DE2155530A1 - - Google Patents

Description

The invention relates to an improved method for producing a bituminous substance from coal tar, like pitch for pitch coke and the usual pitch from coal tar.

Using a conventional process to produce a bituminous substance, such as pitch from coal tar, are aromatic constituents with a low melting point due to it Distillation or steaming removed and if necessary becomes a polycondensation reaction to some desired degree caused by heat treatment or by blowing air, or it becomes distilled oil imported from creosote oil and the like to produce a bituminous substance with the desired properties (viscosity and Softening point).

The most important properties of coal tar and pitch are the softening point, the ash content and the benzene-insoluble content Components, quinoline-insoluble components and the content of bound carbon, etc. For example are the requirements that are made of pitch for electrodes with regard to the properties mentioned

500823/0874

often very severe. The difference between the benzene-insoluble component and the quinoline-insoluble component (ratio of benzene-insoluble component to quinoline-insoluble component) is considered to be very important for β-resins, and it is necessary that the quinoline-insoluble Component is present in the smallest possible amount, while the proportion of the benzene-insoluble component is as big as possible.

According to the conventional pitch generating method, various measures are taken to increase the proportion of ß-resin component applied, such as polycondensation by thermal treatment, blowing in air, adding sulfur. The most frequently performed treatment is the thermal treatment, which, however, has a long duration for the Requires polycondensation reaction. In addition, the thermal treatment not only reduces the proportion of the benzene-insoluble Components, but also the undesirable quinoline-insoluble components (j (-resin) increased and it is therefore very difficult to just increase the proportion of the desired component.

Even if the blowing in of air or the addition of sulfur promote the polycondensation and the proportion of benzene-insoluble-P can increase borrowed components, but these measures are nothing other than auxiliary means for thermal treatment, because, due to their reaction temperature, they are only effective when heated to a temperature between 300 and 400 ° C will.

Thus, in view of the softening temperature and the like, it is impossible to blow an excessively large amount of air or add a large amount of sulfur.

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2155539

- "5 -

There has therefore been a great deal of "effort" to find a method for improving it to find the properties of pitches with which the specified properties can be freely adjusted, in particular the ratio of benzene-insoluble component to quinoline-insoluble component.

The invention has now made available a method with which this object can be achieved. In this process, waste sulfuric acid (waste sulfuric acid, obtained by washing crude benzene and petroleum products with concentrated sulfuric acid, hereinafter referred to as "waste sulfuric acid ¹¹ )", which consists predominantly of sulfonic acid and organic derivatives of sulfuric acid, is used as a catalyst for the improvement of pitches carried out under polymerization. or concentrated sulfuric acid. With the help of this procedure the stated goal can be achieved at a lower heating temperature.

With this method it is possible to determine the proportion of the benzene-insoluble To increase the component at will without increasing the proportion of the quinoline-insoluble component.

The content of bound carbon is also an important factor for the quality of pitches. It could an advantageous embodiment of the method according to the invention can now be found, in which with the aid of an extraction treatment an increase in the content of bound carbon can be achieved using petroleum heavy oils can, which is otherwise quite small.

It was already known that a sludge-like product deposited when a petroleum solvent is added to pitch. However, this precipitate contains a large amount of Solvent and takes the form of a rigid, granular pulp x) called

209822/0874

at. Therefore, it cannot be continuous on an industrial scale can be removed as tar pitch. It has therefore been so far not suggested making tarpeehe using this method and to use.

However, the separation of the deposited pitch component and the extracted pitch component poses a problem with the method mentioned Petroleum solution and under certain conditions a small proportion of the petroleum sehwer oil mixes with the separating pitch component. In this pail comes a extremely large decrease in the content of bound carbon in the pitch, and it is necessary that Conditions such as temperature, hybrid and extraction ratio and the like must be carefully observed.

The invention also eliminates this difficulty overcome and it is made possible, despite the differences in the properties of coal tar »and the Properties of Heavy Oil to produce good quality pitch within a wide range of conditions.

In summary, the invention provides a method by which the extractability of low molecular weight Constituents and the separability of the pitch component The highest possible values can be kept by using petroleum hydrocarbons, which in addition to petroleum heavy oil high boiling point contain or mixed with a small amount of low boiling, saturated hydrocarbon oil are used as extraction agents to remove low-molecular, low-boiling components of coal tar be used.

Those used as solvents for the purposes of the invention Petroleum products (petroleum solvents) have the following properties

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Shafts: An aniline point of more than 20 ° O (preferably more than 40 ° C), boiling range and distillation ratio: At an initial boiling point of -200 ° C: 0 - 30 #, at 200 ° - 360 ° C: 20 - 98 $> and above 360 ° G: 0 - 80 #.

Petroleum solvents that are within the specified range include light oil, heavy oil, mixtures of light oil and heavy oil, mixtures of heavy oil with light oil, kerosene and gasoline and the like and various crude oils.

