DE2062268A1 - Process for the production of carbon hydrogen-containing masses - Google Patents

Description

COMPAGNIE MAlTCAISE DE RAJ ¹ FIMGE SA, Paris »France

Process for the production of masses containing hydrocarbons

The invention relates to a method of manufacture compounds containing hydrocarbons, in particular for road or railway pavements or for use in building houses, whereby an aggregate, a filler and a hydrocarbonaceous one Binders are mixed together *

Such masses are known · The aggregate consists of a granulate, the grains of which are from a sieve with square or round openings of 80 p. Side length or 100 yes diameter are retained, but not by a sieve with square openings of 100 / u side length or round openings of 125 / u diameter. The filler consists of grains, the diameter of which is <80 / U and which are therefore not retained by a sieve with square holes with a side length of 80 / U or »round IjÖ-chem with a diameter of 100 yu Crude oil. Bs consists of asphaltenes and maltenes »

109026 / 1S01

The mentioned hydrocarbon-containing masses, which are composed of the above-mentioned constituents, have certain material constants, such as fatigue resistance, compression fracture load, tensile strength and flow behavior, which can be measured in suitable test arrangements described later, and which are established represent a good statement regarding the behavior of the masses under conditions of use.

Certain improvements of these material constants are relative to compositions which is above ⁰ ° C are to be used, is well known by using a hard binder reachable · The preparation of the mass but then requires an even greater heating of the binder, $ e harder it is.

The object of the invention is to create a manufacturing process which results in masses at which the above-mentioned material constants are improved.

The method according to the invention is characterized in that the mixing of aggregate, filler u & d binders are made with the addition of hard asphalt.

The hard asphalt is advantageously added to the mixture of aggregate and binder as a non-preheated powder and filler introduced or prior to mixing Filler precipitated with the aggregate and the preheated around the filler.

Preferably, the precipitation of the hard asphalt path by adding normal hexane to a suspension of the filler achieved in a solution of asphalt in benzene,

109826/1601

In a further improvement of the invention, so much hard asphalt is used that the hard asphalt / hard asphalt + Filler volume ratio is approximately equal to or preferably greater than the value at which a test specimen in the predetermined temperature range for a given binder and aggregate, the longest service life in a twisting test achieved with constant load and frequency.

In this context, hard asphalt is a substance to be understood, which is rich in asphaltenes (at least 50 wt. ° / o) and has a fraction insoluble in carbon disulphide or cyclohexane substances less than 30 wt.%. The hard asphalts used according to the invention must be sufficiently distributed so that there are no irregularities in the composition of the binder. A grain size corresponding to that of the filler is advantageous, but the grain size is not critical. The maximum grain size of the hard asphalt should not exceed the smallest grain size of the aggregate.

When the hard asphalt is added to the mix of filler, binder and aggregate, it should not be heated prior to admixture so that no agglomeration occurs arises.

As mentioned, another type of admixture is to precipitate the hard asphalt around the filler, preferably by adding normal hexane to a suspension of the filler in a solution of Asphalt in benzene, and then filler and hard asphalt to be added to the mixture of aggregate and binder. Natural asphalt can be used as hard asphalt.

109826/1601

zen after being powdered. Likewise, the portion of a desasphalting pitch which is insoluble in normal heptane or normal hexane or in light gasoline, originating from the desasphalting with propane, or a vacuum distillation residue or the residue of a distillation under atmospheric pressure, if the petroleum is very rich in asphalt, or an oxidized bitumen, originating from a bubbles (soufflage) in a temperature range of I50 to 3OO ⁰ C, one of said substances or a mixture thereof. The hard asphalt used in the invention may contain up to 30 wt.% Of play which are insoluble in carbon disulphide or cyclohexane. Such substances are produced, for example, by crushing the extract from residues from cracking processes or "visbreaking" processes or "hydrovisbreaking" processes, or from pyrolysis of blown, or in the presence of catalysts (such as Po ° 5 U * ¹ * ³ - ZnClp ) polymerize residues, the extraction with normal heptane or normal hexane or light gasoline being carried out.

The hydrocarbon-containing binder is obtained in a known manner. There is no difference in the mechanical properties of those produced according to the invention Determine masses if binders of the same hardness but different origins are used, z. B. natural bitumen, reassembled bitumen or reassembled blown bitumen.

