EP0135943B1 - Process for separating resinous materials from heavy coal oils, and use of the fractions so obtained - Google Patents
Process for separating resinous materials from heavy coal oils, and use of the fractions so obtained Download PDFInfo
- Publication number
- EP0135943B1 EP0135943B1 EP84200689A EP84200689A EP0135943B1 EP 0135943 B1 EP0135943 B1 EP 0135943B1 EP 84200689 A EP84200689 A EP 84200689A EP 84200689 A EP84200689 A EP 84200689A EP 0135943 B1 EP0135943 B1 EP 0135943B1
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- weight
- aromatic
- oil
- solvent
- solvents
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 24
- 239000012260 resinous material Substances 0.000 title claims 2
- 239000010742 number 1 fuel oil Substances 0.000 title 1
- 239000000295 fuel oil Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 12
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003849 aromatic solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000571 coke Substances 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 239000004071 soot Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000002635 aromatic organic solvent Substances 0.000 claims 2
- 239000010692 aromatic oil Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011295 pitch Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 238000000926 separation method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000011883 electrode binding agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002864 coal component Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000011339 hard pitch Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 239000011338 soft pitch Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
- C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
- C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
- C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
- C10L5/16—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders with bituminous binders, e.g. tar, pitch
Definitions
- the invention relates to a process for separating predominantly dissolved resinous substances from coal-derived heavy oils, in which two fluid fractions are obtained, one of which contains only a small proportion of toluene-insoluble substances (TI), and the other enriches the toluene-insoluble (TI) is, as well as the use of these fractions.
- TI toluene-insoluble substances
- the quinoline-insoluble solids (QI) present in the residues are undesirable for many processing processes and are therefore removed, if necessary, by mechanical separation processes.
- the separation effect is achieved either due to the particle size as in filtration or primarily due to the higher density of solids as in centrifugation. It is also known to agglomerate the solid particles by adding a promoter liquid so that they can be removed from the residues under the action of gravity by simply letting them settle (DE-PS-2 810 332).
- the almost QI-free residues are mainly used for the production of highly anisotropic carbons.
- the known processes aim to keep the loss of ⁇ -resins (TI - QI) as low as possible.
- This also has the advantage that the 0.1-rich residue is obtained as an easily manageable granulable solid (DE-OS-3 112 004) or as a non-sticky suspension (DE-OS-2 355 606).
- pitches with a high content of ⁇ -resins are required, which also have a not too low content of quinoline-insoluble.
- Additional ⁇ -resins can be produced in the heavy oils by a gentle thermal treatment, but a simultaneous generation of QI, which is not desirable, cannot be avoided. In addition, such thermal processes are very complex. Mechanical separation processes for TI concentration are not known.
- Hard pitches with a high QI content and a high coking residue are required for the production of abrasion-resistant, hard coke with a high bulk density, as are used, for example, for the carburization of steel and cast iron.
- Such hard pitches have hitherto been produced from normal pitches by thermal treatment and blowing with air and coked in horizontal chamber furnaces.
- pitches with a low TI content and a high Bureau of Mines Correlation Index are an excellent carbon black oil component.
- Methods for the production of such carbon black raw materials are described in the patents DE-2 547 679 and DE-2 560 019.
- the insoluble in toluene is removed in a high-speed centrifuge or with a very fine filter.
- this method appears to be of little use for technical implementation due to the small difference in density between the ⁇ -resins and the other pitch components suitable.
- This object is achieved according to the invention in that the content of toluene-insoluble (TI) in the heavy oil used, obtained from coal, with an aromatic solvent to less than 10 % By weight, preferably less than 5% by weight, and the mixture is mixed with a non-aromatic, organic solvent in a ratio of 1: 3 to 5: 1 and with stirring the heavy, TI-rich phase which settles with a peripheral speed of the stirrer of 0.5 to 6.0 m / s at a temperature between 50 and 200 ° C, preferably between 50 and 100 ° C under the influence of gravity with a clarification surface load of up to 1 t / m 2 h in a TI poor and a TI-rich fraction is separated.
- TI toluene-insoluble
- the amount used per unit of time in relation to the clarification area is referred to as the clarification area load.
- the aromatic solvent can be added to the heavy oil first or together with the non-aromatic solvent. Mixing is not a problem. For example, a static mixer can be used. Mixing in a centrifugal pump is also sufficient, however, if the solvent is metered in evenly before the pump.
- a solvent combination of methylnaphthalene oil and petrol has proven itself for heavy oils with a boiling point of about 300 ° C and above, but other solvent combinations such as xylene and n-heptane also serve the same purpose. For reasons of cost, however, fractions are preferred to pure substances.
- ratio of the container diameter (d) to the filling height (h) also has an influence on the removal of the toluene-insoluble.
- a ratio d / h 2 is particularly advantageous.
- the inventive method makes it possible to reduce the residues from the reprocessing of coal-derived heavy oils with reasonable effort and to partially process them into valuable products. This opens up new areas of application for these residues that were previously reserved for oils obtained by distillation.
- the inventive method is explained in more detail on the basis of a few discontinuous exemplary embodiments, without being limited thereto.
- the process can also be carried out continuously with the same result, the mixture of heavy oil and solvents preferably being fed into the agitator tank in the region of the phase interface.
- the sewage treatment area load is 0.15 t / M 2 h.
- the settling process with stirring at 60 ° C is complete after one hour.
- the two fractions are discontinuously distilled at a top pressure of 93 mbar up to a top temperature of 90 ° C. in order to recover the solvents.
- the residues left are 26.3 parts by weight of a low-TI fraction in which there are still 0.2% by weight of toluene but no methanol, and 13.8 parts by weight of a TI-rich fraction in the no solvent residues can be detected.
- the analysis data are shown in the table.
- the TI-poor fraction has a Bureau of Mines Correlation Index of 175 and is used as a soot raw material.
- the coke yield based on the pitch residue (normal pitch) is 62% by weight.
- the mixture After being left to sit for 2 hours with stirring at 73 ° C., the mixture separated into a light and a heavy phase. At 100 mbar head pressure and a bottom temperature of up to 288 ° C., 25 parts by weight of the upper phase and 1 part by weight of solvent are distilled off from the lower phase. In this way, 6 parts by weight of a TI-rich and 4 parts by weight of a TI-poor fraction are obtained, the analysis data of which are listed in the table.
- the 6 parts by weight of the TI-rich fraction are mixed with 3 parts by weight of coal pitch normal pitch with the same analysis data as the pitch to be extracted and processed by gentle helmet distillation to form electrode binders.
