EP2882514A1 - Verfahren zur entfernung von aromatischen kohlenwasserstoffen aus kokereigas mit biodiesel als waschflüssigkeit und vorrichtung zur durchführung des verfahrens - Google Patents
Verfahren zur entfernung von aromatischen kohlenwasserstoffen aus kokereigas mit biodiesel als waschflüssigkeit und vorrichtung zur durchführung des verfahrensInfo
- Publication number
- EP2882514A1 EP2882514A1 EP13739402.9A EP13739402A EP2882514A1 EP 2882514 A1 EP2882514 A1 EP 2882514A1 EP 13739402 A EP13739402 A EP 13739402A EP 2882514 A1 EP2882514 A1 EP 2882514A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- biodiesel
- stage
- scrubber
- regeneration
- aromatic hydrocarbons
- 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- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
Definitions
- the present invention relates to a process for the removal of aromatic hydrocarbons from Kokereigas, in which biodiesel is conducted as a washing liquid in a circuit, wherein the Kokereigas is brought in a first gas scrubber stage with the biodiesel in contact and separated by absorption aromatic hydrocarbons from the Kokereigas are, wherein the enriched with aromatic hydrocarbons biodiesel is then withdrawn from the first scrubber stage, is heated and the aromatic hydrocarbons are partially driven off by stripping with steam from the biodiesel and the regenerated by stripping biodiesel after cooling, at least a portion, is returned to the first gas scrubber.
- the invention also provides an apparatus for carrying out the method.
- Carbon coking releases aromatic hydrocarbons as part of the resulting coke oven gas.
- they are washed out of the coke oven gas during the preparation of the coking gas, usually after the separation of tar and ammonia.
- a washing oil based on a tar oil fraction is used, which is produced by the processing of hard coal.
- this process step is also generally referred to as BTEX washing, BTX washing or benzene washing.
- the aromatic hydrocarbons mentioned are also collectively referred to as crude benzene, wherein
- the proportion of crude benzene is typically between 20 and 40 grams per normal cubic meter (Nm 3 ), depending on the coal used for the coking process and the process control.
- the crude benzene typically has between 55 to 75% benzene, 13 to 19% toluene and between 5 to 10% xylenes.
- the coking gas also contains multicyclic aromatic hydrocarbons, such as in particular naphthalene, which can be absorbed to some extent by the wash oil.
- the Kokereigas contains impurities, in particular H 2 S, HCN, NH 3 and organic sulfur compounds.
- a typical composition of a coke oven gas has, for example:
- Contact can be achieved on the one hand by a fine atomization of the wash oil and on the other by thin oil films.
- Particularly advantageous is the combination of a sprinkler on the one hand and hordes, packing or other internals on the other hand, wherein the oil droplets coming from the sprinkler are spread to an oil film with the largest possible surface.
- the solubility of benzene, toluene and xylene is particularly dependent on the vapor pressure of the various components, which is why the wash oil is supplied to the scrubber at comparatively low temperatures.
- the wash oil must also have sufficient flowability and low viscosity so that it is easy to disperse and can form a large surface area.
- the aromatic hydrocarbon-enriched wash oil which collects at the bottom of the scrubber, is drawn off, the crude benzene being subsequently driven off at elevated temperature by stripping with steam from the wash oil. The wash oil is then returned to the scrubber after cooling.
- the wash oil is added with an excess to the scrubber.
- large quantities of scrubbing oil are required.
- biodiesel also refers in the context of the present invention to an organic fuel which, in contrast to fossil diesel oil, is not obtained from fossil crude oil but from vegetable oils by transesterification.
- biodiesel is a highly efficient washing liquid with which the aromatic hydrocarbons benzene, toluene, m-, p-, o-xylene and ethylbenzene can be removed.
- Biodiesel is also cost-effective, easy to handle and is also characterized by an improved CO2 balance.
- the proportion of the multicyclic aromatic hydrocarbon naphthalene is also significantly reduced.
- the naphthalene concentration starting from a proportion of typically up to 2 g / Nm 3 (grams per normal cubic meter) at conventional process parameters to a concentration of 100 to 150 mg / Nm 3 (milligrams per standard cubic meter).
- a conventional scrubbing liquid based on mineral oil or tar oil gives significantly higher values in the range between 200 and 300 mg / Nm 3 , since these already have a considerable residual concentration of naphthalene when fresh.
- the object of the present patent application is to further reduce the concentration of naphthalene in the purified coking gas.
- the invention and the solution of the problem are a method according to claim 1 and an apparatus according to claim 8 for carrying out the method.