Any material can be used as the filler, e.g. B. sand, limestone, slag, lime or vulcanized Rubber. Crushed and sieved coke, derived from coal or petroleum, can also be used in a known manner

109826/1601

can be used, or mixtures of fillers.

An unexpected effect of paving hard asphalt In masses containing hydrocarbons, it is possible to reduce the filler content has that the behavior of the masses is improved in an unusual way, especially the temperature insensitivity and thus the flow behavior.

The optimum of the mechanical properties at a certain temperature depends on the ratio of filler and hard asphalt. For example, considering two masses that are to be used at a temperature of about 20 C and 5 ⁰ C, the hard asphalt / hard asphalt + filler volume ratio must be approximately equal to 0.5 and 0.25 to the respective optimum to maintain mechanical properties. According to the invention, the optimal composition is determined with the aid of a rotary bending test at constant load and frequency with test specimens made of hydrocarbon-containing masses of different composition.

109826/160

The invention is explained below with the aid of examples and the attached FIGS. 1 to 4, which properties of the Hassen described in the examples.

Example I.

The binder used in all of the experiments described below has a penetration of 80/100 on (expressed in 1/10 mm at 25 ° C, 100 g load, 5 see. Load duration, needle according to the HFJD 6004 standard). The binder is made by direct distillation of a petroleum Venezuela of the "Boskan" type was preserved.

The hard asphalts come from a precipitation of n-heptane from fine deasphalting pitch. You're in the benzene and carbon disulfide completely soluble. They come as a powder with grains smaller than about 80 microns.

The filler is sieved sand, limestone or a filler made of coke, which through "fluid coking" produced, not fusible, in carbon disulfide is completely insoluble and has the following composition:

Carbon 87.25 wt.%

Hydrogen 2.30 wt.%

Oxygen 4,4% by weight

Ash 0.14 wt.%

Sulfur 5.91 wt. $

The carbon / hydrogen weight ratio is 38 and then the chemical / carbon grami atom ratio

109826/1601

ratio equal to 0.31.

Sand 0/3, which has been sieved beforehand if no sand filler is to be introduced or if it is in Other than the natural proportions are to be introduced, is dried in the oven at 150 G. The aforementioned binder is kept at the same temperature for two hours. Of the Sand is poured into a thermostatic mixer given. Thereafter, the cold filler is dispersed in the sand for five minutes, if necessary. After that, if necessary the cold, hard asphalt added. Then the binder is introduced. Mixing continues in the presence of the Binder five minutes after which samples are made.

Toric Samples prepared whose mean diameter is 30 and whose diameter at the ends is 4-5 mm. In the preparation of These samples are put 200 cnr into a cold mold and immediately with 15 tons by means of two Eolben 30 seconds long compressed. After cooling, the samples are removed from the mold and left in place for a sufficient time to allow a assume thermal equilibrium at the temperature at which the fatigue resistance tests are carried out.

For the compression resistance tests, cylindrical Samples are made which have a diameter of 4-5 mm and have a weight of 300 g. They are pressed under 6 tons for one minute. Regarding the removal from the Form and storage, the precautionary measures outlined above are taken.

The fatigue resistance tests consist of the toric sample at constant load and constant

10 9 8 2 6/1601

Temperature of a turning bend with a frequency of 25 Hertz to subjugate. The toric sample is placed so that its axis is perpendicular without the said load. The lower part of the sample is arranged in the chuck of a spindle with a vertical axis of rotation. The speed is adjustable. A metal ring is placed around the upper part of the sample, around which a ball bearing is arranged. These Device enables a constant transverse tensile load to be applied to the sample. The number of revolutions is determined at which the sample breaks.

The tests to determine the compression resistance consist in compressing the cylindrical sample at a constant speed of > 0 mm / min. That force is determined which is exerted when the sample is broken.

The composition of various samples is given in Table I below. Furthermore, the fatigue resistance and the compression rupture loads are given for each composition. These properties have been determined at 2O ⁰ C. The proportions of additive, filler and hard asphalt are given in percent by volume of aggregate, filler and hard asphalt. The proportion of binder is based on 100 parts by weight of aggregate, filler and hard asphalt.