- a binder with a softening point of 90 ° C. (K.-S.) a QI content of 10.2% by weight, a ⁇ -resin content of 25.3% by weight, an ash content of 0.28% by weight and a coking residue (Conradson) of 52.6% by weight.
- the phase separation is completed within one hour. 24 parts by weight of solvent and tar oils are distilled off from the light phase at a top pressure of 100 mbar and a bottom temperature of up to 350 ° C. The remaining 5 parts by weight of distillation residue are almost free of Ql and contain only 1.3% by weight of ⁇ -resins. The softening point is 62 ° C (K.-S.) and the coking residue is 43.1% by weight. The residue is used as an impregnating agent in graphite electrodes for steel production.
- 0.5 part by weight is distilled off from the 4 parts by weight of the heavy phase at a top pressure of 100 mbar and a bottom temperature of up to 370.degree.
- the residue with a softening point of 90 ° C (K.-S.) and a coking residue (Conradson) of 54.3% by weight has an ash content of 0.3% by weight and a QI content of 9.5 % By weight and a ⁇ -resin content of 26.7% by weight and is used as an electrode binder.
- a coal-based product from which the ash constituents or the quinoline-insoluble matter has at least partially been removed can also be used as the heavy oil. It is known to reduce the ash content in heavy oils by centrifugation, and to at least partially remove the quinoline-insoluble by filtering, separating or allowing accelerated settling. In particular, methods for removing the quinoline-insoluble by letting the promoter accelerate settling can be combined well with the inventive method.
- Example 2 20 parts by weight of normal pitch coal pitch as in Example 2 are mixed with 9 parts by weight of methylnaphthalene oil (boiling range 235 to 245 ° C) and 9 parts by weight of kerosene (boiling range 250 to 300 ° C) in a tip-top container with a reflux condenser for 3 hours with stirring 250 ° C thermally treated. The mixture is then cooled to 180 ° C. by pumping over a cooler. After one hour without stirring, a QI-rich fraction (20% by weight of the mixture) has settled on the bottom and is drained off.
- methylnaphthalene oil oil
- kerosene boiling range 250 to 300 ° C
- Example 2 A normal pitch as in Example 2 is used. The extraction is carried out as in this example, but without stirring. There is no flowable heavy phase. The material that settles out can neither be loosened nor melted completely and must therefore be removed mechanically.
- Example 2 The test is carried out as described in Example 2, with the exception that only 5 parts by weight of white spirit are used.
- the TI content of the solvent-free TI-low fraction is 3.9% by weight.
- the material is not suitable as a soot oil component.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Working-Up Tar And Pitch (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Coke Industry (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Abtrennung von überwiegend gelösten harzartigen Stoffen aus kohlestämmigen Schwerölen, bei dem zwei fluide Fraktionen gewonnen werden, von denen die eine nur einen geringen Anteil an toluolunlöslichen Stoffen (TI) enthält, und in der anderen das Toluolunlösliche (TI) angereichert ist, sowie die Verwendung dieser Fraktionen.The invention relates to a process for separating predominantly dissolved resinous substances from coal-derived heavy oils, in which two fluid fractions are obtained, one of which contains only a small proportion of toluene-insoluble substances (TI), and the other enriches the toluene-insoluble (TI) is, as well as the use of these fractions.
Schweröle, die aus Kohle erhalten werden, insbesondere Kohleverflüssigungsprodukte und Teere aus der Vergasung oder Verkokung von Braunkohle und Steinkohle werden durch destillative Aufarbeitung raffiniert. Dieses thermische Aufarbeitungsverfahren ist auf den verdampfbaren Anteil der Schweröle beschränkt und wird durch ihre Zersetzungstemperatur begrenzt. Der verbleibende Rückstand enthält alle nicht vorher entfernten Asche-, Koksund Kohlebestandteile und die von Anfang an enthaltenen oder neu gebildeten hochmolekularen Feststoffe.Heavy oils obtained from coal, in particular coal liquefaction products and tars from the gasification or coking of lignite and hard coal, are refined by working up by distillation. This thermal work-up process is limited to the evaporable portion of the heavy oils and is limited by their decomposition temperature. The remaining residue contains all ash, coke and coal components not removed beforehand and the high-molecular solids contained or newly formed from the beginning.
Die in den Rückständen vorhandenen in Chinolin unlöslichen Feststoffe (QI) sind für viele weiterverarbeitende Prozesse unerwünscht und werden daher, soweit erforderlich, durch mechanische Trennverfahren entfernt. Der Trenneffekt wird entweder aufgrund der Teilchengröße wie beim Filtrieren oder in erster Linie aufgrund der höheren Dichte der Feststoffe wie beim Zentrifugieren erzielt. Es ist außerdem bekannt, die Feststoffpartikel durch Zugabe einer Promotorflüssigkeit zu agglomerieren, so daß sie unter Einwirkung der Schwerkraft durch einfaches Absetzenlassen aus den Rückständen entfernt werden können (DE-PS-2 810 332).The quinoline-insoluble solids (QI) present in the residues are undesirable for many processing processes and are therefore removed, if necessary, by mechanical separation processes. The separation effect is achieved either due to the particle size as in filtration or primarily due to the higher density of solids as in centrifugation. It is also known to agglomerate the solid particles by adding a promoter liquid so that they can be removed from the residues under the action of gravity by simply letting them settle (DE-PS-2 810 332).
Nach Abdestillieren der Promotorflüssigkeit werden die nahezu QI-freien Rückstände überwiegend für die Herstellung hochanisotroper Kohlenstoffe verwendet. Um eine möglichst hohe Kohlenstoffausbeute zu erzielen, wird bei den bekannten Verfahren angestrebt, den Verlust an β-Harzen (TI - QI) möglichst gering zu halten. Das hat außerdem den Vorteil, daß der 0.1-reiche Rückstand als leichthandhabbarer granulierbarer Feststoff (DE-OS-3 112 004) oder als nicht klebrige Suspension (DE-OS-2 355 606) anfällt.After distilling off the promoter liquid, the almost QI-free residues are mainly used for the production of highly anisotropic carbons. In order to achieve the highest possible carbon yield, the known processes aim to keep the loss of β-resins (TI - QI) as low as possible. This also has the advantage that the 0.1-rich residue is obtained as an easily manageable granulable solid (DE-OS-3 112 004) or as a non-sticky suspension (DE-OS-2 355 606).