If the extraction medium contains a saturated hydrocarbon of low boiling point in addition to the high boiling point Contains heavy oil, the separability is improved due to the lowering of the viscosity during the extraction, and a Part of the paraffin or haphthenic hydrocarbon oil that dissolves in the pitch layer to a very small extent, is converted into a low-boiling hydrocarbon. In this way, the final setting of the softening point can easily be achieved by separation by distillation will.-

When liquid natural gas (petroleum gas) or a hydrocarbon oil with a low boiling point (gasoline) is used as an extraction agent is used so it is necessary to apply pressure to maintain the liquid phase because Heating is required to remove the pitch component in liquid form after the extraction, and the extraction and separation of low molecular weight aromatic components which are not required in the pitch proceeds not satisfactory.

Both disadvantages can be avoided by the invention. According to the invention, it is possible to use good quality pitches

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made from coal tar components with the help of a simplified device.

The invention is described in detail below with reference to the accompanying drawings. In these drawings mean

Pigur 1 is a graph showing the relationship shows between the temperature and the viscosity of pitch produced according to the invention in comparison with pitch, which by a conventional method was obtained;

Figure 2 is a graph showing the relationship between temperature and viscosity of road construction tar, which was produced according to the invention, in comparison with a tar obtained by a conventional method.

example 1

Grade C petroleum heavy oil was added in a ratio of 1: 1 to coal tar and the resulting mixture was added stirred at 50 ° C or 100 ° C and allowed to stand quietly at the temperatures indicated. The separated in this way

ten pitches have the following properties.

Expansion
point of interest Table 1 benzolun
soluble
component Yield,
based on
tar Treatment
lung temp. (Mercury
cathode ° C)
44
61 bound
of coals
material *
10.5
21.4 Jt
38
32 50 ⁰ C
100 ° C 39.6
49.1

215553Q

Example 2

The pitch obtained in Example 1 by treating at 50 ° C was distilled to give a pitch having the following properties.

Table 2

Distillation- Erwei- bound- beneolun-. Yield, temperature chopping point based on carbon-soluble solids

fabric component on tar

C. {Mercury
method ° C) * , 6 ί t
t 29 340 ° C. 67 50 ,8th 23, 2 25th biB
363 ° 88 57 29 3

The analytical values of the properties of the coal tar used as the starting material in this example and the after Pitch formed by a conventional method are shown in Table 3.

Tabel ? bound
of coals
material benzolun
soluble
component Yield,
based
on tar 30.4 *
4.5 * Samples exp
point of interest
(Mercury
method ° C) Starting material __
rial coal tar ~ " 46.5 12.1 58 by conv. method
received bad luck 53.4 27.2 56 blew through gn
Distillation (1) ^{b (} like (1) (2) 88

by conv. Method obtained pitch,

Treatment by 87 57.5 35.2 57 thermal polycondensation

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- 8 - Example 3

That through. Treating the pitch formed in Example 1 at 50 ° C, was subjected to a further treatment at 150 ° C with the addition of grade C heavy oil in a ratio of 1: 1. The pitch thus separated shows the following properties.

Table 4

Softening point of bound benzene-insoluble yield,

Carbon borrowed component

on tar

(Mercury method)

120 ° 0 62.2 # 36.2 % 11 %

Example 4

Grade G heavy oil was added to soft pitch and the mixture was stirred at 80 ° C and 150 ° 0, respectively ten pitches showed the following properties.

Expansion
chungs Tabel 5 benzene
unsolvable quinoline
insoluble Yield,
based Treatment
conditions Point bound
dener grain component on relationship Coals component tar Heavy oil to "
Soft pitch ^{lemp #} 34 ° C material 9.5 * 2.4 * Source material
Soft pitch 66 38.8 % 27.4 8.2 59 1/1 80 ° C 88 42.0 33.5 9.5 30th ⁿ 150 120 57.0 34.9 9.0 20th 1/2 150 54.0

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Example 5

Grade C heavy oil was added in a ratio of 1: 1 to soft pitch and the mixture was stirred at 150 ° C. The pitch thus separated was washed with gasoline (gasoline) and dried. The product shows the following
Properties.

Table 6

Softening point

bound
carbon

benzene-insoluble
component

quinoline-insoluble component

71.0 "G

59.4

20.4

0.4

Example 6

Grade G heavy oil was added at a ratio of 1: 1 to medium pitch and the mixture was stirred and thereafter left standing quietly. The pitch thus separated had the following properties.

Expansion
chungs
Point Table 7 benzene
unsolvable
liche
Compo
nent quinoline
insoluble
liche
Compo
nent density ⁰ G
66.9
88.0 ft
12.1
32.7 *
1.2 1
9.0 1 38/38 ⁰ C
, 263
, 285 rehearse bound
of coals
material Bad luck
with
Heavy fuel oil
Grade 0 be
bad luck 46.5
54.5

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- 10 -

Example 7

A grade heavy oil, B grade heavy oil, and C grade heavy oil were used in the proportions shown in Table 8 added to coal tar and the mixture was stirred and allowed to stand at 80.degree. The soft pitch thus separated was distilled up to 320 ° C to obtain pitch having the following properties.