109826/1601

Table I.

attempt 1 2 3 4th 5 6 · composition Sand 0/3 without
filler
(Vol.%) 84 84 84 84 84 84 Sand filler
(Vol.%) 16 _ _ Μ · mm Limestone-
filler
(Vol.%) 16 Coke filler
(Vol. %) - 16 8th 1 14th Hard asphalt
(Vol.%) - _ 8th 15th 2 binder
(Parts by weight) 8th 8th 8th 8th 8th 8th «=« == »=« == »= = = =» * ======== ======== IS = SS = SS = Sa ======== I.
Mechanical
properties
at 20 ⁰ C ^: Fatigue Resistance:
digkeiti 1,2.1O ⁵ At 7.7 bar
(Number of
Rounds); 5.5--1O ⁵ : 2.5 · 1Ο ⁵ , 5.1O ⁵ > Ί0 ⁷ > 10 ⁷ 3.1O ⁶ At 17 bar i
(Number of s
Rounds); 6.0.1O ⁵ 100 j 7.5.10 ⁴ I. pp.10 ^5; ! Compression \
breaking load I
(bar) \ 110: 100 i 240 j 270 160;

109Ö26 / 1601

From Table I it can be seen that the mechanical. properties of hates 1, 2 and 3 are essentially the same. Different fillers convey when they are present in the respective mass with the same volume fraction, similar mechanical properties.

Experiments 4, 5 and 6 illustrate the properties of masses produced according to the invention. A comparison of the various mechanical properties of these masses and the mass examined in Experiment 3 shows what considerable Increase in the fatigue resistance and the compression rupture load with the method according to the invention is achievable. In addition, it has been shown that these more favorable results are achieved with a reduction in the filler content are achieved.

Example II

This example deals with the case that the hard asphalts embedded in the mass are not completely soluble in carbon disulfide or in cyclohexane. The masses containing hydrocarbons are produced as in Example I, with the difference that instead of the hard asphalt, a substance is used that is produced by precipitating the hard asphalt contained in a "toughened" heating oil with a gasoline that goes over between 60 ° and 100 °, is won. The breaking of the toughness (visbreaking) is carried out at the chopping stand of the vacuum distillation of a petroleum from Iraq. A heating oil with a viscosity of cst is obtained. at 50 ⁰ G and a zylene equivalents of ^ ¹ J. The precipitated hard asphalt has the following properties:

109826/1601

Schiael zpunkt

Insoluble parts in carbon disulfide

Composition: carbon ■ hydrogen oxygen ash
sulfur

280 ° 0
25 wt.%

82.89 wt% 6.5

1 3 "

• 0.88 "

8.43 "

Here is the carbon / hydrogen weight ratio is 12.7 and the hydrogen / carbon gram atomic ratio is 0.94.

The hard asphalt is obtained directly in a form that it can be introduced into the mass without prior grinding or seven.

The composition and the mechanical properties of the mass produced in this way at 20 ^° C. are listed in Table II.

Table II

attempt 1 7th composition Sand 0/3 without I filler (vol%) 84 84 Sand filler (vol%) 16 8th Hard asphalt (Vol%) - 8th Binder (parts by weight) 8th 8th

109826/1601

attempt

Meeh. properties
at 20 ° C

Resistance to retirement

at 7.7 bar (number of revolutions) at 17 bar (number of revolutions)

Compression breaking load (bar)

5.5 '
6.0. 10

110

1 x 10 1.5-10

275

It can be seen that the introduction of hard asphalt with a simultaneous reduction in the amount of manure in the hydrocarbon-containing mass, the mechanical properties of the same are considerably improved.

Example III

This example concerns the influence of temperature on the mechanical properties of the masses and the determination the optimal fill content of hard asphalt and filler, which are embedded in the mass.

The compositions used contain a coke filler identical to that described in Example I.

The hard asphalts, completely soluble in carbon disulfide, are identical to those used in Example I.

The manufacturing process of the samples for determining the mechanical properties corresponds to that in Example I. described.

109826/1601

In Table III the compositions are those tested Masses and the corresponding mechanical properties listed at different temperatures. In the tests to determine the fatigue resistance are the samples at any temperature (35 ° G, 20 ° C and 5 ° C) subjected to the same load (7.7 $ 17 »u ^ -cl 4-2 bar). For comparison, the same temperature is used at the respective temperature Investigating a mass that is not hard asphalt contains and breaks at 35GO cycles.