Die Abtrennung des Toluolunlöslichen ist insbesondere bei einem hohen Anteil an β-Harzen, wie sie in Hochtemperatpr-Steinkohlenteeren vorliegen, nur sehr schwierig durchführbar. Die β-Harze bilden beim Ausfällen mit den chinolinunlöslichen Feststoffen eine klebrige gummiartige Masse, die sich am Boden des Absetzbehälters und in den Rohrleitungen festsetzt und nur mechanisch entfernt werden kann.The removal of the toluene-insoluble is very difficult to carry out, in particular in the case of a high proportion of β-resins, as are present in high-temperature coal tars. When precipitated with the quinoline-insoluble solids, the β-resins form a sticky, rubber-like mass which settles on the bottom of the settling tank and in the pipes and can only be removed mechanically.
Es ist eine Analysenmethode zur Bestimmung des Toluolunlöslichen bekannt, die sich für die Abtrennung auch der β-Harze unter Laborbedingungen eignet. Für die Übertragung auf ein kommerziell verwertbares Verfahren ist sie jedoch wegen des benötigten hohen Lösungsmittelüberschusses von etwa 70 Gew.- Teilen Lösungsmittel auf je 1 Gew.- Teil Schweröle ungeeignet.An analytical method for determining the toluene-insoluble is known, which is also suitable for the separation of the β-resins under laboratory conditions. However, it is unsuitable for transfer to a commercially usable process because of the required high solvent excess of approximately 70 parts by weight of solvent per 1 part by weight of heavy oils.
Für die Herstellung hochwertiger Elektrodenbindemittel werden Peche mit einem hohen Gehalt an β-Harzen benötigt, die außerdem einen nicht zu niedrigen Gehalt an Chinolinunlöslichem aufweisen.For the production of high-quality electrode binders, pitches with a high content of β-resins are required, which also have a not too low content of quinoline-insoluble.
Zusätzliche β-Harze lassen sich zwar in den Schwerölen durch eine schonende thermische Behandlung erzeugen, jedoch ist eine gleichzeitige Erzeugung von QI nicht zu vermeiden, die nicht erwünscht ist. Außerdem sind solche thermischen Verfahren sehr aufwendig. Mechanische Trennverfahren zur TI-Aufkonzentration sind nicht bekannt.Additional β-resins can be produced in the heavy oils by a gentle thermal treatment, but a simultaneous generation of QI, which is not desirable, cannot be avoided. In addition, such thermal processes are very complex. Mechanical separation processes for TI concentration are not known.
Für die Herstellung abriebfester, harter Kokse mit hohem Schüttgewicht, wie sie beispielsweise für die Aufkohlung von Stahl und Gußeisen verwendet werden, werden Hartpeche mit einem hohen QI-Gehalt und hohem Verkokungsrückstand benötigt. Solche Hartpeche werden bisher aus Normalpechen durch thermische Behandlung und Verblasen mit Luft hergestellt und in Horizontalkammeröfen verkokt.Hard pitches with a high QI content and a high coking residue are required for the production of abrasion-resistant, hard coke with a high bulk density, as are used, for example, for the carburization of steel and cast iron. Such hard pitches have hitherto been produced from normal pitches by thermal treatment and blowing with air and coked in horizontal chamber furnaces.
Es ist andererseits bekannt, daß Peche mit einem niedrigen TI-Gehalt und einem hohen Bureau of Mines Correlation Index eine ausgezeichnete Rußölkomponente sind. In den Patentschriften DE-2 547 679 und DE-2 560 019 werden Verfahren zur Herstellung solcher Rußrohstoffe beschrieben. Das Toluolunlösliche wird dabei in einer hochtourigen Zentrifuge oder mit einem sehr feinen Filter entfernt. Abgesehen davon, daß die Wirksamkeit einer Zentrifuge nicht allein von ihrer Drehzahl, sondern zumindest auch von ihrem Durchmesser und der freien Weglänge des abzutrennenden Partikels abhängt, erscheint diese Methode wegen des geringen Dichteunterschiedes zwischen den β-Harzen und den übrigen Pechbestandteilen für eine technische Durchführung wenig geeignet. Es ist weiterhin bekannt, daß β-Harze ohne vorheriges Ausfällen wie etwa in der beschriebenen Analysenmethode nicht durch Filtrieren gewonnen werden können. Selbst das Abtrennen der chinolinunlöslichen Feststoffe ist technisch nur mit entsprechenden Filterhilfsmitteln möglich, wobei der Rückstand als Abfall verworfen wird. Die bekannten Verfahren zeigen zwar, daß aus nahezu TI-freien Pechen im Gemisch mit Steamkrackerölen oder Anthracenöl hochwertige Rußrohstoffe erhalten werden können, die beschriebenen Verfahren zur Abtrennung des Toluolunlöslichen sind jedoch zumindest bei Pechen mit einem hohen β-Harzgehalt technisch nicht durchführbar.On the other hand, it is known that pitches with a low TI content and a high Bureau of Mines Correlation Index are an excellent carbon black oil component. Methods for the production of such carbon black raw materials are described in the patents DE-2 547 679 and DE-2 560 019. The insoluble in toluene is removed in a high-speed centrifuge or with a very fine filter. Apart from the fact that the effectiveness of a centrifuge depends not only on its speed, but at least also on its diameter and the free path length of the particle to be separated, this method appears to be of little use for technical implementation due to the small difference in density between the β-resins and the other pitch components suitable. It is also known that β-resins cannot be obtained by filtration without prior precipitation, such as in the analytical method described. Even the removal of the quinoline-insoluble solids is technically only possible with appropriate filter aids, with the residue being discarded as waste. Although the known processes show that high-quality soot raw materials can be obtained from almost TI-free pitches in a mixture with steam cracker oils or anthracene oil, the processes described for separating the toluene-insoluble are technically not feasible, at least for pitches with a high β-resin content.
Für die Herstellung von Imprägniermitteln für Kohlenstoff-Formkörper werden niedrigviskose, aromatische Rückstandsöle mit hohem Verkokungsrückstand gewünscht. Auch hier sind aus Kohle erhältliche Schweröle mit niedrigem TI-Gehalt geeignete Ausgangsprodukte.Low-viscosity, aromatic residual oils with high coking residues are desired for the production of impregnating agents for carbon moldings. Heavy oils with a low TI content available from coal are also suitable starting products here.
