EP0083670A1 - Procédé pour d'élimination des effluents aqueux contenant des acides de goudron - Google Patents

Procédé pour d'élimination des effluents aqueux contenant des acides de goudron Download PDF

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Publication number
EP0083670A1
EP0083670A1 EP82100048A EP82100048A EP0083670A1 EP 0083670 A1 EP0083670 A1 EP 0083670A1 EP 82100048 A EP82100048 A EP 82100048A EP 82100048 A EP82100048 A EP 82100048A EP 0083670 A1 EP0083670 A1 EP 0083670A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenation
coal
water
gasification
hydrogen
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.)
Withdrawn
Application number
EP82100048A
Other languages
German (de)
English (en)
Inventor
Josef Dr. Rer.Nat. Langhoff
Eckard Dr.-Ing. Wolowski
Hans-F. Dipl.-Ing. Tamm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RAG AG
Original Assignee
Ruhrkohle AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ruhrkohle AG filed Critical Ruhrkohle AG
Priority to EP82100048A priority Critical patent/EP0083670A1/fr
Publication of EP0083670A1 publication Critical patent/EP0083670A1/fr
Withdrawn legal-status Critical Current

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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
    • C10G1/002—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

  • the invention relates to a process for removing tar-containing process waste water from 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.
  • a further quantity of wastewater containing tar acid is obtained in the atmospheric distillation of the coal oil obtained in the hydrogenation with the addition of steam (stripping steam).
  • the process wastewater cannot easily be released into public waters due to the tar acid content and also due to a harmful hydrogen sulfide and ammonia content for environmental protection reasons. For this reason, it was previously necessary to feed the process wastewater to a phenol recovery system with downstream wastewater treatment after the separation of hydrogen sulfide and ammonia. Only the wastewater purified in this way can. with a low residual phenol content. This type of treatment of the process wastewater requires a considerable expenditure in terms of apparatus and energy, which increases the greater the amount of water to be cleaned.
  • the invention is therefore based on the object of improving the treatment of the process wastewater. According to the invention this is achieved in that the process waste water is fed to a carbon gasification process. In carbon gasification, water or steam is the process medium. According to the invention, the waste water is therefore added to the process medium water or steam and / or used as a substitute for fresh water and fresh steam. This is particularly advantageous if the carbon is pumped into the gasification reactor in the form of a carbon liquid suspension (coal / water slurry) or hydrogenation residues.
  • the carbon gasification plant to which the process waste water from the hydrogenation is fed, is preferably connected to the hydrogenation plant in which the process waste water is obtained.
  • the gasification plant supplies the hydrogen required for the hydrogenation.
  • gas flame coal from the Ruhr region is used for a coal liquefaction plant with a throughput of 5,000 t (waf) coal / day.
  • the coal is processed, i.e. it is dried and ground.
  • the coal pretreated in this way is mashed in a second process step 1 .
  • oil from the hydrogenation process is returned, ie it is mashed with circulated oil.
  • the oil added during mashing 1 is referred to as grinding oil.
  • the rubbing oil serves as a solvent in which it is able to release bound hydrogen to the coal. This leads to the beginning of liquefaction, which can also be referred to as hydration or swelling.
  • the solvent also facilitates the actual hydrogenation 2 of the coal, which takes place with the addition of free hydrogen.
  • This hydrogen comes from a gasification plant, which will be explained below.
  • Various separators are arranged after the hydrogenation stage. The gaseous, liquid and solid phases are separated from each other in the separators.
  • a first separation process 3 takes place by cooling and quenching with fresh water.
  • the gaseous phase separates and liquid products separate from the gas.
  • some of the tar acids formed in the hydrogenation 2 from the oxygen contained in the coal pass here into the aqueous phase consisting of quench and reaction water.
  • liquid products, gas and solid-containing residues are formed during the separation.
  • the resulting gas is partly recycled into the hydrogenation 2.
  • the remaining part of the resulting gas is fed to a gas scrubber 4, from which it enters a low-temperature decomposition 5.
  • heating gas, SNG, LPG and H 2 are generated.
  • the hydrogen is also fed to the hydrogenation 2.
  • the liquid products obtained in the separation 3 are distilled atmospherically with the addition of stripping steam.
  • a water phase is formed which contains tar acids.
  • the main product of atmospheric distillation 6, however, are light oil and medium oil, which are subjected to a hydrogenating stabilization in a process step 7.
  • gas is produced, which reaches the low-temperature decomposition 5 via the gas scrubber 4.
  • the gas originating from the distillation 6 is worked up in the same way as the gas originating from the deposition 3.
  • the solid-containing residue obtained in quench 3 is topped in a vacuum distillation 8. This creates on the one hand solvent for mashing 1 and on the other hand a vacuum residue.
  • the vacuum residue from distillation 8 is gasified in a residue gasification 9 using the Texsco gasification process.
  • the high-melting residue can contain up to 50% solids.
  • residue gasification 9 according to the invention, in contrast to an otherwise possible waste water treatment by ammonia extraction 10 with subsequent phenol extraction 11, biological treatment and introduction into public waters, a special dashed line of waste water is shown.
  • the waste water used in the gasification serves to remove the tar acid, without the considerable expenditure in terms of equipment and energy required for the cleaning stage.
  • the pores waste water obtained in the separation and quenching 3 and in the distillation 6 are optionally fed to the residue gasification 9 and / or a coal gasification 12 with an upstream suspension production 13.
  • the coal gasification 12 serves to generate the hydrogen required for the hydrogenation 2 and the stabilizing hydrogenation 7, which may be necessary in addition to the hydrogen from the cycle gas, the low-temperature decomposition and the residue gasification.
  • the gasification 12, like the residue narrowing 9, is a gasification according to the Texaco method. It is an autothermal gasification under pressure. With this gasification, pre-shredded feed material with a grain size of less than 0.1 mm is mixed with water to form a stable, pumpable slurry that contains approx. 55 - 50% solids.
  • This suspension is fed to a burner at the top of the reactor and gasified vertically in the downflow in the reactor under increased pressure in the presence of steam and supply of oxygen.
  • the reaction with oxygen gives temperatures of approx. 1400 ° C.
  • the ash is liquid.
  • Synthesis gas is produced which, with a carbon conversion of approx. 95%, has the following gas analysis:
  • the Texaco process is essentially characterized by the production of the pumpable slurry, which allows the coal or hydrogenation residues to be introduced by means of a pump.
  • Fresh water per se would be required for the production of the slurry, which according to the invention is replaced by the waste water from the separation and quenching 3 and the distillation 6.
  • the fresh water supply to be replaced by the wastewater is shown in dash-dotted lines in the suspension production 13 and corresponds to the water vapor supply in the residue gasification 9 also shown in dash-dotted lines.
  • the wastewater supply to the residue gasification 9 and the suspension production 13 is shown in broken lines.
  • the residue amount resulting in vacuum distillation is approx. 74.2 t / h with a solids content of approx. 40%.
  • a steam addition of approx. 28.9 t / h is necessary.
  • the use of 9.6 t / h of water is necessary to mix this amount of coal.
  • the hydrogen is obtained from the synthesis gas with subsequent conversion and gas scrubbing 14 and fed to the hydrogenation 2 and the stabilization 7.
  • the gasification only produces wastewater that can be discharged into public waters with slight neutralization.

