EP0138235A1 - Procédé de fabrication de brai thermiquement stable et d'huile à partir de résidus aromatiques de la pétrochimie et son utilisation - Google Patents

Procédé de fabrication de brai thermiquement stable et d'huile à partir de résidus aromatiques de la pétrochimie et son utilisation Download PDF

Info

Publication number: EP0138235A1
Authority: EP; European Patent Office
Prior art keywords: aromatic; residues; pitch; residue; pressure
Prior art date: 1983-09-27
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

EP84200680A

Other languages

German (de)

English (en)

Other versions

EP0138235B1 (fr

Inventor

Heinrich Dr. Hörmeyer

Jürgen Dr. Stadelhofer

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.)

1983-09-27

Filing date

1984-05-14

Publication date

1985-04-24

1984-05-14 Application filed by Ruetgerswerke AG filed Critical Ruetgerswerke AG

1985-04-24 Publication of EP0138235A1 publication Critical patent/EP0138235A1/fr

1986-09-10 Application granted granted Critical

1986-09-10 Publication of EP0138235B1 publication Critical patent/EP0138235B1/fr

Status Expired legal-status Critical Current

Links

125000003118 aryl group Chemical group 0.000 title claims abstract description 26
238000004519 manufacturing process Methods 0.000 title claims abstract description 8
239000011295 pitch Substances 0.000 claims abstract description 41
238000000034 method Methods 0.000 claims abstract description 19
238000009835 boiling Methods 0.000 claims abstract description 11
150000001875 compounds Chemical class 0.000 claims abstract description 9
238000007670 refining Methods 0.000 claims abstract description 5
239000007795 chemical reaction product Substances 0.000 claims abstract description 4
239000003921 oil Substances 0.000 claims description 9
CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 6
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
150000001336 alkenes Chemical class 0.000 claims description 4
239000010692 aromatic oil Substances 0.000 claims description 4
229910052799 carbon Inorganic materials 0.000 claims description 3
239000003795 chemical substances by application Substances 0.000 claims description 3
238000010626 work up procedure Methods 0.000 claims description 3
238000002352 steam pyrolysis Methods 0.000 claims 1
238000005984 hydrogenation reaction Methods 0.000 abstract description 5
238000010438 heat treatment Methods 0.000 abstract description 3
238000002156 mixing Methods 0.000 abstract description 2
238000004821 distillation Methods 0.000 description 8
238000004939 coking Methods 0.000 description 6
239000000203 mixture Substances 0.000 description 5
238000000197 pyrolysis Methods 0.000 description 5
UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
239000003054 catalyst Substances 0.000 description 4
239000007789 gas Substances 0.000 description 4
239000002480 mineral oil Substances 0.000 description 4
235000010446 mineral oil Nutrition 0.000 description 4
230000000052 comparative effect Effects 0.000 description 3
239000010779 crude oil Substances 0.000 description 3
238000006116 polymerization reaction Methods 0.000 description 3
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
230000032683 aging Effects 0.000 description 2
230000015572 biosynthetic process Effects 0.000 description 2
239000011280 coal tar Substances 0.000 description 2
238000001914 filtration Methods 0.000 description 2
239000001257 hydrogen Substances 0.000 description 2
229910052739 hydrogen Inorganic materials 0.000 description 2
239000000852 hydrogen donor Substances 0.000 description 2
238000005470 impregnation Methods 0.000 description 2
239000000463 material Substances 0.000 description 2
239000003208 petroleum Substances 0.000 description 2
239000011541 reaction mixture Substances 0.000 description 2
229920000049 Carbon (fiber) Polymers 0.000 description 1
239000004917 carbon fiber Substances 0.000 description 1
238000003776 cleavage reaction Methods 0.000 description 1
239000000571 coke Substances 0.000 description 1
239000000470 constituent Substances 0.000 description 1
238000005336 cracking Methods 0.000 description 1
238000006356 dehydrogenation reaction Methods 0.000 description 1
150000001993 dienes Chemical class 0.000 description 1
230000000694 effects Effects 0.000 description 1
239000011883 electrode binding agent Substances 0.000 description 1
239000000284 extract Substances 0.000 description 1
238000000605 extraction Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
239000000706 filtrate Substances 0.000 description 1
238000010304 firing Methods 0.000 description 1
239000010439 graphite Substances 0.000 description 1
229910002804 graphite Inorganic materials 0.000 description 1
230000003301 hydrolyzing effect Effects 0.000 description 1
238000011835 investigation Methods 0.000 description 1
239000007788 liquid Substances 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
239000011148 porous material Substances 0.000 description 1
239000011347 resin Substances 0.000 description 1
229920005989 resin Polymers 0.000 description 1
238000009738 saturating Methods 0.000 description 1
230000007017 scission Effects 0.000 description 1
239000004071 soot Substances 0.000 description 1
229910001220 stainless steel Inorganic materials 0.000 description 1
239000010935 stainless steel Substances 0.000 description 1
238000004230 steam cracking Methods 0.000 description 1
239000000126 substance Substances 0.000 description 1
238000003878 thermal aging Methods 0.000 description 1
238000007669 thermal treatment Methods 0.000 description 1
230000004580 weight loss Effects 0.000 description 1

