EP0237702B1 - Procédé pour la cokéfaction continue de poix et utilisation du coke obtenu - Google Patents

Procédé pour la cokéfaction continue de poix et utilisation du coke obtenu Download PDF

Info

Publication number
EP0237702B1
EP0237702B1 EP87100270A EP87100270A EP0237702B1 EP 0237702 B1 EP0237702 B1 EP 0237702B1 EP 87100270 A EP87100270 A EP 87100270A EP 87100270 A EP87100270 A EP 87100270A EP 0237702 B1 EP0237702 B1 EP 0237702B1
Authority
EP
European Patent Office
Prior art keywords
coking
pitch
coke
pitches
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87100270A
Other languages
German (de)
English (en)
Other versions
EP0237702A2 (fr
EP0237702A3 (en
Inventor
Manfred Morgenstern
Claus Bertrand
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.)
Rain Carbon Germany GmbH
Original Assignee
Ruetgerswerke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ruetgerswerke AG filed Critical Ruetgerswerke AG
Priority to AT87100270T priority Critical patent/ATE45587T1/de
Publication of EP0237702A2 publication Critical patent/EP0237702A2/fr
Publication of EP0237702A3 publication Critical patent/EP0237702A3/de
Application granted granted Critical
Publication of EP0237702B1 publication Critical patent/EP0237702B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the invention relates to a method for the continuous coking of pitches, in particular hard coal tar pitches, and the use of the coke obtained by this method.
  • the process according to a) is high-temperature coking and, apart from a few special features, corresponds to the known coal coking process.
  • a hard coal tar pitch with a coking residue according to Brockmann-Muck of more than 50% is used as the input product.
  • the coke obtained is very hard and generally does not need to be calcined because of the high coking temperature of at least 1000 ° C.
  • the process is very labor-intensive. Because of the different physical and chemical properties of the hard pitch, the plants, in particular the brick lining, are much more susceptible to repair than those of coal than those of coal coking.
  • the process itself is discontinuous, so that a large number of chambers are necessary in order to enable quasi-continuous operation.
  • the process according to b) is a smoldering process at around 500 ° C.
  • hard coal tar soft pitches are also used.
  • the delayed coker was originally operated as a thermal cracker. However, it was soon recognized that it is an excellent device for producing highly anisotropic special cokes.
  • the smoldering coke obtained must be dried and calcined for further use. The plant costs are high, so that profitability is only given in the production of particularly high-quality coke or valuable oils. This is usually not the case with untreated coal tar pitch.
  • the method itself can be carried out quasi-continuously with at least two coker drums.
  • the process according to c) is also a smoldering process, but is carried out continuously.
  • the fluid coker is a thermal cracker for mineral oil residues.
  • the coke generated as a waste product is used as fuel. This process is less suitable for coal tar pitches because of the low oil and gas yield.
  • the object of the invention is therefore to develop a simple, inexpensive process for the coking of hard coal tar pitches and comparable products and to find suitable fields of application for the coke thus produced.
  • the object is achieved in that the hard pitch is coked in a rotary tube furnace provided with a broaching tool and heated from the outside at temperatures of the inner wall between 500 and 800 ° C. and a residence time of 0.5 to 1.5 hours, the resulting gases and Vapors are passed in countercurrent to the coking pitch, and the smoldering coke obtained is then calcined in the usual manner, preferably without prior cooling.
  • Aromatic residues with a softening point (EP) according to Kraemer-Sarnow (K.-S.) of at least 130 ° C and a coking residue according to Brockmann-Muck (B.-M.) of at least 45% by weight are referred to as hard pitch.
  • E softening point
  • K.-S. Kraemer-Sarnow
  • B.-M. coking residue
  • the rotary kiln should advantageously be divided into several sections that can be heated differently. The segments facing the feed side are heated to an outside temperature of approximately 850 ° C. by external heating. The outside temperature of the following sections can then drop to around 600 ° C.
  • the gases and vapors are conducted in countercurrent to the coking pitch.
  • the vapors are condensed after leaving the rotary kiln and can be used as a soot oil component or can be used for hard pitch production.
  • the feeding of an inert gas on the discharge side of the rotary kiln has proven to be helpful. This shortens the dwell time of the vapors in the coking zone and prevents soot formation and deposits in the subsequent vapor lines.
  • a screw that is conical towards the feed side and weighted with granular material has proven itself, which is at least about 1/3, preferably 1/2 times as long as the rotary tube and its inclination is greater than that of the rotary tube.
  • the broaching tool is preferably self-centering and is moved non-positively by the drum.
  • the pitch can be introduced in pieces, for example via a rotary valve, or in liquid form in the rotary kiln.
  • the smoked coke is discharged in pieces via another rotary valve and can be fed directly to the calciner. Since there is no need to cool the coke with water in the coking processes a) and b), considerably less time and energy is required for the calcination.
  • Rotary kilns are known to be used for the coking or calcination of solid fuels such as smoked coke and lignite or for the pyrolysis of predominantly solid waste
  • solid fuels such as smoked coke and lignite
  • pyrolysis of predominantly solid waste
  • a rotary kiln with an inner diameter of 0.8 m and a heated length of 7.2 m with a 4 m long conical screw in the front part, 75 kg / h of a hard coal tar pitch with an EP (K.-S.) of 150 ° C and a coking residue (B.-M.) of 50%.
  • the oven is divided into 6 sections, which are heated indirectly with gas.
  • the temperature of the outer wall in the area of the inlet is 850 ° C and drops to 700 ° C towards the outlet.
  • the pipe wall outside temperature is approximately 800 ° C on average over the individual heating zones.
  • the rotary tube is driven at 2 rpm.
  • the average residence time of the coking pitch in the rotary kiln is about 1.5 hours.
  • the oven shows no caking and the green coke is produced in pieces (74% by weight greater than 5 mm, 99% by weight greater than 1 mm).
  • the coke has a high density and strength. It is fed into a calcining drum without cooling or intermediate storage and calcined there at 1300 ° C in the usual way.
  • Example 1 is repeated with a throughput of 300 kg / h of pitch at a speed of 6 rpm.
  • the dwell time of the coking pitch in the rotary kiln is reduced to about 0.5 h. 71% by weight of green coke with 3.5% by weight of volatile and a bulk density of 0.5 g / cm 3, 11% by weight of heavy oil, 14% by weight of light oil and 4% by weight of gas and losses are produced .
  • the rotary kiln is flushed with 30 m 3 / h nitrogen in counterflow to the pitch. Gases and vapors leave the furnace on the pitch feed side and are condensed in two stages.
  • the green coke is immediately transferred to a conventional calcining drum and calcined there at 1300 ° C. 89% by weight of calcined coke with a residual hydrogen content of 0.1% by weight and a true density of 2.028 g / cm 3 are obtained.
  • the analyzes of the oils and the gas are contained in Tables I and II.
  • Table 111 the calcined coke (1) obtained according to the invention is compared in its properties with normal petro-coke (2) and with pitch coke from the horizontal chamber furnace (3). As usual, the examinations were carried out on shaped bodies.
  • the coke according to the invention is characterized by low CO 2 burnup and high electrical conductivity. Despite the higher conductivity compared to the usual pitch coke, its structure is finer and more uniformly mosaic-like, as the cross-sectional images show.
  • the advantages of the coking process according to the invention lie in the short coking time of 1.5 to 0.5 hours, the low capital expenditure and the easy operation. It is also possible to return the fine portion of the coke and coke it together with the bad luck.
  • the rods are graphitized at 2700 ° C and their physical properties compared to those of a reactor graphite made from Gilsonite coke:
  • the coke according to the invention is outstandingly suitable for the production of reactor graphite. It has an exceptionally low expansion coefficient and a low anisotropy coefficient for pitch coke made from normal, uncleaned hard pitch. Another advantage is its small pore volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inorganic Fibers (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (3)