- the inventive method is characterized in that the gas scrubbing takes place in at least two stages, wherein the coker gas cleaned in a first gas scrubber stage for further removal of naphthalene is passed through a second scrubber stage, which is supplied by the regenerated biodiesel, a first subset, which a second subset, which is supplied to the first gas scrubber stage, is driven off more.
- biodiesel is usually given as the scrubbing liquid in an excess. That is, the absorption capacity of the biodiesel is chosen so that the BTEX components can be largely removed.
- the concentration of naphthalene in the gas scrubbing of the coke oven gas can be reduced to a concentration of less than 50 mg / Nm 3 .
- the highly expired biodiesel can also be referred to as ultra-pure oil (ultra lean oil), which can be obtained in particular in a separate regeneration stage.
- not circulated part of the naphthalene-enriched biodiesel can be introduced for further enrichment with aromatic hydrocarbons in the first scrubber stage.
- the transfer of this further part of biodiesel is expediently effected directly, i. without another treatment.
- the first scrubber stage and the second scrubber stage may be present in a common scrubber column, with the second scrubber stage located above the first scrubber stage.
- the first heavily aborted subset of the regenerated biodiesel is introduced into the second scrubber stage at the head of the gas scrubber column together with the volume flow conducted in the second regeneration stage.
- the absorption can be effected by the distribution of the washing liquid and / or on the surface of internals within the second scrubber stage.
- a flue bottom is provided, wherein a portion of the scrubbing liquid used in the second scrubber stage in the form of biodiesel in the arranged below the first gas scrubber.
- the biodiesel enriched with the BTEX components and naphthalene is withdrawn at the bottom of the first scrubber stage, ie at the bottom of the scrubber column, and fed to regeneration.
- the biodiesel withdrawn from the first scrubber stage is first supplied to a first regeneration stage for the purpose of removing aromatic hydrocarbons from the biodiesel by stripping with steam, in particular superheated steam having a temperature of more than 150.degree.
- the regenerated biodiesel withdrawn from the first stage of regeneration only has a low content of BTEX components overall and can thus be used for re-BTEX scrubbing.
- the regenerated biodiesel withdrawn from the first regeneration stage is divided into the first subset and the second subset, wherein the second subset is introduced again into the first scrubber stage. In this case, usually only the setting of a desired temperature takes place without a further treatment or change of the washing liquid.
- the first subset is supplied to a further regeneration in a second regeneration stage in order, in particular, to achieve a further separation of naphthalene in the biodiesel as the scrubbing liquid.
- the branching of the first subset is expediently carried out before the heat recovery through the described heat exchanger.
- a particularly efficient process management results if the first regeneration stage is arranged above the second regeneration stage within a common regeneration column.
- the water vapor, in particular a superheated steam having a temperature of more than 150 ° C., is then first introduced completely into the second regeneration stage in a lower region of the regeneration column.
- the steam still has its maximum temperature and the proportion of aromatic hydrocarbons in the previously in the first gas scrubber stage purified biodiesel is low overall, in the naphthalene are effectively removed so that a significant portion of the residual concentration of naphthalene is separated. It can thus be provided a strongly aborted washing liquid, which has almost the properties of fresh biodiesel, which is initially virtually free of naphthalene due to its production from vegetable oils.
- the first partial flow is then fed to the second scrubber stage.
- the invention also provides an apparatus for carrying out the method, which has a first and a second scrubber stage, a first and a second regeneration stage, biodiesel as scrubbing liquid and a conduit and delivery system in order to circulate the biodiesel.
- the gas scrubber stages can be arranged together in a gas scrubber column and the regeneration stages in a common regeneration column.
- the concentration of naphthalene can be considerably reduced with relatively low investment costs with the process according to the invention.
- the BTEX and naphthalene separation from the Kokereigas and the removal of the BTEX component and naphthalene from the biodiesel are combined as washing liquid in a particularly advantageous manner, whereby the Apparative effort can be kept low overall.
- the discharged with the water vapor from the first regeneration stage aromatic hydrocarbons can be separated and used in the usual way in downstream processes from the water vapor.
- the biodiesel is obtained from vegetable oils.
- Typical starting materials are, depending on the local conditions, for example rape, palm, sunflower and soybean oil, from which the corresponding methyl esters formed
- rapeseed oil methyl ester is particularly suitable, which can be produced in large quantities in regions with a moderate climate and is commercially available.
