EP0284213B1 - Improvements in hydropyrolysis - Google Patents
Improvements in hydropyrolysis Download PDFInfo
- Publication number
- EP0284213B1 EP0284213B1 EP19880301632 EP88301632A EP0284213B1 EP 0284213 B1 EP0284213 B1 EP 0284213B1 EP 19880301632 EP19880301632 EP 19880301632 EP 88301632 A EP88301632 A EP 88301632A EP 0284213 B1 EP0284213 B1 EP 0284213B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stage
- coal
- process according
- hydropyrolysis
- catalyst
- 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
Links
- 239000003245 coal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 239000002802 bituminous coal Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000003476 subbituminous coal Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
Definitions
- This invention concerns improvements in hydropyrolysis, and more specially it concerns a hydropyrolysis process which yields significant improvements in the yield of liquid hydrocarbon products.
- UK Patent Specification NO 891,971 describes a hydropyrolysis process having the object of producing high yields of liquids and gas, and a single stage of hydropyrolysis is described, with a rapid cooling or quenching of the reaction products.
- the coal may be treated with ammonium molybdate as catalyst. Yields of gas were indeed high, of the order of 30% or more by weight of the feed coal giving a low selectivity to high value liquid products; gas is of very much lower value than distillable liquids, and such quantities of gas would suggest that the process was not energy efficient for producing liquid products. Publications by the US Bureau of Mines which relate to the process of GB 891,971 indicate that the presence or absence of the catalyst makes very little difference to liquid yields. Some hydropyrolysis processes exist primarily to make high yields of methane.
- the present invention provides a two-stage catalytic hydropyrolysis process comprising treating coal impregnated with from 0.01 to 1% by weight of molybdenum disulphide, or a precursor therefore, with hydrogen at a pressure of from 50 to 300 bar and at a temperature of 470 to 550°C, and catalytically hydrocracking the product therefrom.
- the process of the invention permits a significant yield of coal-derived liquid oils, generally in excess of 50% by weight of the coal feed (calculated as dry, ash-free coal), with only low yields of gas (C1-C4 hydrocarbons), generally less than 10%.
- the liquid oil products are substantially free of heteroatoms and are low-boiling.
- Tests involving a substantially deactivated catalyst for the second stage have yielded product material of which over 80% by wt boiled at under 350°C.
- the liquid oil products may be processed conventionally to obtain fuels and chemical feedstocks. For example, thermal cracking tests indicated that the liquid oil products give up to 70% by wt of alkylbenzenes and olefins.
- the coal starting material is preferably a finely divided (eg-0.5 mm) bituminous coal of high volatile content.
- High volatile sub-bituminous coals or lignites may also be treated by the process. It is preferred to slurry the fine coal with aqueous solution of ammonium tetra thiomolybdate, formula (NH4)2MOS4, or ammonium dioxydithiomolybdate ((NH4)2 MoO2S2), of sufficient concentration to yield the desired catalyst loading.
- the precursor is converted to MoS2 by heating, eg during the early stages of the pyrolysis.
- Preferred catalyst loadings are from 0.1 to 1 by wt.
- the temperature and pressure conditions are relatively mild compared to many advocated for hydropyrolysis.
- Preferred temperatures and pressures are approximately 500°C and approximately 150 bar for the first stage, and approximately 400°C and 150 bar for the second stage.
- Suitable residence times are less than 10 sec. and 5 sec. or more respectively, calculated as the gaseous stream.
- the second stage is desirably carried out without significant delay on the direct products of the first stage, although the products may be cooled and collected and hydrocracked subsequently.
- hydrocracking catalysts available which may be used; in general it has been found that a Ni/Mo on alumina, or Co/Mo on alumina, are suitable for coal-derived liquids.
- the catalyst may be retained in a fixed bed, or may be used in a moving or fluidised bed.
- hydrogen may be in admixture with other gases which do not interfere significantly with the hydropyrolysis, such as steam, CH4, CO and H2S.
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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
- This invention concerns improvements in hydropyrolysis, and more specially it concerns a hydropyrolysis process which yields significant improvements in the yield of liquid hydrocarbon products.
- In the art of coal processing, the process of hydropyrolysis is known. We refer by way of example to our prior UK Patent Specification No 2,007,255 B which teaches a non-catalytic two-stage hydropyrolysis process, in which yields of benzene of up to about 10% by weight could be obtained. However, there was a significant increase in methane production at second stage temperatures above about 750°C needed to hydrocrack the primary (first stage) tar into light aromatic compounds.
- UK Patent Specification NO 891,971 describes a hydropyrolysis process having the object of producing high yields of liquids and gas, and a single stage of hydropyrolysis is described, with a rapid cooling or quenching of the reaction products. The coal may be treated with ammonium molybdate as catalyst. Yields of gas were indeed high, of the order of 30% or more by weight of the feed coal giving a low selectivity to high value liquid products; gas is of very much lower value than distillable liquids, and such quantities of gas would suggest that the process was not energy efficient for producing liquid products. Publications by the US Bureau of Mines which relate to the process of GB 891,971 indicate that the presence or absence of the catalyst makes very little difference to liquid yields. Some hydropyrolysis processes exist primarily to make high yields of methane.
- The present invention provides a two-stage catalytic hydropyrolysis process comprising treating coal impregnated with from 0.01 to 1% by weight of molybdenum disulphide, or a precursor therefore, with hydrogen at a pressure of from 50 to 300 bar and at a temperature of 470 to 550°C, and catalytically hydrocracking the product therefrom.