Images

Classifications

- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)

Definitions

the invention relates to a process for producing thermally stable pitches from highly aromatic, unsaturated compounds containing petrochemical residues with an increased yield of distillable aromatic oils.
a process is known from US Pat. No. 3,238,118 for mixing residues from the hydrogenative splitting of gas oil with residues from crude oil distillation in a ratio of 0.3: 1 to 4: 1 and in a temperature range from 371 to 538 ° C. under a pressure of 48 to be treated thermally up to 69 bar in order to obtain a higher yield of gas oil and other lower-boiling oils.
the residue mixture treated in this way is fed back to the crude oil distillation, the gas oil fraction boiling between 200 and 400 ° C. is split hydrogenatingly into gasoline with the addition of a catalyst.
the residue boiling above 220 ° C is used as a hydrogen donor for the thermal treatment of crude oil residues.
the hydrogenated residues with a relatively low aromatic content of about 40% used in this process have a high boiling point and therefore cannot be separated from the residues by distillation. In addition, they would reduce the aromatic content of highly aromatic pitches.
the object was therefore to treat highly aromatic, unsaturated compound-containing residues of the petrochemical workup by a simple process, avoiding the disadvantages of the processes mentioned, so that a thermally stable pitch and aromatic mixtures are obtained from them in high yield by distillation.
the object is achieved in that the highly aromatic residues from the mineral oil workup containing unsaturated compounds are mixed with residues boiling between 150 and 280 ° C. from the hydrogenating refining of aromatic oils in a ratio of 1: 0.05 to 1: 0.25 and heated to a temperature between 350 and 400 ° C under the autogenous pressure that forms, and the reaction product is rectified under atmospheric or reduced pressure in order to obtain aromatic fractions and a pitch with a Krämer-Sarnow softening point of 50 ° C and higher .
Aromatic extracts and residues from the high-temperature pyrolysis of mineral oil fractions with an initial boiling point of 200 ° C. and higher, in particular from the vapor pyrolysis of gasoline, are used as highly aromatic residues for the production of olefins.
the aromatic fractions obtained can be worked up to form pure aromatics such as naphthalene and valuable aromatic mixtures such as soot oil without the formation of polymerization residues in the same way as coal tar fractions.
That according to the invention Pitch obtained from the process is characterized by a low content of quinoline-insoluble constituents (QI) and a high coking residue. It is therefore suitable for the production of highly anistropic coke for graphite electrodes and carbon fibers as well as for use as an electrode binder and impregnating agent for carbon molded articles.
QI quinoline-insoluble constituents
the pitch (A) was treated under extreme conditions at 250 ° C. in the presence of air for one week (168 h).
a commercially available impregnating pitch of petro origin (B) and a pitch (C) which were obtained in the same way as the pitch (A), but without the addition of hydroaromatics, were subjected to the same thermal aging.
the results of the analyzes are shown in Table 2.
the lowest possible viscosity and a low quinoline-insoluble content (QI) are required in order to achieve a quick and complete impregnation of the carbon molded articles. Aged.
the pitch produced according to the invention has a desired low viscosity at application temperatures with sufficient coking residue.
the petrochemical comparison pitch has similar data, 'wherein the slightly higher coking and the slightly higher viscosity of the resulting higher softening point, which is freely adjustable for all the pitches by distillation.
pitch (A) has a significantly higher coking residue.
hydrogenated stabilized pitch obviously smaller amounts of slightly cracking components remain in the impregnating agent, so that less escapes from the impregnated material during the firing process and the impregnating effect is improved.
the weight loss was less than 0.6% in any case, so that the change in material data can be attributed to chemical changes in pitch.
pitch (C) the hydrogenated pitch (A) shows a tolerable increase in viscosity and insolubility, while pitch (B) increases in viscosity so much that satisfactory processability can no longer be expected.
the figure shows the filtration curves for the pitch (A) produced by the process according to the invention and the pitch (C) produced without addition of hydroaromatics.
the pitch (B) had reciprocal filter capacities of at least 50 cm 2 min / g, aged 90 cm 2 min / g when the filter was quickly blocked.
pitch (A) Both untreated and aged, the values for pitch (A) are more favorable than for pitch (C).
the filter in the aged pitch (C) is blocked after 6.5 g / cm 2 flow, while larger amounts can be filtered by pitch (A).
the Pitch (A) produced according to the invention has significant advantages over comparative pitch (B) in terms of thermal resistance and filterability, and over comparative pitch (C) in terms of coking residue and filterability after aging.