Es bestand daher die Aufgabe, aus Kohle erhältliche Schweröle mit destillativ leicht abtrennbaren Lösungsmitteln oder Lösungsmittelgemischen in zwei fluide Fraktionen aufzutrennen, von denen die eine nur geringe Anteile von toluolunlöslichen Bestandteilen (TI) enthält, und in der anderen das Toluolunlösliche aufkonzentriert ist, und für beide Fraktionen geeignet Einsatzmöglichkeiten aufzuzeigen.It was therefore the task of separating heavy oils obtainable from coal with solvents or solvent mixtures which can be easily removed by distillation into two fluid fractions, one of which contains only a small proportion of toluene-insoluble constituents (TI) and the other of which the toluene-insoluble constituent is concentrated, and for both Fractions suitable to show possible uses.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Gehalt an Toluolunlöslichem (TI) in dem eingesetzten, aus Kohle gewonnenem Schweröl mit einem aromatischen Lösungsmittel auf weniger als 10 Gew.-%, vorzugsweise auf weniger als 5 Gew.-%, eingestellt wird und das Gemisch mit einem nichtaromatischen, organischen Lösungsmittel im Verhältnis 1 : 3 bis 5 : 1 gemischt und unter Rühren der sich absetzenden, schweren, TI-reichen Phase mit einer Umfangsgeschwindigkeit des Rührers von 0,5 bis 6,0 m/s bei einer Temperatur zwischen 50 und 200°C, vorzugsweise zwischen 50 und 100°C unter Schwerkrafteinwirkung bei einer Klärflächenbelastung von bis zu 1 t/m2h in eine TI-arme und eine TI-reiche Fraktion getrennt wird.This object is achieved according to the invention in that the content of toluene-insoluble (TI) in the heavy oil used, obtained from coal, with an aromatic solvent to less than 10 % By weight, preferably less than 5% by weight, and the mixture is mixed with a non-aromatic, organic solvent in a ratio of 1: 3 to 5: 1 and with stirring the heavy, TI-rich phase which settles with a peripheral speed of the stirrer of 0.5 to 6.0 m / s at a temperature between 50 and 200 ° C, preferably between 50 and 100 ° C under the influence of gravity with a clarification surface load of up to 1 t / m 2 h in a TI poor and a TI-rich fraction is separated.
Als Klärflächenbelastung wird die eingesetzte Menge pro Zeiteinheit bezogen auf die Klärfläche bezeichnet.The amount used per unit of time in relation to the clarification area is referred to as the clarification area load.
Das aromatische Lösungsmittel kann dem Schweröl zuerst oder gemeinsam mit dem nichtaromatischen Lösungsmittel zugegeben werden. Das Mischen ist unproblematisch. So kann beispielsweise ein statischer Mischer verwendet werden. Das Durchmischen in einer Kreiselpumpe reicht jedoch ebenfalls aus, wenn dem Einsatzprodukt die Lösungsmittel gleichmäßig vor der Pumpe zudosiert werden.The aromatic solvent can be added to the heavy oil first or together with the non-aromatic solvent. Mixing is not a problem. For example, a static mixer can be used. Mixing in a centrifugal pump is also sufficient, however, if the solvent is metered in evenly before the pump.
Im Grunde können alle üblichen organischen Lösungsmittel verwendet werden, die aromatischen zum Verdünnen des Schweröls und die Aromaten schlecht lösenden, nichtaromatischen zum Ausfällen der β-Harze. Es ist jedoch vorteilhaft, Lösungsmittel zu benutzen, deren Siedepunkt niedriger als der Siedebeginn des Schweröls liegt, wobei das Gemisch möglichst eine Siedelücke aufweisen sollte. Dadurch wird bei der destillativen Wiedergewinnung der Lösungsmittel eine nahezu vollständige Abtrennung der Lösungsmittel von den Schwerölfraktionen erreicht und der Lösungsmittelverlust minimiert. Die zurückgewonnene Lösungsmittel werden wiederverwendet.Basically all common organic solvents can be used, the aromatic for diluting the heavy oil and the aromatics poorly dissolving, non-aromatic for the precipitation of the β-resins. However, it is advantageous to use solvents whose boiling point is lower than the start of boiling of the heavy oil, the mixture should preferably have a boiling gap. As a result, almost complete separation of the solvents from the heavy oil fractions is achieved when the solvents are recovered by distillation and the solvent loss is minimized. The recovered solvents are reused.
Für Schweröle mit einem Siedebeginn von etwa 200° C hat sich insbesondere eine Lösungsmittelkombination aus Toluol und Methanol bewährt, wobei die besten Ergebnisse bei einem Verhältnis Lösungsmittelgemisch zu Schweröl von mindestens 1 : 1 und einem Überschuß an Methanol erzielt wurden. Um eine gute Fließfähigkeit der TI-reichen Fraktion zu erhalten, darf der Gehalt an Toluolunlöslichem in der Fraktion 50 Gew.-% nicht überschreiten.For heavy oils with an initial boiling point of around 200 ° C., a solvent combination of toluene and methanol has proven particularly effective, the best results being achieved with a ratio of solvent mixture to heavy oil of at least 1: 1 and an excess of methanol. In order to maintain good flowability of the TI-rich fraction, the toluene-insoluble content in the fraction must not exceed 50% by weight.
Bei Schwerölen mit einem Siedebeginn von etwa 300° C und darüber hat sich eine Lösungsmittelkombination aus Methylnaphthalinöl und Benzin bewährt, aber auch andere Lösungsmittelkombinationen wie beispielsweise aus Xylol und n-Heptan erfüllen den gleichen Zweck. Aus Kostengründen werden jedoch Fraktionen den reinen Stoffen vorgezogen.A solvent combination of methylnaphthalene oil and petrol has proven itself for heavy oils with a boiling point of about 300 ° C and above, but other solvent combinations such as xylene and n-heptane also serve the same purpose. For reasons of cost, however, fractions are preferred to pure substances.
