DE1645784A1 - Process for the production of bitumens with a penetration index of less than -1 - Google Patents

Description

The present invention relates to a method of manufacture of bitumina with a penetration index of less than -1

In the production of bitumina from hydrocarbon oil residues by distillation, oxidation, extraction or cleavage processes, products are obtained whose properties depend to a large extent on the starting material used and the method of production. Of these properties, temperature sensitivity is of particular importance, especially for certain applications.

001120/1721

purposes only bitumina with a high to a very high one Temperature sensitivity can be used.

It is common in the art to classify bitumens by reference to their penetration index. The penetration index and temperature sensitivity of a bitumen are in close relationship to each other ο In general it can be said that a bitumen is all the more sensitive to changes in the tea temperature, the lower its penetration index · The importance of the penetration index for the classification of the various Types of bitumen and the way in which the penetration index is determined in practice are discussed in detail in the well-known monograph by J.Ph. Pfeiffer "The Properties of Asphaltic Bitumen "(Eisvier Publishing Company, Ineo, New York 1950, see page 166).

The penetration index of a bitumen obtained by means of conventional processes is generally between -1, depending on the hydrocarbon oil residues used as the starting material and +8. You applicant has found that the production of bitumens with a penetration index below -1 by means of conventional processes using hydrocarbon oil residues as starting material presents considerable difficulties in practice. Firstly, special starting materials which are only available in limited quantities have to be used for this purpose. In addition, these starting materials only provide the desired types of bitumen with a low penetration index in a very low yield.

009820/1721

It has now been found that bitumens with a penetration index of less than -1 can be produced in a very simple manner if distillates of hydrocarbon oils are used as the source material for their production.For this purpose, a hydrocarbon oil distillate is selected whose final boiling point is below 250 ° G and this distillate is then subjected to a thermal cracking treatment above 600 ° G. Then those cracking products with an initial boiling point above the final boiling point of the starting material are ^{subjected to a heat treatment between 100 and 310 0} O, whereby volatile components are removed and the desired Bituraina with a Penetration index of less than -1 as lagging behind «

The invention accordingly relates to a process for Her "position of bitumens with a Fenetrationsindex of less than" t _r which is characterized in that a Kohlem / is asserstofföldestillat with a final boiling point below 25O ⁰ C at a temperature above 600 ° C thermally cleaved and that the decomposition products with an initial boiling point above the final boiling point of the starting material are subjected to a heat treatment between 100 and 310 ° C., the volatile components being removed and the desired bitumen remaining as a residue.

Examples of hydrocarbon oil distillates having a final boiling untorhalb 250 ⁰ C ₁ are suitable in the present invention as Ausgangematerialien for the bitumen production, Benainfraktionen can, for example ". Light petrol ^ medium and specialty petrol,

009820/1721

and KeroBinfraktionen, SB Leichtkeroein and Mittelkeroain, and finally GaeUlfraktionen as a light gas oil, ge "are Nannt" Bevoraugt be Kohlenwaseerstoffäldeetillate with a boiling range ewischen 30 and 185 ⁰ C. Special favorable results are obtained using Kohlenwasserstoffb'ldestillaten with boiling ranges between 30 and 100 ⁰ C or between 65 and 185 ⁰ G obtained as starting material.

The Kohlenwaeeerstofföldestillat is preferably thermally cracked at a temperature above 750 ⁰ O. Processes in which hydrocarbon oil distillates having final boiling points under "half 250 ⁰ C are thermally cracked at temperatures above 75O ⁰ C, come in the art frequently used, 2 · · Β in the production of ethylene. These thermal cleavage processes can be carried out in a wide variety of ways.

With regard to the bitumen production according to the invention, very favorable results are achieved if such splitting processes are used in which superheated steam (steam splitting) or a bath with a molten salt (salt bath splitting) is used. With steam splitting, the raw material to be split is! passed after mixing with überhitstem steam through a reactor in which is carried out the cleavage at a temperature of about 800 ⁰ C. In the split bath, the starting material to be split is introduced into a bath of molten saline, which is kept at the required splitting temperature of around BOO ⁰ O. In this process, the sales products leaving the reactor or saline bath are rapidly cooled in order to

Report occurrence of undesirable side reactions *

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The applicant has found "that the conditions" under which the heat treatment of the fission products is carried out, a strong influence on the bitumen yield and also on the Properties of bitumen have

If the heat treatment is carried out at an elevated temperature, not only is the yield of bitumen with a low penetration index relatively low, but products with a high percentage of insolubles in benzene are also obtained. a number of applications less suitable <> to Anmelderir has found, however, that in the case of performing the heat treatment of the cleavage products in the temperature range -from 100 to 310 ⁰ C, the desired bitumens can be obtained with a low penetration index in a high yield, as well as containing only a very low Percentage of substances contained in Ben »oT uriISelichini. Although cheap Resvuate be obtained when the heat treatment in the temperature range between 100 and 31o C ⁰ is performed j, should preferably be selected a Behändlungetemperattir between 150 and 25O ⁰ C *

This heat treatment of the fission products primarily serves to isolate the bitumen. Because during the heat treatment the volatile components are removed and the bitumen with a low penetration index remains as a residue

