EP0497155A1 - Procédé de décokéfaction de fours de pyrolyse - Google Patents

Procédé de décokéfaction de fours de pyrolyse Download PDF

Info

Publication number: EP0497155A1
Authority: EP; European Patent Office
Prior art keywords: gas; decoking; cracked; decoking gas; cracking
Prior art date: 1991-01-31
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.): Granted

Application number

EP92100682A

Other languages

German (de)

English (en)

Other versions

EP0497155B1 (fr

Inventor

Gerhard Dr.-Ing. Merz

Gunther Dipl.-Ing. Schmidt

Heinz Dr.-Ing. Zimmermann

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.)

Linde GmbH

Original Assignee

Linde GmbH

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.)

1991-01-31

Filing date

1992-01-16

Publication date

1992-08-05

1992-01-16 Application filed by Linde GmbH filed Critical Linde GmbH

1992-08-05 Publication of EP0497155A1 publication Critical patent/EP0497155A1/fr

1994-10-05 Application granted granted Critical

1994-10-05 Publication of EP0497155B1 publication Critical patent/EP0497155B1/fr

2012-01-16 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

238000005235 decoking Methods 0.000 title claims abstract description 41
238000000197 pyrolysis Methods 0.000 title abstract 2
238000000034 method Methods 0.000 claims abstract description 16
UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
230000003197 catalytic effect Effects 0.000 claims abstract description 8
238000004227 thermal cracking Methods 0.000 claims abstract description 6
239000007789 gas Substances 0.000 claims description 58
238000005336 cracking Methods 0.000 claims description 15
230000003647 oxidation Effects 0.000 claims description 6
238000007254 oxidation reaction Methods 0.000 claims description 6
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
239000003054 catalyst Substances 0.000 claims description 5
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
238000001816 cooling Methods 0.000 claims description 2
229910052760 oxygen Inorganic materials 0.000 claims description 2
239000001301 oxygen Substances 0.000 claims description 2
239000000203 mixture Substances 0.000 abstract description 4
238000006243 chemical reaction Methods 0.000 description 6
CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
238000002485 combustion reaction Methods 0.000 description 4
239000003546 flue gas Substances 0.000 description 4
230000005855 radiation Effects 0.000 description 4
230000004992 fission Effects 0.000 description 3
238000010438 heat treatment Methods 0.000 description 3
239000004215 Carbon black (E152) Substances 0.000 description 2
229910002092 carbon dioxide Inorganic materials 0.000 description 2
239000001569 carbon dioxide Substances 0.000 description 2
238000004140 cleaning Methods 0.000 description 2
239000000571 coke Substances 0.000 description 2
238000004939 coking Methods 0.000 description 2
238000007086 side reaction Methods 0.000 description 2
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
239000005977 Ethylene Substances 0.000 description 1
150000001336 alkenes Chemical class 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
230000006866 deterioration Effects 0.000 description 1
238000009826 distribution Methods 0.000 description 1
230000007613 environmental effect Effects 0.000 description 1
238000005194 fractionation Methods 0.000 description 1
239000000446 fuel Substances 0.000 description 1
239000003517 fume Substances 0.000 description 1
238000009413 insulation Methods 0.000 description 1
239000007788 liquid Substances 0.000 description 1
238000013021 overheating Methods 0.000 description 1
238000010791 quenching Methods 0.000 description 1
239000000779 smoke Substances 0.000 description 1