Überraschenderweise hat es sich gezeigt, daß durch das langsame Rühren der schweren Phase, wobei die niedrigen Umfangsgeschwindigkeiten für die bevorzugt verwendeten Rührer mit großem Durchmesser im Verhältnis zum Behälterdurchmesser wie z.Blatt-, Balken-oder Ankerrührer und die höheren bei Rührern mit kleinem Durchmesser wie Propeller- oder Turbinenrührer angewandt werden, nicht nur die Bildung klebriger gummiartiger Stoffe vermieden wird, sondern auch die Abtrennung des Toluolunlöslichen verstärkt wird. Die Abscheidung harzartiger Komponenten aus der langsam mitbewegten leichten Phase wird unterstützt, und die Ausscheidung der TI-armen Fraktion aus der schweren Phase verstärkt. Die Rührerdrehzahl muß dabei weit unterhalb der kritischen Drehzahl bleiben, um ein Vermischen beider Phasen zu vermeiden. ,Surprisingly, it has been shown that by slowly stirring the heavy phase, the low peripheral speeds for the preferred stirrers with a large diameter in relation to the container diameter, such as, for example, flat, bar or anchor stirrers, and the higher for stirrers with a small diameter, such as Propeller or turbine stirrers are used, not only the formation of sticky rubber-like substances is avoided, but also the separation of the toluene-insoluble is increased. The separation of resinous components from the slowly moving light phase is supported, and the elimination of the TI-poor fraction from the heavy phase is increased. The stirrer speed must remain well below the critical speed in order to avoid mixing the two phases. ,
Es hat sich außerdem gezeigt, daß auch das Verhältnis von Behälterdurchmesser (d) zur Füllhöhe (h) einen Einfluß auf die Abtrennung des Toluolunlöslichen hat. Besonders vorteilhaft ist ein Verhältnis d/h 2.It has also been shown that the ratio of the container diameter (d) to the filling height (h) also has an influence on the removal of the toluene-insoluble. A ratio d / h 2 is particularly advantageous.
Durch das erfinderische Verfahren ist es möglich, die Rückstände aus der Aufarbeitung von kohlestämmigen Schwerölen mit vertretbarem Aufwand zu verringern und teilweise zu wertvollen Produkten weiterzuverarbeiten. Dadurch werden diesen Rückständen neue Anwendungsgebiete erschlossen, die bisher destillativ gewonnenen Ölen vorbehalten waren.The inventive method makes it possible to reduce the residues from the reprocessing of coal-derived heavy oils with reasonable effort and to partially process them into valuable products. This opens up new areas of application for these residues that were previously reserved for oils obtained by distillation.
Das erfinderische Verfahren wird anhand einiger diskontinuierlicher Ausführungsbeispiele näher erläutert, ohne darauf beschränkt zu sein. Das Verfahren läßt sich mit gleichem Ergebnis auch kontinuierlich durchführen, wobei das Gemisch aus Schweröl und Lösungsmitteln vorzugsweise im Bereich der Phasengrenzfläche in den Rührwerksbehälter eingespeist wird.The inventive method is explained in more detail on the basis of a few discontinuous exemplary embodiments, without being limited thereto. The process can also be carried out continuously with the same result, the mixture of heavy oil and solvents preferably being fed into the agitator tank in the region of the phase interface.
40 Gew.-Teile eines abgetoppten Hochtemperatur-Steinkohlenteers (Siedebeginn = 224°C, TI = 8,1 Gew.- %, QI = 1,9 Gew.-%, Aschegehalt 0,1 Gew.-% ) werden zunächst bei 60°C in 30 Gew.-Teilen Toluol gelöst und über einen statischen Mischer mit 30 Gew.-Teilen Methanol gemischt. Das Gemisch wird in einen zylindrischen Rührwerksbehälter mit Klöpperboden (D/h = 2,5) geleitet, in dem sich in Bodennähe ein Ankerrührer mit einer Umfangsgeschwindigkeit von 0,8 m/s dreht. Die Klärflächenbelastung beträgt 0,15 t/M 2h. Der Absetzvorgang unter Rühren bei 60° C ist nach einer Stunde beendet. Nach der Phasentrennung werden die beiden Fraktionen bei einem Kopfdruck von 93 mbar diskontinuierlich bis zu einer Kopftemperatur von 90°C destilliert, um die Lösungsmittel wiederzugewinnen. Als Rückstände verbleiben 26,3 Gew.-Teile einer TI-armen Fraktion, in der sich noch 0,2 Gew.-% Toluol, aber kein Methanol befinden, und 13,8 Gew.-Teile einer TI-reichen Fraktion, in der keine Lösungsmittelreste nachgewiesen werden können. Die Analysendaten sind in der Tabelle wiedergegeben.40 parts by weight of a topped high-temperature coal tar (boiling point = 224 ° C, TI = 8.1% by weight, QI = 1.9% by weight, ash content 0.1% by weight) are initially at 60 ° C in 30 parts by weight of toluene and mixed with 30 parts by weight of methanol on a static mixer. The mixture is fed into a cylindrical agitator tank with a dished bottom (D / h = 2.5), in which an anchor stirrer rotates at a peripheral speed of 0.8 m / s near the bottom. The sewage treatment area load is 0.15 t / M 2 h. The settling process with stirring at 60 ° C is complete after one hour. After phase separation, the two fractions are discontinuously distilled at a top pressure of 93 mbar up to a top temperature of 90 ° C. in order to recover the solvents. The residues left are 26.3 parts by weight of a low-TI fraction in which there are still 0.2% by weight of toluene but no methanol, and 13.8 parts by weight of a TI-rich fraction in the no solvent residues can be detected. The analysis data are shown in the table.
Die TI-arme Fraktion hat einen Bureau of Mines Correlation Index von 175 und wird als Rußrohstoff verwendet.The TI-poor fraction has a Bureau of Mines Correlation Index of 175 and is used as a soot raw material.
In einem Furnacereaktor werden aus diesem Material in 44,2 %-iger Ausbeute typgerechte Gummiruße erzeugt.In a furnace reactor, rubber soot of this type is produced in 44.2% yield from this material.
Die TI-reiche Fraktion wird in üblicher Weise wie abgetoppter Teer destillativ aufgearbeitet. Dabei fällt bezogen auf den eingesetzten abgetoppten Teer ein Rückstand von nur 33,8 Gew.-% gegenüber 59,3 Gew.-% der üblichen rein destillativen Aufarbeitung an. Der Rückstand hat einen Erweichungspunkt nach Krämer-Sarnow (EP) = 73° C (K.-S.).The TI-rich fraction is worked up by distillation in the usual way, like topped tar. Based on the topped tar used, a residue of only 33.8% by weight is obtained compared to 59.3% by weight of the usual purely distillative workup. The residue has a softening point according to Krämer-Sarnow (EP) = 73 ° C (K.-S.).
