EP0129680B1 - Verfahren zur Behandlung von Prozessabwässern und Abwässern bei der Hydrierung von Kohle - Google Patents
Verfahren zur Behandlung von Prozessabwässern und Abwässern bei der Hydrierung von Kohle Download PDFInfo
- Publication number
- EP0129680B1 EP0129680B1 EP84105177A EP84105177A EP0129680B1 EP 0129680 B1 EP0129680 B1 EP 0129680B1 EP 84105177 A EP84105177 A EP 84105177A EP 84105177 A EP84105177 A EP 84105177A EP 0129680 B1 EP0129680 B1 EP 0129680B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coal
- waste waters
- water
- hydrogenation
- treatment
- 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
- 239000002351 wastewater Substances 0.000 title claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 18
- 239000003245 coal Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 11
- 239000011269 tar Substances 0.000 description 8
- 239000011289 tar acid Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000010742 number 1 fuel oil Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 101150010353 Ascl1 gene Proteins 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
-
- 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
Definitions
- the invention relates to a process for the treatment of process water and waste water in the hydrogenation of coal.
- Coal hydrogenation is usually understood to mean the addition of molecular hydrogen to coal under pressure and under cracking conditions, with catalysts generally being present.
- Oxygen contained in the coal is partly in the hydrogenation in tar acids, i.e. H. Phenols, cresols and xylenols converted. Another proportion of oxygen leads to the formation of water of reaction.
- the hydrogenation is followed by separators in which the hydrogenation products are separated.
- the so-called cold separator separates the CARBON OIL and the aqueous phase.
- Quench water is injected to prevent blockages due to salt formation in the pipes upstream of the cold separator. Together with the water of reaction in the cold separator, this forms the aforementioned aqueous phase.
- the tar acids are very water-soluble products. Some of them go into the reaction and quench water.
- the listed wastewater cannot be released into public waters due to environmental protection reasons because of the tar acid content and the hydrogen sulfide and ammonia still contained in them.
- the state of the art is to feed them to a phenol recovery system with a downstream wastewater treatment after separation of hydrogen sulfide and ammonia.
- the wastewater cleaned in this way can be discharged with a remaining permissible residual phenol content.
- An older proposal (DE-30 36 259 A 1) provides for the use of the waters containing tar acid to be used in a Texaco gasification plant connected to the hydrogenation plant to solve the sewage problems.
- the Texaco plant is used to generate hydrogen from vacuum residues or coal, the vacuum residues or the coal being introduced into the reactor in a water suspension.
- the suspension is created from the tar-containing water.
- the resulting disposal option does not require any intermediate cleaning stages for the water.
- the invention is therefore based on the object of simplifying the treatment of the process water and waste water in such cases. According to the invention this is achieved in that the tar-containing wastewater from atmospheric distillation and / or vacuum distillation is used as quench water and thus to reduce the necessary amount of demineralized water to be supplied. At the same time, the total amount of waste water from the hydrogenation system is reduced by the amount returned. This is ultimately associated with an increase in the amount of coal oil used by reducing the amount of tar acid that passes into the aqueous phase as a result of the initial concentration of tar acid already contained in the return water.
- Dried coal is mashed with solvent in a slurry 1 and hydrogenated in a reactor 2 with the addition of hydrogen.
- the reaction products are separated in a hot separator downstream of the hydrogenation reactor 1.
- gases and vapors are drawn off overhead; a liquid phase, which contains the solids, is removed from the sump into the vacuum distillation 4.
- the top product of the hot separator 3 is passed to a downstream cold separator 5.
- the liquid phase is water, which is partly formed from the oxygen chemically bound in the coal and partly consists of injection water (quench water). This quench water is injected into the vapor phase behind the hot separator 3 in order to avoid blockages caused by crystallizing ammonium salts.
- the water contains part of the tar acids (phenols, cresols, xylenols), which are also formed in the hydrogenation from the oxygen contained in the coal.
- tar acids phenols, cresols, xylenols
- coal oil obtained is distilled atmospherically with addition of stripping steam in an atmospheric distillation 6.
- the water phase resulting from the cooling of the top product in turn contains tar acids.
- Light and medium oil of atm. Distillation 6 are subjected to a hydrogenating stabilization 7.
- the outgoing gas phase of the cold separator 5 is divided into recycled cycle and discharge gas after an oil wash carried out under process pressure.
- the discharge gas is cleaned in a gas scrubber 8 and broken down into hydrogen, heating gas, SNG and LPG in a low-temperature separation plant 9.
- the solid-containing residue of the hot separator 3 is topped in the vacuum distillation 4.
- the resulting heavy oil is extracted from the atm together with heavy and medium oil. Distillation as solvent in the mash 1.
- Steam jets are used to generate vacuum.
- the condensate of the propellant steam used contains tar components.
- the water generated in the hydrogenation is composed of the residual moisture of the coal, the injection and formation water.
- the amount of injection water is 34.8 t / day, i. H. the wastewater from the distillations 30.4 t / day can cover this water requirement approximately.
- the amount of waste water containing tar acid is advantageously reduced by this value. Instead of 76.1 t / day, only 45.7 t / day are incurred.