- the composition and the chemical and physical properties of biodiesel are described, for example, in the standards DIN EN 14214 (November 2003) and ASTM D 6751 -07A. These standards refer to the use of biodiesel as fuel. Against this background, in addition to the standardized types of biodiesel, variants of biodiesel can be used for use as a washing liquid for the absorption of aromatic hydrocarbons, which can differ to some extent from the standards mentioned.
- the invention will be explained in the following with reference to a drawing showing only one exemplary embodiment.
- the single figure shows a schematic representation of an apparatus for removing aromatic hydrocarbons from Kokereigas, is guided in the biodiesel as a washing liquid in a circuit.
- An essential component of the plant for the removal of aromatic hydrocarbons from a Kokereigas COG are according to the illustrated embodiment, a scrubber column 1 and a regeneration column 2.
- the Kokereigas COG is introduced through a supply line in a lower portion of the scrubber column 1 and flows through the gas scrubber column 1 in vertical Direction, wherein it is brought into contact with biodiesel as a washing liquid, whereby aromatic hydrocarbons are absorbed by the biodiesel and thus separated from the Kokereigas COG.
- the purified Kokereigas COG is then discharged in an upper region of the gas scrubber column 1 through a discharge line.
- a first scrubber stage 3 and above a second scrubber stage 4 are provided within the scrubber column.
- the biodiesel enriched with aromatic hydrocarbons is withdrawn as scrubbing liquid and fed to the regeneration column 2.
- a temperature slightly above the gas inlet temperature is preferably set in the biodiesel as the scrubbing liquid. to avoid condensation of the water contained in the gas.
- the temperature refers to a subset (second subset) of the biotaste that is introduced directly into the first scrubber stage 3 after its regeneration.
- a temperature increase of the biotube is provided as the scrubbing liquid, for which purpose the biodiesel drawn off from the first scrubber stage 3 is first passed through a heat exchanger 5 and then through a heating device 6.
- sensors for the flow control DK and for the temperature control TK are provided in the line system.
- the levels in the regeneration column 2 can be checked by sensors of a level control FK.
- the entire biodiesel as washing liquid is then introduced at a central part of the regeneration column 2 in a first regeneration stage 7,
- the biodiesel in the first regeneration stage 7 has a temperature of about 170 ° C to 190 ° C.
- the specified temperature range is above the boiling points of the BTEX components, so that they dissolve out of the biodiesel as a washing liquid.
- Particularly effective is a drive off of the crude benzene with water vapor, in particular with superheated steam, which has a temperature of more than 150 ° C.
- Particularly preferred is a stripping temperature of about 180 ° C to 190 ° C, wherein the biodiesel is not evaporated or decomposed as a washing liquid, even at such a temperature to a significant extent.
- the biodiesel which has been cleaned in the first regeneration stage 7 as washing liquid, is subsequently divided into a first subset and into a second subset.
- the washing liquid is discharged at the bottom of the first regeneration stage 7 and divided outside the regeneration column 2 in the first subset and the second subset, the first subset is fed to further regeneration of a second regeneration stage 8, while the second subset after setting a suitable temperature by means of the heat exchanger 5 and a cooler 9 is again introduced into the first gas scrubber stage 3 for the removal of the BTEX components.
- a division into the first subset and the second subset take place in that only the second subset is discharged from the regeneration column 2, while the first subset for further purification directly into the second Regeneration stage 8 arrives.
- the regeneration takes place by means of steam which is introduced into the second regeneration stage 8 through a steam feed 10 in a lower region of the regeneration column 2. Since the entire water vapor is brought into contact only with the first subset of the entire scrubbing liquid, this proportion of the scrubbing liquid has already been largely purified and the steam still has its original temperature, additional purification of the biodiesel in the second regeneration stage 8 can be achieved. in particular, naphthalene is efficiently removed.
- the more heavily driven first portion of the biodiesel of the second scrubber stage 4 is supplied and mixed with a partial stream of biodiesel, which is performed at the second scrubber stage 4 in a separate circuit 1 1.
- the second scrubber stage 4 only a part of the discontinued scrubbing liquid is collected and circulated, while another part passes into the first scrubber scrubber stage 3 arranged thereunder.
- the amount of biodiesel transferred from the second scrubber stage 4 into the first scrubber stage 1 in this case corresponds to the subset of the regenerated biodiesel which is supplied to the second scrubber stage 4 in the heavily aborted state.
- the BTEX components removed from the biodiesel as washing liquid and the naphthalene removed from the washing liquid leave the regeneration column 2 at its head and can be recovered and used in a manner known per se.