Images

Classifications

- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation

Definitions

the invention relates to a method for decoking a cracking furnace for the thermal cracking of hydrocarbons, in which a decoking gas is passed through coked plant parts, a decoking exhaust gas being produced.
the thermal cracking of hydrocarbons is of great technical importance.
the thermal splitting of the hydrocarbons usually takes place in canned tubes which are arranged in a heatable cracking zone.
the fission products are cooled in a downstream fission gas cooler in order to bring the fission reactions to a standstill.
a number of side reactions occur which lead to economically uninteresting or even disruptive products.
Such a disruptive side reaction can be seen in the coking of parts of the plant, in particular the canned tubes and the cracked gas cooler, since it leads to a deterioration in the heat transfer and, in extreme cases, even the laying individual line elements can result.
a decoking gas e.g. a mixture of air and / or water vapor
the canned pipes which are heated from the outside, and the cooled chilled gas cooler are passed.
the high temperatures of the decoking which are, for example, between 600 and 1050 ° C., the deposits are burned off by oxidation or water gas reaction.
the resulting decoking exhaust gas can have, for example, peak values of up to approximately 20,000 vol ppm carbon monoxide in the dry exhaust gas. Since direct release of the decoking gas to the atmosphere should be avoided for environmental reasons, the decoking gas is introduced into the furnace of the cracking furnace for post-combustion in the prior art. Since the amount of the decoking gas in relation to the amount of revenge gas resulting from the underfired output of the cracking furnace is large during the decoking, a great deal of effort must be expended for a uniform supply of the decoking gas over the entire combustion chamber in order to be able to operate the furnace burners safely and without problems. This requires a complex gas duct system.
the object of the present invention is to design a method of the type mentioned in such a way that extensive cleaning of the decoking gas is achieved in an economical manner, so that it can be released into the atmosphere without hesitation.
This object is achieved in that the decoking exhaust gas is treated catalytically.
the process is considerably simplified.
the carbon monoxide components and other unburned components in the decoking gas are reduced to such an extent that the decoking gas can be released directly into the atmosphere.
An oxidation catalyst is expediently used, which permits extensive oxidation, for example of carbon monoxide to carbon dioxide, at the given exhaust gas temperatures.
the catalytic treatment of the decoking gas is preferably carried out at an exhaust gas temperature of approximately 200 to 600 ° C.
the cracked tubes are usually followed by a cracked gas cooler for cooling the cracked products, which, like the cracked tubes, cokes during the cracking operation.
the decoking gas is therefore passed over the cracked gas cooler and, after leaving the cooler, has the desired temperature of approximately 200 to approximately 600 ° C., so that it does not have to be heated or cooled for catalytic afterburning.
the catalytic converter can be installed in the exhaust pipe to the chimney, which is required anyway.
a gas stream containing water vapor and / or oxygen, in particular a water vapor / air mixture, is preferably used as the decoking gas.
a particular advantage of the process according to the invention is the fact that the catalyst does not require any operating resources, which makes the process extremely economical.
the process reduces the amount of carbon monoxide in the decoking flue gas to below the currently strictest flue gas limit values with high operational reliability.
no complex exhaust gas distribution system is required in the furnace of the cracking furnace.
the combustion chamber insulation does not have to be broken through the exhaust gas inlet, so that heat losses and the risk of supplying false air are avoided. Therefore, in the method according to the invention, the heating gas requirement is significantly lower in all operating modes than in the known methods, in particular there is no disturbance to the furnace operation, e.g. unfavorable change in the flame pattern and the resulting overheating of individual zones.
a cracking furnace 1 is shown in a highly simplified form, which is designed for the thermal cracking of hydrocarbons, such as naphtha or gas oil. It essentially consists of a radiation zone 2 and a convection zone 3.
the high temperatures required for the thermal splitting of the hydrocarbons are generated by burners 4.
the burners 4 are supplied with liquid or gaseous fuel via line 5.
the hot flue gases formed during the combustion pass at the upper end of the radiation zone 2 via a connecting channel 6 into the laterally offset convection zone 3.
Fresh hydrocarbon feedstock is fed via line 11 to the heat exchanger 7 arranged in the upper region of the convection zone and is preheated there against flue gas which has already largely cooled. It is then fed via lines 12 and 13 into heat exchangers 8 and 9 in order to be further heated there. It then reaches the radiation zone 2 via line 14 and is heated there to the desired reaction temperature in a radiation-heated coil 15.
the hot cracked gases exit the cracking furnace 1 at 16 and are immediately cooled in a quench cooler 17 in order to bring the cracking reactions to a standstill.
the cooled cracked gases leave the system shown here via line 18 and are fed to a fractionation.
the decoking gas is withdrawn at 16 from the cracking furnace 1 and passed over the cracking gas cooler 17. There the decoking gas is cooled down to a temperature of approx. 400 ° C. The decoking gas now has a temperature suitable for catalytic conversion of the carbon monoxide to carbon dioxide. After leaving the gap cooler 17, the decoking gas is fed to an oxidation catalyst 21. The cleaned decoking exhaust gas drawn off from the catalytic converter 21 is fed to the chimney 10 via line 22 and the exhaust pipe 23. The proportion of carbon monoxide in the cleaned exhaust gas is so low that it is safe to release it into the atmosphere.

