | 1994-03-02 | Exxon Research Engineering Co | Coal depolymerisation and hydroprocessing |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006041870A1 (de) * | 2006-09-06 | 2008-03-27 | Studiengesellschaft Kohle Mbh | Lösungsmittelfreie Hydrierung / Hydrogenolyse von hochinkohlten Steinkohlen mit Boran- und Iod-Katalysatoren |
DE102013107865A1 (de) | 2012-07-26 | 2014-01-30 | Studiengesellschaft Kohle Mbh | Verfahren zur direkten Kohleverflüssigung |
WO2014015861A1 (fr) | 2012-07-26 | 2014-01-30 | Studiengesellschaft Kohle Mbh | Procédé de liquefaction directe du charbon |
Also Published As
Publication number | Publication date |
---|---|
DE10032316A1 (de) | 2002-01-17 |
AU2001285793A1 (en) | 2002-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3502564A (en) | Hydroprocessing of coal | |
US4561964A (en) | Catalyst for the hydroconversion of carbonaceous materials | |
EP0055556B1 (fr) | Conversion de déchets municipaux en combustibles | |
Chakrabartty et al. | Studies on the structure of coals. 3. Some inferences about skeletal structures | |
Xiao-Ming et al. | Solid superacid-catalyzed hydroconversion of an extraction residue from Lingwu bituminous coal | |
Sugano et al. | Effects of hydrogen transfer by exchanged cobalt upon liquefaction of low rank coal | |
US2119647A (en) | Production of valuable hydrocarbons | |
DE3233344A1 (de) | Verfahren zur verfluessigung von kohle | |
WO2002002719A1 (fr) | Hydratation/hydrogenolyse de charbon au moyen de catalyseurs au borane | |
Zhao et al. | Catalytic hydroconversion of extraction residues from two Chinese lignites to arenes | |
Kershaw et al. | Chemical nature of coal hydrogenation oils part I. The effect of catalysts | |
WO2009009976A1 (fr) | Combinaison catalytique et procédé de liquéfaction directe de matières carbonées à l'aide de celle-ci | |
US2606142A (en) | Hydrogenation liquefaction of coal employing zinc catalysts | |
US4511454A (en) | Process for use of novel boride catalyst | |
DE3329222A1 (de) | Verfahren zur kohleverfluessigung mit einem aktivierten zinksulfidkatalysator | |
DD156920A5 (de) | Verfahren zur umwandlung aschehaltiger foerderkohle | |
Suzuki et al. | Highly active coal liquefaction catalyst: soluble ruthenium complexes as catalyst precursors | |
WO2008028459A1 (fr) | Hydrogénation/hydrogénolyse exempte de solvant de charbons hautement carbonés au moyen de catalyseurs au borane et à l'iode | |
DD147680A5 (de) | Kohleverfluessigungsverfahren mit mehreren einsatzkohlen | |
AT159616B (de) | Verfahren zur Herstellung von Kohlenwasserstoffen. | |
Liu et al. | Hydrogen-donating behavior and hydrogen-shuttling mechanism of liquefaction solvents under Fe-and Ni-based catalysts | |
DE570558C (de) | Verfahren zur Verarbeitung hochmolekularer organischer Stoffe auf Stoffe niederer Molekulargroesse | |
Onu | Zinc Chloride Catalysis in Coal and Biomass Liquefaction at Prepyrolysis Temperatures | |
DE695269C (de) | Verfahren zur Herstellung von Kohlenwasserstoffoelen aus Kohlen, Teeren, Mineraloelen, deren Destillations-, Spalt- und Druckhydrierungsprodukten | |
DE711315C (de) | Verfahren zur Herstellung klopffester niedrigsiedender Kohlenwasserstoffoele |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA JP US ZA |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application |