FR2486092A1 - PITCHER-LIKE PRODUCTS AND PROCESS FOR OBTAINING SAME - Google Patents

Abstract

THE INVENTION CONCERNS PRODUCTS OF THE BRAIS TYPE. THESE PRODUCTS ARE OBTAINED BY HEATING OILS OF CARBO- OR PETROLEOCHEMICAL ORIGIN OF LOW VALUE IN QUANTITIES OF 15 - 25 SULFUR. THE PROCESS GIVES MORE OR LESS HARD BRAIS AT WILL.

Description

Pitch type products and the Rour process for obtaining them. The invention

  relates to new products of the pitch type and a process for obtaining them. It relates more particularly to products which can be obtained by reaction of oil from coal or

petroleum with sulfur.

  The pitches normally obtained by distillation of tars find a very varied use for example as binders for agglomerates, for artificial coals for electrodes, for mineral substances or cellulose fibers, for making tar for roads, roofing sheets of roofs, or coke of pitches as well as in varnishes, insulating coating products or for

  insulating masses. For this reason there is a demand

  important for these products and we are looking for possibilities to artificially increase the

  pitches in line with demand.

  On the other hand, there are only limited possibilities of use for certain tar oils forming in the distillation of tar as well as for certain fractions of the distillation of petroleum, so that it seems logical from the point of view view of using the raw material to transform these oils into more like pitches

great value.

  The object of the invention is therefore to prepare

  pitch-like products from such oils.

  The solution according to the invention consists of new products.

  grazing-like calves with a softening temperature in the range of 70-18000, a sulfur content of 4-9% o, a content of constituents insoluble in quinoline of 0.2 - 3% and a content of insoluble constituents in toluene from 32 - 50%, and tun ratio

O / H from 1.25 - 1.65.

  Ia preparation of these artificial pitches takes place by reaction of oils from coal or petroleum with 15 - 25% by weight of sulfur at temperatures of 115-16000 and immediately after by heating for several hours the tar oil adduct - sulfur at temperatures

from 180 - 30000.

  The reaction of sulfur with tar oils or mineral oils, known as sulfurization of these oils, is known. In this operation, the oils are treated with approximately 1 - 2o of sulfur hot (approximately 200 0), an operation in which a thickening of the oils takes place and

forms consistent lubricants.

  In other processes, the tar or mineral oil or tar is boiled with addition of rosin or resin oil with dilute sulfuric acid and thus a synthetic rubber, a modified resin is prepared

or artificial asphalt.

  In French Patent No. 1,112,076, the manufacture of artificial asphalt is described by treatment of tar or tar oil with sulfur or chloride.

  sulfur. In this reaction, a solidification is obtained.

  tion by addition of sulfur on the double bonds present and no gas evolution is observed, since the temperature of about 10000 is too low for condensation reactions. In contrast to this, we treat, according to German patent DRP 332 888, anthracene residues containing sulfur (approximately 1 - 2%.) long enough and sufficiently energetically with sulfur until a substance can be used as a replacement for asphalt. Likewise, British Patent No. 306,421 describes pitch as an oil polymerization product.

2486-092

  tar and sulfur. As in the two preceding documents, however, here too, the reaction is reacted with relatively little (1-3%) sulfur at 200-300 0, that is to say that the sulfur introduced is released almost quantitatively in the form of hydrogen sulfide. In contrast, according to the invention, products of the pitcher type are prepared by mixing oils from coal or also petroleum with 15-25% sulfur at temperatures of 115-160o0, that is to say say at temperatures

  slightly above the melting point of sulfur.

  During this operation the first reactions already occur. Sulfur adds to reactive centers

  present in oils. The first reticu-

  lations and the viscosity of the reaction mixture increases.

  For an additional temperature rise above 180o0 the second possibility of sulfur reaction begins. It acts as a dehydrogenator and is released in the form of hydrogen sulfide. During this operation, new reactive centers are formed in the oils, which can crosslink either directly with each other, or by sulfur bridges. By varying the quantity of sulfur as well as the reaction time and the reaction temperatures, it is possible to adjust in the range of 70-1800 any temperature of

softening.

  To ensure the plasticity of the pitches according to the invention, sulfur additions were used in% relative to the stoichiometric hydrogen equivalents of the oils used, each time below 40%, using filtered anthracene oil even in

below 25%.