However, the applicant has found that the bitumen yield obtained from the cleavage products also depends on the period of time

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Vl 645784

during which the heat treatment is carried out »

-4

In general it can be said that, within certain limits, the yield of bitumen with a low penetration index is umeo is higher, the longer the duration of the heat treatment of the cleavage

products is chosen. It is believed that certain, during the heat treatment, which allows polymerization · "and occur Kondeneationsreaktionen, whereby the yield index of bitumen having a low penetration be obtained from a given amount of cleavage products ₀ · rises Moreover, it has been found that the thermal stability of the Bitumens with a low penetration index produced according to the invention also depend on the period of time during which the heat treatment is carried out. Just like the yield, the thermal stability of the bitumens with a low penetration index increases within certain limits with the duration of the heat treatment

It has been shown that very favorable results are obtained if the duration of the heat treatment 1/2 to 5 hours and especially 1 to 3 hours.

The heat treatment of the fission products can be varied Way. Depending on the specific embodiment chosen, the heat treatment serves to a greater or lesser extent threefold purpose, namely the removal of volatile constituents, the improvement of the thermal stability of the bitumen and one Increase in the yield in bitumen production

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Examples of different embodiments of the heat treatment are given below

The cleavage products can be subjected to distillation at normal or reduced pressure.Ee it is true that in such a process the bitumens with low penetration index are obtained in a very quick and simple manner as distillation residue, but they generally have a poor thermal stability . For purposes in which the thermal stability is of little importance, such distillate residues can be used without further ado. If, however, the thermal stability has to meet certain requirements, the bitumens obtained in this way are subjected to an extended heat treatment / 2 to 5 hours, under total RUokflussbedingungen at a temperature between 100 and 310 ⁰ C holds. It has been shown that the bitumens treated in this way are thermally stable up to a temperature which corresponds to the temperature used for the extended heat treatment. This thermal stability means, for example, that the softening point and the penetration of such bitumens no longer change when the Bitumina heated under total reflux below the specified temperature limit and then cooled again

The heat treatment required in the context of the bitumen production according to the invention can also be carried out in the following manner! 009820/1721

The cleavage products are kept for a certain period "which is often between 1/2 and 5 hours, at a temperature between 100 and 310 ^° C. in a pressurized closed vessel. The volatile constituents are then distilled off." The bitumens produced in this way are also up to to the tempering door used in the heat treatment, thermally stable «

Both the execution of the heat treatment in which the cleavage products are distilled under normal or reduced pressure and the distillation residue is further heated under total reflux, as well as the execution form in which the cleavage products are first heated in a closed pressure vessel and then the volatile constituents are distilled off, provides in high yield a thermally stable bitumen with a low penetration index of ₀

The invention is illustrated in more detail by the following examples: example 1

A Kohlenwaeserstofföldestillat with a Anfangesiedepunkt 65 ⁰ O and an end boiling point of 185 ° C is thermally cracked using superheated Dampftei a temperature of about 800 ° 0 on an industrial scale. The cleavage products with an initial boiling point of 220 ⁰ C and higher are distilled under reduced pressure, and the maximum bottoms temperature is maintained at below 220 ⁰ C. The distillation is carried out in two ways, namely once in üaboratqriimanmB

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stab (chamfering capacity of the distillation gases; 2 liters) and once on a semi-industrial scale (capacity of the distillation vessel: 20 liters), the results obtained are summarized in Table X, test UrA.If the test is repeated, the distillation is only carried out in the laboratory carried out. The results obtained have also been included in Table II (Experiment Mir »2).

example 2

A iiohlenwasserstofföldestillat having an initial boiling point of 50 ⁰ C and a final boiling point of 10O ⁰ C a bath of molten salt is thermally cleaved in the semi-industrial scale at a temperature of about 800 ⁰ C using. The cleavage products having an initial boiling point of 150 ⁰ O and higher are under reduced pressure at maximum bottom temperature of 152 ⁰ C or "197 ⁰ C distilled. The results are summarized in Table II.

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- to -

TABEL

Type of distillation Experiment No. 1 60.7
1.5 53.0 semi-technical
scale attempt Mr • 2 70.5
60 67,
3 5 63.5
1.5 C.
C. Bitumen yield, wt. ^
Penetration at 25 ⁰ C ₉ 0.1 mm Laboratory
scales 68.2 63.0 42.0
8th Laboratory
scale 8.5 IC
α Penetration at 40 ^° C., 0.1 mm 69.5
44.5 74.5
66 23.5 C. Penetration at 5O ⁰ C ₉ 0.1 mm 116.5 mmt Penetration at 60 ^° C., 0.1 mm 76 105 44 64, 5 70.5 md : Softening point, ring and ball, ⁰ C -1.8 -1.9 62 72 141 -2.4 -2, 6th -2.5 Penetration areaχ 47 26.7 32.0 -1.9 43.5 23.0 Conradson test, coking rebate, wt. ^ -2.2 24.6 -2.3 18.4 Content of n-heptane asphaltenes, wt. ^ 23.0 30.5 20.0 99 Temperature at which the viscosity
20,000 cS, at ⁰ C. 88 ' CO
cn Temperature at which the viscosity
Is 2,000 cS, in ° C 109 15Cg Temperature at which the viscosity
200 cS, in ⁰ C 139