Table III

attempt 8th 9 10 11 12th 13th composition Sand 0/3 without
filler
(Vol.%) 84 84 84 84 84 84 Coke filler
(Vol.%) 16 12th 8th 4th 2 16 Hard asphalt
(Vol. %) ■ Mt 4th 8th 12th 14th . binder
(Parts by weight) 8th 8th 8th 8th 8th 8th Volume of the
Hard asphalt
It i_ ^tes 0 0.25 0.50 0.75 0.87 0 Vol. Hart
asphalt +
Vol
material sssatscs = = BS = S = S = S CSSsSSr = S = ssssssssssssssss = :: 35 ⁰ O 35 ⁰ C 35 ⁰ C 35 ° 0 35 ⁰ O 20 ⁰ C Mechanical
ligenechaf t s
at a tem
temperature from 45 105 150 165 180 100 Compression
breaking load
(bar) 3,5-1O- ³ 1.6.10 ⁵ 8.10 ⁵ 1.1. 10 ⁶ 7.1O ⁵ 3,5.10 ³ Anti-fatigue
stood (number
of the circulations) 7.7 7.7 7.7 7.7 7.7 17th load
(bar)

109826/1601

Continuation ...

fS

Table- III

attempt 14th 15th 16 17th 17th 18th 19th composition Sand 0/3 without
filler
(Vol.%) 84 84 84 84 84- 84 Coke filler
(Vol.%) 12th 8th 4th 16 12th 8th Hard asphalt
(Vol.%) 4th 8th 12th 4th 8th binder
(Parts by weight) 8th 8th 8th 8th 8th 8th Volume of the
Hard asphalt
• p tes Vol. Hart
asphalt +
Vol
material 0.25 0.50 0.75 0 0.25 0.50 Mechanical
properties
at a tem
temperature from 20 ⁰ G 20 ⁰ C 20 ⁰ G 5 ⁰ G 5 ⁰ G 5 ⁰ G Compression
breaking load
(bar) 190 240 260 240 350 400 Anti-fatigue
stood (number
of the circulations) 3.10 ⁴ 7 5.10 ⁴ 4th 3.5.10 ³ 9.1O ⁵ 3.5.10 ³ load
(bar) 17th 17th 42 42 42

10 9 8 2 6 / 160t

1, 2 and 3 show in graphical representation the results of the experiments. In Pig. 1 is the breaking load (expressed in bar) as a puncture of the value R, which represents the volume ratio of hard asphalt to the sum of hard asphalt and filler. Be it notes that this sum is constant, since the addition of hard asphalt takes place at the expense of the amount of filler. the Pig. 2 shows the fatigue resistance, measured in terms of the life of the test specimens, and expressed in the number of with constant load and frequency, load changes occurred as a function of that defined in accordance with FIG. 1 before the breakage Value E. FIG. 3 shows various breaking loads (expressed in bar) as a function of the sample temperature. Man can observe that the permissible breaking load is an increasing puncture of the hard asphalt portion, which is at the expense of the filler is introduced into the mass, except at a temperature of 5 ° G, at which a maximum Breaking load exists. In contrast, the fatigue resistance always shows a maximum, which with increasing The proportion of hard asphalt in the mass is growing. The position of this maximum changes with temperature. At the middle temperatures of 5 ° Ο, 20 C and 35 C have the relevant Mass a maximum of the fatigue resistance at R «0.25 and 0.5 and 0.75, respectively.

It is therefore possible, if one knows the temperature range in which the mass is to be used, the value of R, which influences the most interesting mechanical properties, and thus the ratio of hard asphalt and filler. For this purpose, the curves that show the fatigue resistance as a function of R are used as well like the curves that show the breaking load as a puncture of R.

109826/1601

It is preferable to choose the value of R corresponding to the maximum fatigue resistance when the mass is used Production of road surfaces is intended. In contrast, the one associated with an increased compression rupture load is selected Value E if the material is used in the manufacture of molding compounds, for example for use in house construction, is used. Values of the ratio E which are somewhat larger than the maxima at a given temperature values assigned to the service life represent a good compromise between fatigue resistance and breaking load resistance as well as creeping.