1. Procédé pour la cokéfaction en continu de brais, caractérisé en ce qu'un brai dur ayant un point de ramollissement (Kraemer-Sarnow) d'au moins 130°C et un résidu de cokéfaction (Brockmann-Muck) d'au moins 45% en poids est cokéfié dans un four tubulaire rotatif équipé d'un outil dégorgeoir et pouvant être chauffé depuis l'extérieur à des températures de la paroi intérieure entre 500 et 800°C et un temps de séjour de 0,5 à 1,5 heures, les gaz et les vapeurs produits étant menés à contre-courant vers le brai à cokéfier et le semi-coke ou coke de basse carbonisation obtenu étant subséquemment calciné selon la manière habituelle, de préférence sans refroidissement préliminaire.
2. Procédé selon la revendication 1, caractérisé en ce qu'un gaz inerte est introduit sur le côté de déchargement du four tubulaire rotatif.
3. Utilisation du coke produit selon la revendication 1 pour la production de graphite de réacteur.
EP87100270A 1986-03-20 1987-01-12 Procédé pour la cokéfaction continue de poix et utilisation du coke obtenu Expired EP0237702B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87100270T ATE45587T1 (de) 1986-03-20 1987-01-12 Verfahren zur kontinuierlichen verkokung von pechen und verwendung des gewonnenen kokses.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863609348 DE3609348A1 (de) 1986-03-20 1986-03-20 Verfahren zur kontinuierlichen verkokung von pechen und verwendung des gewonnenen kokses
DE3609348 1986-03-20