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  • 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)
  • Processing Of Solid Wastes (AREA)
EP82100048A 1982-01-07 1982-01-07 Procédé pour d'élimination des effluents aqueux contenant des acides de goudron Withdrawn EP0083670A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP82100048A EP0083670A1 (fr) 1982-01-07 1982-01-07 Procédé pour d'élimination des effluents aqueux contenant des acides de goudron

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP82100048A EP0083670A1 (fr) 1982-01-07 1982-01-07 Procédé pour d'élimination des effluents aqueux contenant des acides de goudron

Publications (1)

Publication Number Publication Date
EP0083670A1 true EP0083670A1 (fr) 1983-07-20

Family

ID=8188808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82100048A Withdrawn EP0083670A1 (fr) 1982-01-07 1982-01-07 Procédé pour d'élimination des effluents aqueux contenant des acides de goudron

Country Status (1)

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EP (1) EP0083670A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2146039A (en) * 1983-08-25 1985-04-11 British Gas Corp Gasification of carbonaceous materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR852043A (fr) * 1939-03-23 1940-01-22 Int Hydrogeneeringsoctrooien Procédé pour hydrogéner destructivement des matières carbonées et déphénoler les eaux résiduelles
US3617471A (en) * 1968-12-26 1971-11-02 Texaco Inc Hydrotorting of shale to produce shale oil
AU466181B2 (en) * 1973-02-01 1975-10-23 Texaco Development Corporation Multi-hydrotorting of coal
US4211540A (en) * 1978-12-29 1980-07-08 Fluor Corporation Process for the manufacture of fuel gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR852043A (fr) * 1939-03-23 1940-01-22 Int Hydrogeneeringsoctrooien Procédé pour hydrogéner destructivement des matières carbonées et déphénoler les eaux résiduelles
US3617471A (en) * 1968-12-26 1971-11-02 Texaco Inc Hydrotorting of shale to produce shale oil
AU466181B2 (en) * 1973-02-01 1975-10-23 Texaco Development Corporation Multi-hydrotorting of coal
US4211540A (en) * 1978-12-29 1980-07-08 Fluor Corporation Process for the manufacture of fuel gas

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2146039A (en) * 1983-08-25 1985-04-11 British Gas Corp Gasification of carbonaceous materials

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19821029

AK Designated contracting states

Designated state(s): BE FR GB IT NL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19850419

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TAMM, HANS-F., DIPL.-ING.

Inventor name: LANGHOFF, JOSEF, DR. RER.NAT.

Inventor name: WOLOWSKI, ECKARD, DR.-ING.