  As starting material, it is possible to use both oils from coal and oils from petroleum such as anthracene oils (boiling range (300-450oC), washing oils (boiling range 230 - 29000) or also the pyrolysis residue oils from olefin plants and their

  distillation fractions (distillation domain 210-41O00).

  These oils are processed almost quantitatively.

  There is no need to flush out the oil afterwards.

  The pitches obtained according to the invention are characterized

  feels by a low content (0.2 - 3%) of constituents insoluble in quinoline, while the contents of constituents soluble in toluene with 30 - 50% are in the field of good normal and hard commercial pitches. Thus the pitches according to the invention can be used for example for insulation, covering

or sealing.

  the following examples describe the pitches according to the invention and their preparation:

EXAMPLE t -

  250 g of filtered anthracene oil, a liquid fraction from the distillation of coal tar (distillation range 300-45000) are mixed at 13000 for 15 min, respectively with 15 and 16.25% by weight of liquid sulfur , then it is heated for 1.5 h at 2800C. From 1700 onwards a strong release of hydrogen sulfide begins and these gases are separated in a sodium hydroxide solution in a manner known per se. The reaction mixtures are left for a further 1 hour at 2800C. After cooling, 2 pitches are obtained, the properties of which are shown in the following table and which are compared with a control sample, to which the filtered anthracene oil has been subjected.

  at the same heat treatment without addition of sulfur.

(Table 1 next page)

Table 1

Addition of sulfur (% by weight) 15

EP / -OC 7 (K.S.) 1 69

S content (%) 4.35

IQ (%) 2) 0.3

TI (%) 3) 32.9

  C / H ratio 1.62 Yield (%) 4) 83 16.25 Control sample

94 -

. 01 1.21

0.5 0.0

36.8 0.05

1.62 1.35

82 -

  1) Softening temperature according to Krâmer-Sarnow 2) IQ = Constituents insoluble in quinoline 3) TI - Constituents insoluble in toluene 4) Compared to the anthracene oil used

EXAMPLES. 2 - 5 -

  Different oils from coal or petroleum are mixed in a similar manner to the procedure given in Example 1 at 130-150 with different quantities of sulfur, heated 1.5 h at 260-2800C and left for 2 hours

at this temperature.

  The characteristics of the pitches obtained are given in the following table: Oil introduced

Table 2

  Oil Mixture, Mixture washing oils of tar drone tar oils tar coal hard coal

(Field of ebul-

_ __ 210-28G0 edition)

Addition of sou-

  fre (weight%) 25 w oC_7 (L.s) 82 S content (%) 5.57

IQ (%) 0.3

TI (%) 42.1

  C / H ratio 1.55 Yield (%)) 102 1) Compared to the oil, 07 1, - 41.1 1.55 used. 8.90 3.1, 7 1.62 Fraction of pyrolysis oil from the steam cracking of diesel oil into olefins 7.64 0.2 34.3 1.27

Claims (7)

  1. Products of the pitcher type, characterized in that they have a softening temperature in the range of 70-1800C, a sulfur content of 4-9%, a content of constituents insoluble in quinoline of 0.2 -3% and a content of constituents insoluble in the   toluene of 32-50% and a C / H ratio of 1.25-1.65%.   2. Process for the preparation of products of the pitcher type according to claim 1, characterized in that oils from coal or boiling tar are reacted in the range 210-45000, with -25% by weight of sulfur at temperatures of 115-160OC and then heating the oil-sulfur adducts 1-3 h to temperatures of 180-30000.   3. Method for preparing products of the pitches type according to claim 1, characterized in that   tar oils are reacted with sulfur.   4. Method for preparing products of the pitches type according to claim 2 or 3, characterized in that the tar oil used is anthracene oil filtered with a boiling range of 300-4500C.   5. Process for the preparation of products of the   pitch according to one of claims 2 to 4, characterized by   the fact that the tar oil-sulfur adduct is heated at 2800C.   6. Process for the preparation of products of the   pitch according to one of claims 2 to 5, characterized   by the fact that we leave the coal tar adduct sulfur 1 to 3 hours at 2800C.   7. A method of preparing products of the type, pitches according to claim 2, characterized in that aromatic oils are reacted from petroleum with sulfur.