- The process of the invention permits a significant yield of coal-derived liquid oils, generally in excess of 50% by weight of the coal feed (calculated as dry, ash-free coal), with only low yields of gas (C₁-C₄ hydrocarbons), generally less than 10%. Because of the second stage hydrocracking, the liquid oil products are substantially free of heteroatoms and are low-boiling. Tests involving a substantially deactivated catalyst for the second stage have yielded product material of which over 80% by wt boiled at under 350°C. The liquid oil products may be processed conventionally to obtain fuels and chemical feedstocks. For example, thermal cracking tests indicated that the liquid oil products give up to 70% by wt of alkylbenzenes and olefins.
- The coal starting material is preferably a finely divided (eg-0.5 mm) bituminous coal of high volatile content. High volatile sub-bituminous coals or lignites may also be treated by the process. It is preferred to slurry the fine coal with aqueous solution of ammonium tetra thiomolybdate, formula (NH₄)₂MOS₄, or ammonium dioxydithiomolybdate ((NH₄)₂ MoO₂S₂), of sufficient concentration to yield the desired catalyst loading. The precursor is converted to MoS₂ by heating, eg during the early stages of the pyrolysis. Preferred catalyst loadings are from 0.1 to 1 by wt.
- The temperature and pressure conditions are relatively mild compared to many advocated for hydropyrolysis. Preferred temperatures and pressures are approximately 500°C and approximately 150 bar for the first stage, and approximately 400°C and 150 bar for the second stage. Suitable residence times are less than 10 sec. and 5 sec. or more respectively, calculated as the gaseous stream.
- The second stage is desirably carried out without significant delay on the direct products of the first stage, although the products may be cooled and collected and hydrocracked subsequently. There are many commercially available hydrocracking catalysts available which may be used; in general it has been found that a Ni/Mo on alumina, or Co/Mo on alumina, are suitable for coal-derived liquids. The catalyst may be retained in a fixed bed, or may be used in a moving or fluidised bed.
- Although our experiments were carried out using pure hydrogen as the gas feed to the first stage, hydrogen may be in admixture with other gases which do not interfere significantly with the hydropyrolysis, such as steam, CH₄, CO and H₂S.
- The invention will now be described by way of example only
- Coal from Lindby Colliery, England (a high volatile UK bituminous coal of 82% carbon dmmf basis) was crushed to - 0.25 - 0.5 mm, and was slurried with an aqueous solution of ammonium dioxydithiomolybdate. The impregnated coal was dried under vacuum at 50°C to yield a coal material containing 1% by wt MoS₂ (formed in situ), and packed in 5 g samples in a fixed bed in an electrically heated tubular reactor. The coal was heated at 2°C/min to the reaction temperature. Hydrogen was passed through the fixed bed at 500°C. Some tests were carried out on the first stage only, using a dry ice cooled trap for liquid collection, and a pressure let-down valve connected to a gas sampling instrument. In tests using the second stage, a similar tubular reactor was used having a downstream fixed bed of 8 g of pre-sulphided commercial Ni/Mo on alumina catalyst, in addition to the coal bed. The first stage was maintained at 500°C and 150 bar pressure; the second stage was enclosed in an electrically heated furnace, maintaining a catalyst bed temperature of 400°C, and using the same trap as used in the single stage test.
- The results obtained are given in the table below, with results for the crushed Linby coal without catalyst impregnation but otherwise treated in precisely the same manner, given for comparison purposes.
- Tests were also carried out to compare the effects on the yields of total liquids (tar and water), gas (C₁-C₄-hydrocarbons) and char residue of varying temperature at a constant pressure and varying pressure at a constant temperature. The results are shown graphically in Figs 1 and 2 accompanying this description.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8707224 | 1987-03-26 | ||
GB8707224A GB2202545B (en) | 1987-03-26 | 1987-03-26 | Improvments in hydropyrolysis |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0284213A2 EP0284213A2 (en) | 1988-09-28 |
EP0284213A3 EP0284213A3 (en) | 1989-07-26 |
EP0284213B1 true EP0284213B1 (en) | 1991-06-12 |
Family
ID=10614685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19880301632 Expired EP0284213B1 (en) | 1987-03-26 | 1988-02-25 | Improvements in hydropyrolysis |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0284213B1 (en) |
DE (1) | DE3863212D1 (en) |
GB (1) | GB2202545B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9827986D0 (en) * | 1998-12-19 | 1999-02-10 | Univ Strathclyde | Improvements in hydropyrolysis |
US8123934B2 (en) | 2008-06-18 | 2012-02-28 | Chevron U.S.A., Inc. | System and method for pretreatment of solid carbonaceous material |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1890438A (en) * | 1927-12-17 | 1932-12-06 | Standard Ig Co | Conversion of carbonaceous materials into fuels of relatively low boiling point range |
US3502564A (en) * | 1967-11-28 | 1970-03-24 | Shell Oil Co | Hydroprocessing of coal |
GB2007255B (en) * | 1977-11-08 | 1982-03-03 | Coal Industry Patents Ltd | Coal pyrolysis |
US4331530A (en) * | 1978-02-27 | 1982-05-25 | Occidental Research Corporation | Process for the conversion of coal |
US4300996A (en) * | 1979-12-26 | 1981-11-17 | Chevron Research Company | Three-stage coal liquefaction process |
-
1987
- 1987-03-26 GB GB8707224A patent/GB2202545B/en not_active Expired - Lifetime
-
1988
- 1988-02-25 EP EP19880301632 patent/EP0284213B1/en not_active Expired
- 1988-02-25 DE DE8888301632T patent/DE3863212D1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
GB2202545B (en) | 1990-09-26 |
EP0284213A3 (en) | 1989-07-26 |
EP0284213A2 (en) | 1988-09-28 |
GB2202545A (en) | 1988-09-28 |
DE3863212D1 (en) | 1991-07-18 |
GB8707224D0 (en) | 1987-04-29 |
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