Durch Verblasen wird hieraus in einer Ausbeute von 82 Gew.-% ein Hartpech mit einem Erweichungspunkt von 172°C (K.-S.) hergestellt, das in einem Horizontalkammerofen über 24 Stunden bei 1050°C zu einem makroskopisch nahezu isotropen Koks verkokt wird mit einem Schüttgewicht von 520 kg/m3 und einer Micum-Trommelfestigkeit von M10 = 8,2 Gew.-%.By blowing, a hard pitch with a softening point of 172 ° C (K.-S.) is produced from this in a yield of 82% by weight, which is coked in a horizontal chamber furnace at 1050 ° C for 24 hours to give a macroscopically almost isotropic coke with a bulk density of 520 kg / m 3 and a Micum drum strength of M 10 = 8.2% by weight.
Die Koksausbeute auf den Pechrückstand (Normalpech) bezogen beträgt 62 Gew.-%.The coke yield based on the pitch residue (normal pitch) is 62% by weight.
10 Gew.-Teile Steinkohlenteernormalpech (EP = 72°C (K.-S.), TI = 19,2 Gew.-%, Ql = 6,5 Gew.-%, Aschegehalt 0,18 Gew.-%), werden mit 10 Gew.-Teilen Methylnaphthalinöl (Siedebereich 235 bis 265°C) verdünnt, und das Gemisch mit 16 Gew.-Teilen Testbenzin (Siedebereich 140 bis 170°C) über eine Kreiselpumpe in einen Rührwerksbehälter mit Flachboden (d/h = 3,2) gefördert. In Bodennähe dreht sich ein Kreuzbalkenrührer mit einer Umfangsgeschwindigkeit von 1 m/s. Die Klärflächenbelastung beträgt 0,2 t/m2h. Das Gemisch hat sich nach einem 2-stündigen Absetzenlassen unter Rühren bei 73°C in eine leichte und eine schwere Phase getrennt. Bei 100 mbar Kopfdruck und einer Sumpftemperatur bis 288°C werden diskontinuierlich aus der oberen Phase 25 Gew.-Teile und aus der unteren Phase 1 Gewichtsteil Lösungsmittel abdestilliert. Auf diese Weise werden 6 Gew.-Teile einer TI-reichen und 4 Gew.Teile einer TI-armen Fraktion gewonnen, deren Analysendaten in der Tabelle aufgeführt sind.10 parts by weight of coal tar pitch (EP = 72 ° C (K.-S.), TI = 19.2% by weight, Ql = 6.5% by weight, ash content 0.18% by weight), are diluted with 10 parts by weight of methylnaphthalene oil (boiling range 235 to 265 ° C), and the mixture with 16 parts by weight of white spirit (boiling range 140 to 170 ° C) via a centrifugal pump into a stirrer tank with a flat bottom (d / h = 3 , 2) promoted. A cross-bar stirrer rotates near the ground at a peripheral speed of 1 m / s. The sewage treatment area load is 0.2 t / m 2 h. After being left to sit for 2 hours with stirring at 73 ° C., the mixture separated into a light and a heavy phase. At 100 mbar head pressure and a bottom temperature of up to 288 ° C., 25 parts by weight of the upper phase and 1 part by weight of solvent are distilled off from the lower phase. In this way, 6 parts by weight of a TI-rich and 4 parts by weight of a TI-poor fraction are obtained, the analysis data of which are listed in the table.
Die 4 Gew.-Teile der TI-armen Fraktion werden mit 4 Gew.-Teilen filtriertem Anthracenöl gemischt. Der Bureau of Mines Correlation Index dieser Mischung ist 179. In einem Furnacereaktor werden daraus in 45,1 %- iger Ausbeute typgerechte Gummiruße hergestellt.The 4 parts by weight of the TI-poor fraction mixed with 4 parts by weight of filtered An t hracenöl mixed. The Bureau of Mines Correlation Index of this mixture is 179. In a furnace reactor it is used to produce rubber soot in a 45.1% yield.
Die 6 Gew.-Teile der TI-reichen Fraktion werden mit 3 Gew.-Teilen Steinkohlenteernormalpech mit den gleichen Analysendaten wie das zu extrahierende Pech flüssig gemischt und durch eine schonenden Helmdestillation zu Elektrodenbindemittel vearbeitet. In 92 %-iger Ausbeute wird ein Bindemittel mit einem Erweichungspunkt von 90°C (K.-S.), einem QI-Gehalt von 10,2 Gew.-%, einem β-Harzgehalt von 25,3 Gew.-%, einem Aschegehalt von 0,28 Gew.-% und einem Verkokungsrückstand (Conradson) von 52,6 Gew.-% erhalten.The 6 parts by weight of the TI-rich fraction are mixed with 3 parts by weight of coal pitch normal pitch with the same analysis data as the pitch to be extracted and processed by gentle helmet distillation to form electrode binders. In 92% yield, a binder with a softening point of 90 ° C. (K.-S.), a QI content of 10.2% by weight, a β-resin content of 25.3% by weight, an ash content of 0.28% by weight and a coking residue (Conradson) of 52.6% by weight.
10 Gew.-Teile eines Weichpechs aus der Vergasung von Braunkohle (EP = 34°C (K.-S.), TI = 9,8 Gew.-%, QI = 3,1 Gew.-%, Aschegehalt 0,1 Gew.-%) werden mit einem Lösungsmittelgemisch aus 7 Gew.-Teilen Xylol und 16 Gew.-Teilen n-Heptan Bei 85°C in einem Rohrabschnitt durch eine Bypass-Schaltung mit 90 %-iger Rückführung gemischt und in einen Spitzbodenbehälter (d/h = 2,0) geleitet, in dessen konischem Teil ein der Behältergeometrie angepaßter Blattrührer die schwere Phase mit einer Umfangsgeschwindigkeit von 0,7 m/s bewegt. Die Klärflächenbelastung beträgt 0,4 t/m2h. Bei 85°C ist die Phasentrennung innerhalb einer Stunde abgeschlossen. Aus der leichten Phase werden bei einem Kopfdruck von 100 mbar und einer Sumptemperatur bis zu 350°C 24 Gew.-Teile Lösungsmittel und Teeröle abdestilliert. Die verbleibenden 5 Gew.-Teile Destillationsrückstand sind nahezu- und Ql-frei und enthalten nur noch 1,3 Gew.-% β-Harze. Der Erweichungspunkt beträgt 62°C (K.-S.) und der Verkokungsrückstand 43,1 Gew.-%. Der Rückstand wird als Imprägniermittel bei Graphitelektroden für die Stahlerzeugung eingesetzt.10 parts by weight of a soft pitch from the gasification of brown coal (EP = 34 ° C (K.-S.), TI = 9.8% by weight, QI = 3.1% by weight, ash content 0.1 % By weight) are mixed with a solvent mixture of 7 parts by weight of xylene and 16 parts by weight of n-heptane at 85 ° C. in a pipe section through a bypass circuit with 90% recirculation and placed in a pointed bottom container (i.e. / h = 2.0), in the conical part of which a blade stirrer adapted to the container geometry moves the heavy phase at a peripheral speed of 0.7 m / s. The sewage treatment area load is 0.4 t / m 2 h. At 85 ° C the phase separation is completed within one hour. 24 parts by weight of solvent and tar oils are distilled off from the light phase at a top pressure of 100 mbar and a bottom temperature of up to 350 ° C. The remaining 5 parts by weight of distillation residue are almost free of Ql and contain only 1.3% by weight of β-resins. The softening point is 62 ° C (K.-S.) and the coking residue is 43.1% by weight. The residue is used as an impregnating agent in graphite electrodes for steel production.