Example IV

This example relates to hydrocarbonaceous compositions for use as road paving. These crowds were subjected to a wear test (experimental method of the LABOEAiDOISE- GENTEAL DES POHTS ET OHAUSSEES-Eesistance LCPO). The tests were carried out for two different binders. The first binder has a penetration from 80/100 and comes from a softening (fluxage) of a deasphalting pitch with an aromatic oil extract, obtained using furfural. The bad luck stems from the desasphalting of a vacuum distillation residue with propane. The second, significantly more fluid, binding agent is a vacuum distillation residue from a petroleum from Iraq, with a viscosity of 900 cst. at 99 O.

During the production of the samples, the binder at a temperature of 150 ^{° C. is added to the aggregate previously dried at a temperature of 140 °} C. if it is a penetration binder

109826/1601

80/100 acts, or with a (temperature of 120 ⁰ G, if it is the vacuum distillation residue. Hach approx. 15 seconds. Kneading is added to the coke filler preheated ^{to 140 0 G} the non-preheated hard asphalt, the composition of which was "already described in Example 1", is added 18 ⁰ C (Resistance LCPC) is subjected.

Table IV shows the composition of the hydrocarbon-containing compositions and the wear resistance at 18 ^° C. The composition of the aggregate, the filler and the hard asphalt are given in percentages by volume of the three components. The proportion of the binder is given in percent by weight of the three components. The grain size of the aggregate is given in millimeters.

109826/1601

WSPECTCO

Table IV

composition 1 2 3 4th 5 6th 7th 8th 9 10 Sand 0/3 without POIlstoff (Vol%) 37.1 37.1 37.1 37.1 37.1 37.1 37.1 37.1 37.1 37.1 Split 3/5 (Vol #) 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 ■ 18.5 18.5 Split 5/8 (Vol%) 18.5 ■ 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 ο
co Split 8/12 (Vol%) 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 18.5 co
IO Oil filler CD (Vol%) 7.4 5.6 3.7 1.8 - 7.4 5.6 3.7 1.8 - ar) Hard asphalt O (Vol%) - 1.8 3.7 5.6 7.4 - 1.8 3.7 5.6 7.4 Bitumen 80/100
(Parts by weight) 6.2 6.2 6.2 6.2 6.2 Vacuum de silent
backlog
(Parts by weight) 6.2 6.2 6.2 6.2 6.2 Resistance LCPC
at 18 ^oC Kg / cm 41 58. 75 95 95 22nd 27 35 47 58

O CD NJ K)

Fig. 4- shows a compilation of the curves
the dependence of the wear resistance on the ratio R, as it has been defined in connection with! ig · 1.
The conclusions that can be drawn from this are the same as those already shown in Example III. The curve, based on the 80/100 binder, must be compared with the curve for 20 ^° C. 1, although this does not show a maximum. It turns out that among the above
a mass with R ■ about 0.75 or higher represents an excellent road surface. The curve based on the mass with a vacuum distillation residue as a binder is to be compared with the curve for the temperature 35 ^° C. in FIG. 1, in this case the
Binder is harder: the highest values of R are the
most advantageous.

109826/1601

Claims (5)

Expectations 1. Process for the preparation of hydrocarbon-containing Masses, in particular for road or runway coverings or for use in house building, with an aggregate ! Filler and a hydrocarbon-based binder with, are mixed with one another, characterized in that the mixing takes place with the addition of hard asphalt. 2. The method according to claim 1, characterized in that the hard asphalt as a non-preheated powder into the mixture is introduced from aggregate, binder and! filler. J. The method according to claim 1, characterized in that the Hard asphalt before the filler is mixed with the aggregate and the preheated binder around the filler is precipitated around. 4. The method according to claim 3, characterized in that to precipitate the hard asphalt, normal hexane to form a suspension of the filler in a solution of asphalt in benzene is added. 5. The method according to any one of claims 1 to 4-, wherein the masses to be produced are intended for use in a certain temperature range, characterized in that so much hard asphalt is used that the hard asphalt / hard asphalt + U ¹ UIl st off volume ratio is approximately the same or is preferably greater than the value at which a test specimen ■ in the predetermined temperature range for a given binding 10 0 8 2 6/1601 dematerial and aggregate the longest service life in one Rotary bending test with constant load and frequency achieved. 10 9 8 2 6/1601 Blank page *