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EP0078701B1 - Procédé pour la préparation d'asphaltes modifiés - Google Patents

Procédé pour la préparation d'asphaltes modifiés Download PDF

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Publication number
EP0078701B1
EP0078701B1 EP19820305812 EP82305812A EP0078701B1 EP 0078701 B1 EP0078701 B1 EP 0078701B1 EP 19820305812 EP19820305812 EP 19820305812 EP 82305812 A EP82305812 A EP 82305812A EP 0078701 B1 EP0078701 B1 EP 0078701B1
Authority
EP
European Patent Office
Prior art keywords
sulfur
asphalt
temperature
oxidant
range
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
EP19820305812
Other languages
German (de)
English (en)
Other versions
EP0078701A2 (fr
EP0078701A3 (en
Inventor
Bernard Chavet
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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 Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0078701A2 publication Critical patent/EP0078701A2/fr
Publication of EP0078701A3 publication Critical patent/EP0078701A3/en
Application granted granted Critical
Publication of EP0078701B1 publication Critical patent/EP0078701B1/fr
Expired legal-status Critical Current

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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
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone

Definitions

  • This invention relates to a process for preparing a sulfur-modified asphalt.
  • asphalt is employed herein synonymously with the term bitumen.
  • solid oxidants for example, chromium trioxide and phosphorus. pentasulfide are not suitable.
  • a suitable liquid oxidant is hydrogen peroxide.
  • the oxidant is air or oxygen.
  • the normally preferred temperature of contact in step (a) is in the range 145°C to 155°C.
  • the duration of the contact is not more than one hour, typically 10 to 20 minutes depending on the feedstock being processed.
  • the product of step (a) is one in which the softening point of the starting material is not significantly altered.
  • the product of this step of the process is a deliberately mildly oxidized asphalt and hence is very different from the well-known oxidized or "blown" asphalt products which are normally prepared by oxidation for from 4 to 8 hours at 240°C to 290°C.
  • the product is also very different from that disclosed in United Kingdom Patent 278,679 published in 1928.
  • the disclosure there is of a tar, tar oil or anthracene oil oxidized with air, or a liquid oxidant such as nitric acid, to an extent that the product (i) retains a sufficient degree of fluidity (ii) is insensitive to water, so that it can be directly used in road construction.
  • FR 1.567.671-A broadly discloses a process in which a paraffinic petroleum bitumen is treated at 110 to 150°C, for an unspecified period of time, with air in the presence of certain types of catalysts. There is no reference to, or evidence of, the products so made having reduced reactivity toward sulfur. Moreover, in the only two specific examples relating to the air treatment a temperature of 130°C is employed, either for 1 hour or 2 hours. This is a lower temperature and, in the second case, a longer time than required for step (a) of the process of the present invention.
  • step (b) of the process of the invention the mildly oxidized product of step (a) is blended with sulfur at a temperature in the range 120°C to 170°C.
  • the steps (a) and (b) are preferably conducted at substantially the same temperature in the range 140°C to 170°C, more especially 145°C to 155°C.
  • the step of contacting with sulfur need not necessarily immediately follow step (a) but can, if desired, follow later, for example, at a road-making site.
  • the sulfur may be employed in amount from up to 45 wt%, more especially 30 wt%.
  • the asphalt feedstock employed in processes of the invention may be any one of the known non-oxidized materials, for example, the penetration grade asphalts such as 40/60 to 180/220, preferably 80/100.
  • the penetration grade asphalts such as 40/60 to 180/220, preferably 80/100.
  • such softer petroleum residua can be employed, for example, those with penetrations of about 600, or higher, including the light 600-800 grade (ASTM D 5).
  • Table 1 shows for each material its crude oil origin, its penetration and the said H 2 S quantity evolved.
  • the first six materials show essentially the same reactivity to sulfur independent of the crude oil origin. Moreover, as indicated by Tests 2 and 3, the reactivity is substantially independent of the penetration, so that short and long run vacuum residua produced from the same crude oil behave substantially similarly when treated with the sulfur.
  • Tests Nos 7 and 8 were conducted with two different blends of straight run vacuum residua and oxidized vacuum residua, that is to say the normal fully oxidized material.
  • the blends show less reactivity with sulfur under the stated conditions.
  • Tests 9 and 10 were conducted with two mildly blown materials made in accordance with step (a) of the invention. Both materials show a considerably reduced reactivity with sulfur under the stated conditions, the origin of crude oil being unimportant. It will be seen that the reactivity is appreciably less than even the blends 7 and 8; indicating that the results obtainable by means of the invention cannot be achieved by mereblend- ing of known blown and un-blown materials.
  • Fig. 1 is a plot of relative reactivity of the various oxidized materials thus produced with sulfur, against oxidation time. With all materials H 2 S is reduced by 50% after only 15 mins air blowing, and by 75% after 1 hour.
  • step (a) of the invention illustrates that the mildly oxidized product of step (a) of the invention retains its low reactivity to sulfur over a storage period at 150°C of ten or more days. This is very important in practice in that the oxidized product can be made and hot-stored in one location and thereafter blended with sulfur at another location days later.
  • Fig. 2 shows the results obtained with an asphalt of penetration 80 to 100 from an Arabian Heavy crude and a residue from the vacuum distillation of an Arabian Light crude. The figure clearly shows that even after 10 days storage, both products are still considerably less reactive with sulfur than the corresponding unblown materials.
  • the sulfur-modified asphalts of the invention have considerable importance as binding agents in road-making and road-surfacing operations, among other uses.
  • H 2 S evolution has hitherto presented problems which sometimes rule out the possibility of using sulfur-modified asphalts even though they have desirable properties.
  • H 2 S evolution can be reduced, thereby widening the practical scope of use of sulfur-modified asphalts, since the important properties of those are not significantly affected in the products made according to the present invention.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Working-Up Tar And Pitch (AREA)