Publications (3)

Publication Number Publication Date
EP0237702A2 EP0237702A2 (fr) 1987-09-23
EP0237702A3 EP0237702A3 (en) 1988-02-10
EP0237702B1 true EP0237702B1 (fr) 1989-08-16

Family

ID=6296819

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87100270A Expired EP0237702B1 (fr) 1986-03-20 1987-01-12 Procédé pour la cokéfaction continue de poix et utilisation du coke obtenu

Country Status (11)

Country Link
US (1) US4764318A (fr)
EP (1) EP0237702B1 (fr)
JP (1) JPS62227991A (fr)
AT (1) ATE45587T1 (fr)
AU (1) AU585436B2 (fr)
CA (1) CA1268438A (fr)
CS (1) CS274289B2 (fr)
DE (2) DE3609348A1 (fr)
ES (1) ES2000091B3 (fr)
PL (1) PL151853B1 (fr)
ZA (1) ZA87673B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118066A (ja) * 1993-10-22 1995-05-09 Tokai Carbon Co Ltd 高強度等方性黒鉛材の製造方法
US20060074598A1 (en) * 2004-09-10 2006-04-06 Emigholz Kenneth F Application of abnormal event detection technology to hydrocracking units
US7720641B2 (en) * 2006-04-21 2010-05-18 Exxonmobil Research And Engineering Company Application of abnormal event detection technology to delayed coking unit
US8862250B2 (en) 2010-05-07 2014-10-14 Exxonmobil Research And Engineering Company Integrated expert system for identifying abnormal events in an industrial plant
US10836969B2 (en) * 2016-09-27 2020-11-17 Cleancarbonconversion Patents Ag Process reacting organic materials to give hydrogen gas

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2357621A (en) * 1941-07-30 1944-09-05 Max B Miller & Co Inc Apparatus for coking petroleum residues
US3316183A (en) * 1963-12-12 1967-04-25 Exxon Research Engineering Co Shaped carbon articles and method of making
DE1796129A1 (de) * 1968-09-05 1972-03-02 Metallgesellschaft Ag Verfahren zur kontinuierlichen Erzeugung von metallurgischem Formkoks
US3756791A (en) * 1971-06-09 1973-09-04 Bethlehem Steel Corp Al and or coal derivatives method for simultaneously calcining and desulfurizing agglomerates co
US4053365A (en) * 1975-12-02 1977-10-11 Great Lakes Carbon Corporation Rotary calciner
DE2627479C2 (de) * 1976-06-18 1983-09-22 Bergwerksverband Gmbh, 4300 Essen Verwendung eines Formkokses als Adsorptionsmittel für Schwefeloxide aus Abgasen
FR2385786A1 (fr) * 1977-03-28 1978-10-27 Nord Pas Calais Houilleres Procede permettant d'obtenir du coke moule a partir de charbons non cokefiables
US4218288A (en) * 1979-02-12 1980-08-19 Continental Oil Company Apparatus and method for compacting, degassing and carbonizing carbonaceous agglomerates
DE2925202A1 (de) * 1979-06-22 1981-01-15 Rupert Hoell Verfahren und vorrichtung zur pyrolyse von kunststoff, kohlenwasserstoffhaltigem sondermuell etc.
US4303477A (en) * 1979-06-25 1981-12-01 Babcock Krauss-Maffei Industrieanlagen Gmbh Process for the pyrolysis of waste materials
CH645401A5 (de) * 1980-08-21 1984-09-28 Alusuisse Verfahren zur herstellung von entschwefeltem koks fuer in der aluminiumelektrolyse eingesetzte anoden.
US4369171A (en) * 1981-03-06 1983-01-18 Great Lakes Carbon Corporation Production of pitch and coke from raw petroleum coke
DE3125609A1 (de) * 1981-06-30 1983-01-13 Rütgerswerke AG, 6000 Frankfurt Verfahren zur herstellung von kohlenstofformkoerpern
CA1260868A (fr) * 1984-04-11 1989-09-26 Izaak Lindhout Methode de grillage du coke vert