Landscapes

Chemical & Material Sciences (AREA)
Oil, Petroleum & Natural Gas (AREA)
Engineering & Computer Science (AREA)
Physics & Mathematics (AREA)
Chemical Kinetics & Catalysis (AREA)
General Chemical & Material Sciences (AREA)
Thermal Sciences (AREA)
Organic Chemistry (AREA)
Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Exhaust Gas Treatment By Means Of Catalyst (AREA)
Treating Waste Gases (AREA)
Fire-Extinguishing Compositions (AREA)
Processing Of Solid Wastes (AREA)
Carbon And Carbon Compounds (AREA)

EP92100682A 1991-01-31 1992-01-16 Procédé de décokéfaction de fours de pyrolyse Expired - Lifetime EP0497155B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE4102862A DE4102862A1 (de)	1991-01-31	1991-01-31	Verfahren zur entkokung von spaltoefen
DE4102862		1991-01-31

Publications (2)

Publication Number	Publication Date
EP0497155A1 true EP0497155A1 (fr)	1992-08-05
EP0497155B1 EP0497155B1 (fr)	1994-10-05

Family

ID=6424086

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP92100682A Expired - Lifetime EP0497155B1 (fr)	1991-01-31	1992-01-16	Procédé de décokéfaction de fours de pyrolyse

Country Status (4)

Country	Link
EP (1)	EP0497155B1 (fr)
AT (1)	ATE112588T1 (fr)
DE (2)	DE4102862A1 (fr)
ES (1)	ES2065077T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
HRP930942A2 (en) *	1993-05-31	1995-02-28	Inos D O O	Process for the production of vinyl chloride
EP2048217A2 (fr)	2007-10-12	2009-04-15	Linde Aktiengesellschaft	Procédé de décocage de fours de craquage
CN113701172A (zh) *	2020-05-20	2021-11-26	中国石化工程建设有限公司	处理乙烯裂解炉烧焦气的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0036151A1 (fr) *	1980-03-15	1981-09-23	BASF Aktiengesellschaft	Procédé de décokage de refroidisseurs de gaz craqués
EP0337446A2 (fr) *	1988-04-13	1989-10-18	Phillips Petroleum Company	Oxydation de monoxyde de carbone et catalyseur à cet effet

1991
- 1991-01-31 DE DE4102862A patent/DE4102862A1/de not_active Withdrawn
1992
- 1992-01-16 AT AT92100682T patent/ATE112588T1/de not_active IP Right Cessation
- 1992-01-16 DE DE59200572T patent/DE59200572D1/de not_active Expired - Fee Related
- 1992-01-16 ES ES92100682T patent/ES2065077T3/es not_active Expired - Lifetime
- 1992-01-16 EP EP92100682A patent/EP0497155B1/fr not_active Expired - Lifetime

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0036151A1 (fr) *	1980-03-15	1981-09-23	BASF Aktiengesellschaft	Procédé de décokage de refroidisseurs de gaz craqués
EP0337446A2 (fr) *	1988-04-13	1989-10-18	Phillips Petroleum Company	Oxydation de monoxyde de carbone et catalyseur à cet effet

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
HRP930942A2 (en) *	1993-05-31	1995-02-28	Inos D O O	Process for the production of vinyl chloride
EP2048217A2 (fr)	2007-10-12	2009-04-15	Linde Aktiengesellschaft	Procédé de décocage de fours de craquage
DE102007048984A1 (de)	2007-10-12	2009-04-16	Linde Aktiengesellschaft	Verfahren zur Entkokung von Spaltöfen
CN113701172A (zh) *	2020-05-20	2021-11-26	中国石化工程建设有限公司	处理乙烯裂解炉烧焦气的方法
CN113701172B (zh) *	2020-05-20	2024-03-12	中国石化工程建设有限公司	处理乙烯裂解炉烧焦气的方法

Also Published As

Publication number	Publication date
ES2065077T3 (es)	1995-02-01
DE59200572D1 (de)	1994-11-10
ATE112588T1 (de)	1994-10-15
EP0497155B1 (fr)	1994-10-05
DE4102862A1 (de)	1992-08-06

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1992-06-18	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
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1994-06-30	ITF	It: translation for a ep patent filed
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