Landscapes

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

EP84200680A 1983-09-27 1984-05-14 Procédé de fabrication de brai thermiquement stable et d'huile à partir de résidus aromatiques de la pétrochimie et son utilisation Expired EP0138235B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE19833334842 DE3334842A1 (de)	1983-09-27	1983-09-27	Verfahren zur herstellung thermisch stabiler peche und oele aus hocharomatischen petrochemischen rueckstaenden und deren verwendung
DE3334842		1983-09-27

Publications (2)

Publication Number	Publication Date
EP0138235A1 true EP0138235A1 (fr)	1985-04-24
EP0138235B1 EP0138235B1 (fr)	1986-09-10

Family

ID=6210133

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP84200680A Expired EP0138235B1 (fr)	1983-09-27	1984-05-14	Procédé de fabrication de brai thermiquement stable et d'huile à partir de résidus aromatiques de la pétrochimie et son utilisation

Country Status (4)

Country	Link
EP (1)	EP0138235B1 (fr)
JP (1)	JPS6092388A (fr)
DE (2)	DE3334842A1 (fr)
ES (1)	ES8503312A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP4534629A1 (fr)	2022-06-02	2025-04-09	Resonac Corporation	Procédé pour la production de brai de pétrole et de brai de pétrole

Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2953513A (en) *	1956-03-05	1960-09-20	Exxon Research Engineering Co	Hydrogen donor diluent cracking process
DE1815568A1 (de) *	1968-12-19	1970-06-25	Ruetgerswerke Ag	Verfahren zur Gewinnung von aromatischen Kohlenwasserstoffen aus aromatenreichen OElen mit einem hohen Gehalt an ungesaettigten Verbindungen
DE2927457A1 (de) *	1978-07-14	1980-01-24	Nippon Oil Co Ltd	Verfahren zur herstellung von bindemittelpech aus erdoel
EP0063053A2 (fr) *	1981-04-13	1982-10-20	Nippon Oil Co. Ltd.	Brais précurseurs pour fibres de carbone
EP0067581A1 (fr) *	1981-06-12	1982-12-22	E.I. Du Pont De Nemours And Company	Procédé de fabrication de brais

1983
- 1983-09-27 DE DE19833334842 patent/DE3334842A1/de not_active Withdrawn
1984
- 1984-05-14 EP EP84200680A patent/EP0138235B1/fr not_active Expired
- 1984-05-14 DE DE8484200680T patent/DE3460676D1/de not_active Expired
- 1984-06-29 ES ES533880A patent/ES8503312A1/es not_active Expired
- 1984-09-27 JP JP59200716A patent/JPS6092388A/ja active Pending

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2953513A (en) *	1956-03-05	1960-09-20	Exxon Research Engineering Co	Hydrogen donor diluent cracking process
DE1815568A1 (de) *	1968-12-19	1970-06-25	Ruetgerswerke Ag	Verfahren zur Gewinnung von aromatischen Kohlenwasserstoffen aus aromatenreichen OElen mit einem hohen Gehalt an ungesaettigten Verbindungen
DE2927457A1 (de) *	1978-07-14	1980-01-24	Nippon Oil Co Ltd	Verfahren zur herstellung von bindemittelpech aus erdoel
EP0063053A2 (fr) *	1981-04-13	1982-10-20	Nippon Oil Co. Ltd.	Brais précurseurs pour fibres de carbone
EP0067581A1 (fr) *	1981-06-12	1982-12-22	E.I. Du Pont De Nemours And Company	Procédé de fabrication de brais

Also Published As

Publication number	Publication date
JPS6092388A (ja)	1985-05-23
ES533880A0 (es)	1985-03-01
EP0138235B1 (fr)	1986-09-10
ES8503312A1 (es)	1985-03-01
DE3334842A1 (de)	1985-04-04
DE3460676D1 (en)	1986-10-16

Legal Events

Date	Code	Title	Description
1985-02-22	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
1985-04-24	AK	Designated contracting states	Designated state(s): BE DE FR GB IT NL
1985-05-09	ITCL	It: translation for ep claims filed	Representative=s name: BARZANO' E ZANARDO ROMA S.P.A.
1985-05-15	17P	Request for examination filed	Effective date: 19850227
1985-06-03	TCNL	Nl: translation of patent claims filed
1985-07-19	EL	Fr: translation of claims filed
1986-04-09	17Q	First examination report despatched	Effective date: 19860224
1986-06-24	ITF	It: translation for a ep patent filed
1986-07-26	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
1986-09-10	AK	Designated contracting states	Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL
1986-10-16	REF	Corresponds to:	Ref document number: 3460676 Country of ref document: DE Date of ref document: 19861016
1987-01-09	ET	Fr: translation filed
1987-07-08	PLBE	No opposition filed within time limit	Free format text: ORIGINAL CODE: 0009261
1987-07-08	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT
1987-08-26	26N	No opposition filed
1991-05-31	ITTA	It: last paid annual fee
1993-06-03	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: DE Payment date: 19930603 Year of fee payment: 10
1994-05-04	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: GB Payment date: 19940504 Year of fee payment: 11
1994-05-11	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: FR Payment date: 19940511 Year of fee payment: 11
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1995-11-30	BERE	Be: lapsed	Owner name: RUTGERSWERKE A.G. Effective date: 19950531
1995-12-01	PG25	Lapsed in a contracting state [announced via postgrant information from national office to epo]	Ref country code: NL Effective date: 19951201
1996-01-10	GBPC	Gb: european patent ceased through non-payment of renewal fee	Effective date: 19950514
1996-02-01	NLV4	Nl: lapsed or anulled due to non-payment of the annual fee	Effective date: 19951201
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