Also Published As

Publication number Publication date
CS186187A2 (en) 1990-09-12
ATE45587T1 (de) 1989-09-15
CS274289B2 (en) 1991-04-11
CA1268438A (fr) 1990-05-01
ZA87673B (en) 1987-09-16
US4764318A (en) 1988-08-16
ES2000091A4 (es) 1987-12-01
DE3609348A1 (de) 1987-09-24
PL264723A1 (en) 1988-05-12
DE3760453D1 (en) 1989-09-21
AU7043487A (en) 1987-09-24
EP0237702A2 (fr) 1987-09-23
ES2000091B3 (es) 1989-10-16
JPS62227991A (ja) 1987-10-06
AU585436B2 (en) 1989-06-15
PL151853B1 (en) 1990-10-31
EP0237702A3 (en) 1988-02-10

Similar Documents

Publication Publication Date Title
DE2456575C2 (de) Verfahren zur Herstellung von Elektrodenkoks
DE2730233C2 (de) Verfahren zur Herstellung von hochkristallinem Petroleumkoks
DE10138657A1 (de) Herstellung von Kohlenteer und Kohlenwasserstoffmischungs-Pech unter Anwendung eines Hochleistungs Verdampfungsdestillationsverfahrens
DE2700554B2 (de) Verfahren zur Verkokung lignitartiger Kohle
DE69721315T2 (de) Methode zur erhöhung der ausbeute von flüssigen produkten in einem verzögerten verkokungsprozess
DE2747495C2 (de) Verfahren zum kontinuierlichen Herstellen eines Kokses
DE102004035934B4 (de) Verfahren zur Erzeugung von Nadelkoks
EP0237702B1 (fr) Procédé pour la cokéfaction continue de poix et utilisation du coke obtenu
DE2458169A1 (de) Verfahren zum herstellen von koks
DE3630986C2 (de) Verfahren zur Herstellung von hochreinem Koks
DE3147677C2 (de) Verfahren zur verzögerten Verkokung
DE2903884C3 (de) Verfahren zum Calcinieren und thermischen Entschwefeln von rohem Petrolkoks
DE2548946A1 (de) Verfahren zum extrahieren von kohle
DE2637097C3 (de) Verfahren zur Herstellung von geformtem Koks für metallurgische Zwecke
DE3335484C2 (fr)
DE4234785C2 (de) Verfahren zur Herstellung von geformter Aktivkohle
DD144171A5 (de) Verfahren zur umwandlung von altgummi
DE2150376C3 (de) Verfahren zur Erzeugung von Koks hoher Qualität mit nadeiförmiger Struktur
EP0290002B1 (fr) Procédé de production d'une huile de pyrolyse
DE19621252C1 (de) Verfahren zur Herstellung eines Holzkohleersatzstoffes oder von Aktivkohle
EP0174035B1 (fr) Procédé de fabrication de coke aciculaire à petite expansion volumétrique irréversible à partir de brai de goudron de charbon
DE2542842C3 (de) Verfahren zur Herstellung von Petrolkoks mit ausgezeichnet1™·"11'11"11 Gefüge und Vorrichtung zur Durchführung des Verfahrens
EP0316450B1 (fr) Procede d'obtention de coke
DE2116504A1 (de) Verfahren zur Herstellung von Spezialkoksen
DE2218764C3 (de) Verfahren zur Herstellung von Formkoks

Legal Events

Date Code Title Description
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

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT DE ES FR GB IT NL

ITCL It: translation for ep claims filed

Representative=s name: BARZANO' E ZANARDO ROMA S.P.A.

TCNL Nl: translation of patent claims filed
GBC Gb: translation of claims filed (gb section 78(7)/1977)
EL Fr: translation of claims filed
PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19880126

17Q First examination report despatched

Effective date: 19890124

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT DE ES FR GB IT NL

REF Corresponds to:

Ref document number: 45587

Country of ref document: AT

Date of ref document: 19890915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3760453

Country of ref document: DE

Date of ref document: 19890921

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940105

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19940111

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19940113

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19940128

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19940131

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940202

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950112

Ref country code: AT

Effective date: 19950112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950801

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950929

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19950801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19951003

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050112