Aus den 4 Gew.-Teilen der schweren Phase werden 0,5 Gew.-Teile bei einem Kopfdruck von 100 mbar und einer Sumpftemperatur bis zu 370°C abdestilliert. Der Rückstand mit einem Erweichungspunkt von 90°C (K.-S.) und einem Verkokungsrückstand (Conradson) von 54,3 Gew.-% hat einen Aschegehalt von 0,3 Gew.-%, einen QI-Gehalt von 9,5 Gew.-% und einen β-Harzgehalt von 26,7 Gew.-% und wird als Elektrodenbindemittel verwendet.0.5 part by weight is distilled off from the 4 parts by weight of the heavy phase at a top pressure of 100 mbar and a bottom temperature of up to 370.degree. The residue with a softening point of 90 ° C (K.-S.) and a coking residue (Conradson) of 54.3% by weight has an ash content of 0.3% by weight and a QI content of 9.5 % By weight and a β-resin content of 26.7% by weight and is used as an electrode binder.
Als Schweröl kann auch ein kohlestämmiges Produkt verwendet werden, aus dem zuvor die Aschebestandteile oder das Chinolinunlösliche zumindest teilweise entfernt wurde. Es ist bekannt, den Aschegehalt in Schwerölen durch Zentrifugieren zu vermindern, und das Chinolinunlösliche durch Filtrieren, Separieren oder promotorbeschleunigtes Absetzenlassen zumindest teilweise zu entfernen. Insbesondere lassen sich Verfahren zur Entfernung des Chinolinunlöslichen durch promotorbeschleunigtes Absetzenlassen gut mit dem erfinderischen Verfahren kombinieren.A coal-based product from which the ash constituents or the quinoline-insoluble matter has at least partially been removed can also be used as the heavy oil. It is known to reduce the ash content in heavy oils by centrifugation, and to at least partially remove the quinoline-insoluble by filtering, separating or allowing accelerated settling. In particular, methods for removing the quinoline-insoluble by letting the promoter accelerate settling can be combined well with the inventive method.
20 Gew.Teile Steinkohlenteernormalpech wie in Beispiel 2 werden mit 9 Gew.-Teilen Methylnaphthalinöl (Siedebereich 235 bis 245°C) und 9 Gew.-Teilen Kerosin (Siedebereich 250 bis 300°C) in einem Spitzenbodenbehälter mit Rückflußkühler 3 Stunden unter Rühren bei 250° C thermisch behandelt. Danach wird das Gemisch durch Umpumpen über einen Kühler bis auf 180° C abgekühlt. Nach einer Stunde ohne Rühren hat sich eine QI-reiche Fraktion (20 Gew.-% des Gemisches) am Boden abgesetzt und wird abgelassen. Die 30,4 Gew.-Teile der zurückbleibenden Fraktion (QI = 0,04 Gew.-%, TI = 7,25 Gew.-%) werden mit weiteren 7,5 Gew.-Teilen Methylnaphthalinöl und 16,5 Gew.-Teilen Kerosin durch Umpumpen über den Kühler gemischt und auf 75°C abgekühlt. Das d/h-Verhältnis beträgt 2,1 und der Blattrührer dreht sich mit der gleichen Geschwindigkeit wie in Beispiel 3. Nach zwei Stunden hat sich das Gemisch in eine leichte und eine schwere Phase getrennt. Nach Abdestillieren der Lösungsmittel werden 8 Gew.-Teile einer TI-armen Fraktion mit 0,1 Gew.-% Toluolunlöslichem, die als Rußölkomponente verwendet werden, und 7 Gew.-Teile einer TI-reichen Fraktion mit einem TI-Geahlt von 31,3 Gew.-% erhalten, die durch Verkokung in einem Delayed Coker mit einer Ausbeute von 73 Gew.-% in einem hochanisotropen Grünkoks umgewandelt werden. Nach dem Kalzinieren bei 1300°C hat dieser Koks einen thermischen Volumenausdehnungskoeffizienten von 3,1 - 10-5K-1 zwischen 25 und 200° C.20 parts by weight of normal pitch coal pitch as in Example 2 are mixed with 9 parts by weight of methylnaphthalene oil (boiling range 235 to 245 ° C) and 9 parts by weight of kerosene (boiling range 250 to 300 ° C) in a tip-top container with a reflux condenser for 3 hours with stirring 250 ° C thermally treated. The mixture is then cooled to 180 ° C. by pumping over a cooler. After one hour without stirring, a QI-rich fraction (20% by weight of the mixture) has settled on the bottom and is drained off. The 30.4 parts by weight of the remaining fraction (QI = 0.04% by weight, TI = 7.25% by weight) are mixed with a further 7.5 parts by weight of methylnaphthalene oil and 16.5 parts by weight. Parts of kerosene are mixed by pumping over the cooler and cooled to 75 ° C. The d / h ratio is 2.1 and the blade stirrer rotates at the same speed as in Example 3. After two hours the mixture has separated into a light and a heavy phase. After the solvents have been distilled off, 8 parts by weight of a low-TI fraction with 0.1% by weight of toluene-insoluble, which are used as the carbon black oil component, and 7 parts by weight of a TI-rich fraction with a TI content of 31 3 wt .-% obtained, which are converted by coking in a delayed coker with a yield of 73 wt .-% in a highly anisotropic green coke. After calcining at 1300 ° C, this coke has a thermal expansion coefficient of 3.1 - 10 -5 K -1 between 25 and 200 ° C.