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)
- Industrial Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3322784 | 1983-06-24 | ||
DE19833322784 DE3322784A1 (de) | 1983-06-24 | 1983-06-24 | Verfahren zur behandlung von prozessabwaessern und abwaessern bei der hydrierung von kohle |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0129680A2 EP0129680A2 (de) | 1985-01-02 |
EP0129680A3 EP0129680A3 (en) | 1987-05-06 |
EP0129680B1 true EP0129680B1 (de) | 1988-08-17 |
Family
ID=6202299
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84105177A Expired EP0129680B1 (de) | 1983-06-24 | 1984-05-08 | Verfahren zur Behandlung von Prozessabwässern und Abwässern bei der Hydrierung von Kohle |
Country Status (9)
Country | Link |
---|---|
US (1) | US4597851A (enrdf_load_stackoverflow) |
EP (1) | EP0129680B1 (enrdf_load_stackoverflow) |
JP (1) | JPS6013886A (enrdf_load_stackoverflow) |
AU (1) | AU557994B2 (enrdf_load_stackoverflow) |
BR (1) | BR8403056A (enrdf_load_stackoverflow) |
CA (1) | CA1231655A (enrdf_load_stackoverflow) |
DE (2) | DE3322784A1 (enrdf_load_stackoverflow) |
PL (1) | PL146219B1 (enrdf_load_stackoverflow) |
ZA (1) | ZA844751B (enrdf_load_stackoverflow) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6437303A (en) * | 1987-08-03 | 1989-02-08 | Komatsu Mfg Co Ltd | Liquid gnawing seal type continuous liquid/viscous object packaging method and equipment |
JPH01153410A (ja) * | 1987-12-10 | 1989-06-15 | Komatsu Ltd | 液かみシール型連続液体・粘体包装装置 |
US6533945B2 (en) | 2000-04-28 | 2003-03-18 | Texaco Inc. | Fischer-Tropsch wastewater utilization |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1931550A (en) * | 1925-02-14 | 1933-10-24 | Standard Ig Co | Conversion of solid fuels and products derived therefrom or other materials into valuable liquids |
US1983234A (en) * | 1925-02-14 | 1934-12-04 | Standard Ig Co | Conversion of solid fuels and product derived therefrom or o'ther materials into valuable liquids |
US1994075A (en) * | 1925-02-14 | 1935-03-12 | Standard Ig Co | Conversion of solid fuels and products derived therefrom or other materials into valuable liquids |
US1996009A (en) * | 1925-02-14 | 1935-03-26 | Standard Ig Co | Conversion of solid fuels and products derived therefrom or other materials into valuable liquids |
US1990708A (en) * | 1930-08-22 | 1935-02-12 | Standard Ig Co | Production of valuable hydrocarbons |
GB522037A (en) * | 1938-12-03 | 1940-06-06 | Int Hydrogeneeringsoctrooien | Improvements in the destructive hydrogenation of carbonaceous materials and in dephenolising waste water |
US3503866A (en) * | 1968-04-24 | 1970-03-31 | Atlantic Richfield Co | Process and system for producing synthetic crude from coal |
US3909390A (en) * | 1972-09-15 | 1975-09-30 | Universal Oil Prod Co | Coal liquefaction process |
US3926775A (en) * | 1973-11-01 | 1975-12-16 | Wilburn C Schroeder | Hydrogenation of coal |
US3944480A (en) * | 1974-03-29 | 1976-03-16 | Schroeder Wilburn C | Production of oil and high Btu gas from coal |
US3954596A (en) * | 1974-06-03 | 1976-05-04 | Schroeder Wilburn C | Production of low sulfur heavy oil from coal |
US4260471A (en) * | 1979-07-05 | 1981-04-07 | Union Oil Company Of California | Process for desulfurizing coal and producing synthetic fuels |
US4350582A (en) * | 1979-10-18 | 1982-09-21 | Chevron Research Company | Two-stage coal liquefaction process with process-derived solvent |
-
1983
- 1983-06-24 DE DE19833322784 patent/DE3322784A1/de not_active Withdrawn
-
1984
- 1984-05-08 EP EP84105177A patent/EP0129680B1/de not_active Expired
- 1984-05-08 DE DE8484105177T patent/DE3473472D1/de not_active Expired
- 1984-06-21 AU AU29703/84A patent/AU557994B2/en not_active Ceased
- 1984-06-22 ZA ZA844751A patent/ZA844751B/xx unknown
- 1984-06-22 CA CA000457191A patent/CA1231655A/en not_active Expired
- 1984-06-22 JP JP59127695A patent/JPS6013886A/ja active Granted
- 1984-06-22 PL PL1984248360A patent/PL146219B1/pl unknown
- 1984-06-22 BR BR8403056A patent/BR8403056A/pt not_active IP Right Cessation
- 1984-06-25 US US06/624,105 patent/US4597851A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
AU557994B2 (en) | 1987-01-15 |
DE3473472D1 (en) | 1988-09-22 |
EP0129680A2 (de) | 1985-01-02 |
AU2970384A (en) | 1985-01-31 |
PL146219B1 (en) | 1989-01-31 |
JPH037237B2 (enrdf_load_stackoverflow) | 1991-02-01 |
BR8403056A (pt) | 1985-05-28 |
JPS6013886A (ja) | 1985-01-24 |
EP0129680A3 (en) | 1987-05-06 |
DE3322784A1 (de) | 1985-01-03 |
ZA844751B (en) | 1985-05-29 |
PL248360A1 (en) | 1985-04-24 |
US4597851A (en) | 1986-07-01 |
CA1231655A (en) | 1988-01-19 |
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