TABEL

II

Maximum floor temperature
during the distillation, 0 152 197 Bitumen yield, weight, * 25.4 19.7 Softening point, ring and ball, ⁰ O 37.5 94 Penetration at 25 ° C, 0.1 mm 140 - · Penetration at 60 ° C, 0.1 mm 15th Penstration Index -2.5 -1.5

Example 3

A hydrocarbon oil distillate with an initial boiling point of 65 ° G and an end boiling point of 185 ° C is thermally cracked using superheated steam on an industrial scale at a temperature of about 80O ⁰ C. The cleavage products Rait a Anfangosiedepunkt ⁰ 200 G and higher for some time be kept at an elevated temperature in a pressure vessel. The duration of the heat treatment and the temperature used are varied in a number of trials. The heat treatment is followed by a dilution to remove the volatile constituents. The results obtained are summarized in Table III. in this test, v / ground the bitumens ^l j hours under total reflux at 200 ⁰ G heated. the bitumen is as thermally considered stable, wen is the difference in softening point before and after the test is less than 3 ⁰ C. the results of the stability tests have also been included in Table JII.

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BABKLlE

III

! Temperature at which the heat
action is carried out, C 120 160 , 5 9 250 ⁰ C , 5 201 5 C. 1 203 2 3OQ ⁰ C 2 3 200 , 5 5 156 7th 195 I.
I. Duration of the heat treatment in hours 68 , 3 62 , 0 -1 5 30th
, 7 -1.1 56, C.
Φ 196 1 51.8 140 143 3 51 60, 5 53.1 19 I.
-1.3
35 r 2 axial soil temperature during
external distillation, ⁰ C ⁰ C 56 77 178 104, 107 56, 5 101.5 63 200 65, 5 99 55, 93 34o2 Bitumen harvest, wt. $ 15th , 9 60.4 92 . 80, 51 , 1 51, 43, 15th 95 Softening point, ring and ball, 90 t 22nd , 5 98 4th
4th 68 , 3
, 0 2 Penetration at 25 ° C, 0.1 min -2 7th
0 -1.4
31.8 9 10
3 -1 , 2 _- g Penetration at 40 ^° C., 0.1 mm t
* -2, 38.6 -2 34 , 5 Penetration at 6O ⁰ C, 0.1 mm
Penetration index
Sonradson test, coking
Rücketand, weight ^ i 100 10
, 4 -1,
33 » 100 Content of n-heptane compounds _f 30, Softening point, collar ball
after stability test, ⁰ C 100

Example 4

The cleavage products obtained in the cleavage process according to Example 3 have an initial boiling point of 200 ° 0 and higher distilled under reduced pressure at the lowest possible soil temperature until a bitumen with a softening point of 90 ° ö remains as a residue, with the resultant Bitumen is the stability test described in Example 3 carried out. The result is shown in the following Table IV (Experiment A),

TABELIE

IV

attempt A. B. C. Bitumen yield ρ weight fi 55.5 60.4 69.0 Maximum floor temperature
during distillation, C 180 142 Softening point, ring and
Sphere, ⁰ C 90 90 90.5 Penetration at 60 ⁰ G, 0.1 mm 28 30th 28 Penetration index -1.2 -1.1 .1.1 Softening point, ring and Ku
gel after stability test, C 104 92 93

example 5

The cleavage products obtained in the cracking process according to Example 3 with a Anfangesledepunkt of 200 ° to 0 or higher are distilled at reduced pressure and the geringstmögliohen bottom temperature until a bitumen having a softening point of 54 ⁰ G remains as a residue. This bitumen is heated for 5 hours under total reflux to 240 ⁰ G and in certain tent abatement

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the softening point is measured. At the end of the 5 hours Treatment is the softening point 90.5 ° C »you further Measurement results are compiled in Table V.

The so obtained gymnastic with a softening point of 90.5 ⁰ O is then subjected to the stability test described in Example 3 "The result obtained has been recorded in Table IV (Test 0)"

For comparison purposes, Table IV also contains the result for the bitumen with a softening point of 90 ° 0 from Table III (see Table IV, Experiment B) ₀

T Λ B E I · L E V

Duration of the heat treatment in
hours Softening point, ring
and sphere, c O
0.5
1
3
4th
5 54
73
83
87.5
89
90.5

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Claims (2)

A process for the preparation of bitumens having a penetration index of less ale -1, characterized in that a hydrocarbon oil distillate having a! Bnd boiling point below 250 ⁰ C at a temperature above 600 ° 0 is thermally cracked and that the cleavage products with a Anfangssie "depunkt above the Endsiedepunktee Auögangemateriale of a heat treatment between 100 and 31o C ⁰ are subjected to, the volatiles are removed and the remaining ge "wish bitumen as a residue. 2. The method according to claim 1, characterized in that the Farmer's heat treatment is 1/2 to 5 hours ο 009120/1771