- the process parameters in the first scrubber stage 3 are adjusted so that the BTEX components can be effectively washed out, while the parameters in the second scrubber stage 4 are optimized for the removal of naphthalene. Due to the different, in particular temperature-dependent equilibria, a higher temperature of the scrubbing liquid than in the first scrubber stage 3 is preferably set for the removal of naphthalene in the second scrubber stage 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Industrial Gases (AREA)
- Gas Separation By Absorption (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012107336.8A DE102012107336A1 (de) | 2012-08-09 | 2012-08-09 | Verfahren zur Entfernung von aromatischen Kohlenwasserstoffen aus Kokereigas mit Biodiesel als Waschflüssigkeit und Vorrichtung zur Durchführung des Verfahrens |
PCT/EP2013/064964 WO2014023526A1 (de) | 2012-08-09 | 2013-07-16 | Verfahren zur entfernung von aromatischen kohlenwasserstoffen aus kokereigas mit biodiesel als waschflüssigkeit und vorrichtung zur durchführung des verfahrens |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2882514A1 true EP2882514A1 (de) | 2015-06-17 |
Family
ID=48808327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13739402.9A Withdrawn EP2882514A1 (de) | 2012-08-09 | 2013-07-16 | Verfahren zur entfernung von aromatischen kohlenwasserstoffen aus kokereigas mit biodiesel als waschflüssigkeit und vorrichtung zur durchführung des verfahrens |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP2882514A1 (de) |
AR (1) | AR092082A1 (de) |
CA (1) | CA2881218A1 (de) |
DE (1) | DE102012107336A1 (de) |
TW (1) | TW201414827A (de) |
WO (1) | WO2014023526A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2014390004B2 (en) * | 2014-04-09 | 2018-12-06 | Nohbell Corporation | Removal of target compounds from gases |
CN105331395B (zh) * | 2014-08-08 | 2018-02-16 | 宝钢工程技术集团有限公司 | 以脱苯热贫油为热源的无蒸汽煤气净化装置及其使用方法 |
CN104789273A (zh) * | 2015-03-27 | 2015-07-22 | 山东钢铁股份有限公司 | 利用荒煤气余热回收焦炉荒煤气苯类物质的*** |
CN104962322B (zh) * | 2015-06-12 | 2018-05-15 | 江苏永钢集团有限公司 | 焦炉煤气净化*** |
CN104962323B (zh) * | 2015-06-26 | 2017-10-27 | 山东钢铁股份有限公司 | 一种负压脱苯循环洗油的再生方法 |
CN109847546B (zh) * | 2019-02-15 | 2021-07-27 | 邢台恒禄科技有限公司 | 一种环保零排放尾气处理工艺 |
CN113999703A (zh) * | 2021-10-28 | 2022-02-01 | 宣化钢铁集团有限责任公司 | 一种高效洗脱焦炉煤气苯族烃***及工艺 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4198378A (en) * | 1976-11-12 | 1980-04-15 | Giuseppe Giammarco | Process for removing CO2, H2 S and other gaseous impurities from gaseous mixtures |
US6800120B1 (en) * | 1998-11-23 | 2004-10-05 | Fluor Corporation | Split-flow process and apparatus |
JP4690659B2 (ja) * | 2004-03-15 | 2011-06-01 | 三菱重工業株式会社 | Co2回収装置 |
AU2007216457B2 (en) * | 2006-02-14 | 2011-02-24 | Basf Se | Refitting plants for acid gas removal |
AR067187A1 (es) | 2007-06-29 | 2009-09-30 | Uhde Gmbh | Procedimiento para separar hidrocarburos aromaticos de gas de hornos de coque |
-
2012
- 2012-08-09 DE DE102012107336.8A patent/DE102012107336A1/de not_active Withdrawn
-
2013
- 2013-07-16 WO PCT/EP2013/064964 patent/WO2014023526A1/de active Application Filing
- 2013-07-16 CA CA2881218A patent/CA2881218A1/en not_active Abandoned
- 2013-07-16 EP EP13739402.9A patent/EP2882514A1/de not_active Withdrawn
- 2013-08-05 TW TW102127992A patent/TW201414827A/zh unknown
- 2013-08-08 AR ARP130102826A patent/AR092082A1/es unknown
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2014023526A1 * |
Also Published As
Publication number | Publication date |
---|---|
TW201414827A (zh) | 2014-04-16 |
CA2881218A1 (en) | 2014-02-13 |
WO2014023526A1 (de) | 2014-02-13 |
AR092082A1 (es) | 2015-03-18 |
DE102012107336A1 (de) | 2014-02-13 |
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