Claims (5)

1. Procédé de préparation d'un asphalte modifié au soufre, caractérisé en ce que:
(a) l'asphalte est mis en contact avec un oxydant liquide ou gazeux, éventuellement en présence d'un catalyseur, à une température comprise de 140°C à 170°C pendant une durée allant jusqu'à une heure, de sorte que le point de ramollisement de l'asphalte n'est pas sensiblement modifié; et
(b) le produit obtenu est ensuite mis en contact avec du soufre non combiné chimiquement ou non lié, à une température dans le domaine de 120°C à 170°C.
2. Procédé selon la revendication 1, caractérisé en ce que l'oxydant employé dans l'étape (a) est l'oxygène ou l'air.
3. Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce que la mise en contact avec le soufre succède pratiquement immédiatement à la mise en contact avec l'oxydant.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les étapes (a) et (b) sont toutes les deux réalisées pratiquement à la même température, cette température étant comprise dans le domaine de 140°C à 170°C, de préférence de 145°C à 155°C.
5. Asphalte modifié au soufre lorsqu'il est produit par le procédé revendiqué dans l'une quelconque des revendications précédentes.
EP19820305812 1981-11-06 1982-11-02 Procédé pour la préparation d'asphaltes modifiés Expired EP0078701B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8133560 1981-11-06
GB08133560A GB2108998A (en) 1981-11-06 1981-11-06 Modified asphalts

Publications (3)

Publication Number Publication Date
EP0078701A2 EP0078701A2 (fr) 1983-05-11
EP0078701A3 EP0078701A3 (en) 1984-02-22
EP0078701B1 true EP0078701B1 (fr) 1986-01-15

Family

ID=10525694

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820305812 Expired EP0078701B1 (fr) 1981-11-06 1982-11-02 Procédé pour la préparation d'asphaltes modifiés

Country Status (3)

Country Link
EP (1) EP0078701B1 (fr)
DE (1) DE3268597D1 (fr)
GB (1) GB2108998A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7374659B1 (en) 2004-06-22 2008-05-20 Asphalt Technology, Llc. Methods and systems for modifying asphalts
US7906011B2 (en) 2008-06-13 2011-03-15 Asphalt Technology Llc Methods and systems for manufacturing modified asphalts

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3630789A1 (de) * 1986-09-10 1987-01-29 Al Douri Amad Dipl Ing Verfahren zur herstellung von oxidationsbitumen durch reaktion mit luft in gegenwart von radikalbildnern
RU2149170C1 (ru) * 1999-10-06 2000-05-20 Ненахов Михаил Николаевич Способ получения битума из малосернистых, и/или сернистых, и/или высокосернистых нефтей
CN100365098C (zh) * 2004-10-29 2008-01-30 中国石油化工股份有限公司 一种水工沥青的制备方法
CN106433730A (zh) * 2016-11-14 2017-02-22 广西泓达生物能源科技有限公司 一种沥青轻度氧化加工方法
CN113046109B (zh) * 2021-03-11 2021-12-07 山西中科化美科技有限责任公司 一种低硫低氮环保沥青的制备方法及应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR778523A (fr) * 1934-07-12 1935-03-18 Procédé pour modifier le pouvoir adhésif des goudrons et des hydrocarbures analogues et pour modifier les sous-produits que l'on en retire
US2182837A (en) * 1936-02-25 1939-12-12 Texas Gulf Sulphur Co Method of paving
US2148869A (en) * 1936-10-30 1939-02-28 Standard Oil Co Manufacture of asphalt
FR1435913A (fr) * 1965-02-23 1966-04-22 Raffinage Cie Francaise Bitumes émulsionnables et leur procédé de fabrication
FR1567671A (fr) * 1968-06-04 1969-05-16

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7374659B1 (en) 2004-06-22 2008-05-20 Asphalt Technology, Llc. Methods and systems for modifying asphalts
US7988846B1 (en) 2004-06-22 2011-08-02 Asphalt Technology Llc Methods and systems for modifying asphalts
US8252168B1 (en) 2004-06-22 2012-08-28 Asphalt Technology Llc Methods and systems for modifying asphalts
US7906011B2 (en) 2008-06-13 2011-03-15 Asphalt Technology Llc Methods and systems for manufacturing modified asphalts
US8377285B2 (en) 2008-06-13 2013-02-19 Asphalt Technology Llc. Methods and systems for manufacturing modified asphalts

Also Published As

Publication number Publication date
GB2108998A (en) 1983-05-25
EP0078701A2 (fr) 1983-05-11
DE3268597D1 (en) 1986-02-27
EP0078701A3 (en) 1984-02-22

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