Eingesetzt wird ein Normalpech wie in Beispiel 2. Die Extraktion wird wie in diesem Beispiel, jedoch ohne Rühren, durchgeführt. Es entsteht keine fließfähige schwere Phase. Das sich absetzende Material läßt sich weder lösen noch völlig aufschmelzen und muß daher mechanisch entfernt werden.A normal pitch as in Example 2 is used. The extraction is carried out as in this example, but without stirring. There is no flowable heavy phase. The material that settles out can neither be loosened nor melted completely and must therefore be removed mechanically.
Von der leichten Phase werden 29 Gew.-Teile vorsichtig von oben abgezogen. Nach kurzer Zeit fallen bereits harzartige Bestandteile aus infolge unzureichender Abtrennung der β-Harze. Das Gemisch wird in einer Rührwerksretorte unter einem Druck von 100 mbar bis zu einer Sumpftemperatur von 275°C destilliert, um die Lösungsmittel zu entfernen. Der pechartige Rückstand (4 Gew.-Teile) hat die in der Tabelle angegebenen Analysendaten. Ein Vergleich mit den Analysedaten des Beispiels 2 zeigt deutlich den Einfluß des Rührens auf die Abtrennung des Toluolunlöslichen.29 parts by weight of the light phase are carefully removed from above. After a short time, resinous constituents already precipitate out due to inadequate separation of the β-resins. The mixture is distilled in a stirrer retort under a pressure of 100 mbar to a bottom temperature of 275 ° C. in order to remove the solvents. The pitch-like residue (4 parts by weight) has the analysis data given in the table. A comparison with the analysis data of Example 2 clearly shows the influence of stirring on the removal of the insoluble in toluene.
Der Versuch wird wie im Beispiel 2 beschrieben durchgeführt mit der Ausnahme, daß nur 5 Gew.-Teile Testbenzin verwendet werden. Der TI-Gehalt der von Lösungsmitteln befreiten TI-armen Fraktion beträgt 3,9 Gew.-%. Das Material ist nicht als Rußölkomponente geeignet.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833335316 DE3335316A1 (en) | 1983-09-29 | 1983-09-29 | METHOD FOR SEPARATING RESINY MATERIALS FROM CARBONATE HEAVY OILS AND USE OF THE FRACTION RECOVERED |
| DE3335316 | 1983-09-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0135943A2 EP0135943A2 (en) | 1985-04-03 |
| EP0135943A3 EP0135943A3 (en) | 1987-03-11 |
| EP0135943B1 true EP0135943B1 (en) | 1989-01-04 |
Family
ID=6210422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84200689A Expired EP0135943B1 (en) | 1983-09-29 | 1984-05-15 | Process for separating resinous materials from heavy coal oils, and use of the fractions so obtained |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4582591A (en) |
| EP (1) | EP0135943B1 (en) |
| JP (1) | JPS6092389A (en) |
| DE (2) | DE3335316A1 (en) |
| ZA (1) | ZA845600B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2594839B1 (en) * | 1986-02-26 | 1988-11-04 | Inst Francais Du Petrole | PROCESS FOR THE FRACTIONATION OF SOLID ASPHALTS |
| DE3609988C2 (en) * | 1986-03-25 | 1994-08-04 | Metallgesellschaft Ag | Combined process for separating and treating asphaltenes with high softening temperature |
| DE3610375A1 (en) * | 1986-03-27 | 1987-10-01 | Ruetgerswerke Ag | METHOD FOR PRODUCING A CARBON FIBER PRE-PRODUCT AND CARBON FIBERS MADE THEREOF |
| DE3636560A1 (en) * | 1986-10-28 | 1988-05-05 | Ruetgerswerke Ag | METHOD FOR THE DESALINATION OF CARBON TARES AND PITCHES |
| US5855768A (en) * | 1997-08-21 | 1999-01-05 | Natural Resources Canada | Process for removing contaminants from thermally cracked waste oils |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3153626A (en) * | 1960-03-30 | 1964-10-20 | Consolidation Coal Co | Methanol extraction of lowtemperature tar |
| JPS5839770B2 (en) * | 1974-12-28 | 1983-09-01 | トウヨウカ−ボン カブシキガイシヤ | Tanso Shikei Tai no Seizouhou |
| JPS6041111B2 (en) * | 1976-11-26 | 1985-09-13 | 新日鐵化学株式会社 | Method for preparing raw materials for coke production |
| US4116815A (en) * | 1977-06-21 | 1978-09-26 | Nittetsu Chemical Industrial Co., Ltd. | Process for preparing needle coal pitch coke |
| US4208267A (en) * | 1977-07-08 | 1980-06-17 | Exxon Research & Engineering Co. | Forming optically anisotropic pitches |
| DE2810332C2 (en) * | 1978-03-10 | 1982-08-05 | Rütgerswerke AG, 6000 Frankfurt | Process for the separation of quinoline-insoluble constituents from coal tar pitch |
| US4184942A (en) * | 1978-05-05 | 1980-01-22 | Exxon Research & Engineering Co. | Neomesophase formation |
| US4277324A (en) * | 1979-04-13 | 1981-07-07 | Exxon Research & Engineering Co. | Treatment of pitches in carbon artifact manufacture |
| GB2056423B (en) * | 1979-08-16 | 1983-02-23 | Lancashire Tar Distillers Ltd | Porous carbon |
-
1983
- 1983-09-29 DE DE19833335316 patent/DE3335316A1/en not_active Withdrawn
-
1984
- 1984-05-15 DE DE8484200689T patent/DE3475919D1/en not_active Expired
- 1984-05-15 EP EP84200689A patent/EP0135943B1/en not_active Expired
- 1984-07-19 ZA ZA845600A patent/ZA845600B/en unknown
- 1984-08-06 US US06/637,934 patent/US4582591A/en not_active Expired - Lifetime
- 1984-09-28 JP JP59202097A patent/JPS6092389A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3335316A1 (en) | 1985-04-11 |
| JPS6092389A (en) | 1985-05-23 |
| DE3475919D1 (en) | 1989-02-09 |
| EP0135943A3 (en) | 1987-03-11 |
| EP0135943A2 (en) | 1985-04-03 |
| ZA845600B (en) | 1985-03-27 |
| US4582591A (en) | 1986-04-15 |
| JPH0458519B2 (en) | 1992-09-17 |
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