Table 8

Ratio- extender- benzene- quinoline- bound- yield,

nis tar / ching-insoluble-insoluble ner coal-related

Heavy oil point component on carbon

Compoteer

nent

⁰ C 26.9 * % 35 Heavy fuel oil,
Grade A
1 / 0.5 91 25.2 6.8 60.6 30th Heavy fuel oil,
Grade B.
1 / 0.5 88 32.3 ",1 57.6 53 Heavy fuel oil,
Grade 0
1/1 92 7.7 58.7 Example 8

A heavy oil, grade C, was used in proportions of 1: or 1: 0.5 coal tar added. The mixtures were stirred at 70 ° C. and 50 ° C. and then left to stand. The properties the bituminous products separated in this way were made with a view to the standards set for road construction tar examined. The results obtained are shown below.

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! Table 9

Properties of road construction tar

Yer Ratio Temp, The Yield

such nis tar / heavy oil on road

Mr. heavy fuel oil

lung tar

BYT Dense acid naphthatoluene flame oil gel insoluble point hold hold borrowed

Compo-

nent

Foam test

• * «v O

1 2 3

1/1 1/1 1 / 0.5

70 ⁰ C

50

70

25/25 ⁰ O

35 96 60, 4 ⁰ C 1, 1182 ο, $ 5 ■ 1, 4 96 16 , 3 96 140 ⁰ C Well · I. 40 47, 6th 1, 165 ο, 6th 1, 6th 11 ,8th 135 Well H
H 37 42, 2 1, 162 0, 8th 2, 0 10 Ȇ 132 Well 1

Test the fractionated distillation 170 ⁰ C 27O ⁰ C 30O ⁰ C 0 #
0
0 4.7 96
6.5 ■
7.2 9.1 96
14.8
15.2

Tabel

Degree

Softening point (Hg method) benzene-insoluble quinoline-insoluble bound Liehe component Liehe component carbon

conventional
method

"C * Middle peh 67 12.1 Hard luck 88 27.2 Hard luck
(heat modifi-
icated) 87 35.2 Bad luck
(Example 2) 67 23.2 Bad luck
(Ex, 5) 71 20.4 Hard luck
(Example 2) 88 29.3 Hard luck
(Example 5) 91 26.9

1.2 46.5 ι 3.6 53.4 H 0.0 57.1 I. 3.1 50.6 0.4 59.4 7.6 57.8

method according to the invention

6.8

60.6

Table 10 shows the properties of those produced according to the invention Pitch compared to pitch made by the conventional method.

Further, in Figure 1, the curve 1, the temperature-viscosity Eurve a pitch is prepared by the conventional method (softening temperature 90 ⁰ C, thermal treatment), and curve 2 represents the temperature-viscosity curve of a pitch, the was produced by the process according to the invention (softening temperature 91.8 ° G, addition of heavy oil grade 0 in a ratio of 1: 0.5 »thermal treatment at 80 ° C).

As can be seen from FIG. 1, the pitch produced according to the invention shows reduced temperature sensitivity Comparison with the pitch formed by the conventional method. This inclination is also used in road builders observed, which was made according to the invention, thereby eliminating the disadvantage of conventional road paving will.

FIG. 2 shows measured values of the temperature-viscosity relationship. Fig. 1 shows a viscosity-temperature curve of road construction tar formed by a conventional method (RVT 62 ° C.) and FIG. 2 shows the viscosity-temperature curve of road construction tar manufactured according to the invention. From Figure 2 it can be seen that the temperature sensitivity the viscosity of road construction tar produced by the method according to the invention is significantly lower than that of the tar obtained by the conventional method.

Example 9

1 to 5 # of precipitated sulfuric acid is added to medium ^{pitch or soft pitch heated to 100 to HO 0} C and the mixture is stirred for 15 minutes. The results obtained are listed in Tables 11 and 12.

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Table 11

adding Waste sulfuric acid too Expansion
chungs
Point benzene
unsolvable
liche
Compo
nent Bad luck bound
ner
Coals
material Total-
heavy
rim-
isalt additive
from
fallschwe
ficic acid 56 density ⁰ C 56 quinoline
insoluble
liche
Compo
nent 96 96 30 / 3O ⁰ O 66.9 12.11 56 46.46 0.38 O 1.263 72.2 18.96 1.22 47.93 0.58 1 1,270 75.9 22.71 2.46 48.63 - 2 1.282 77.7 27.04 2.86 48.43 0.90 3 1.282 78.7 32.07 2.99 51.41 - VJI 1.293 ! Table 12 2.40

Adding waste sulfuric acid to soft pitch

additive
from
fallschwe
rock acid 76 density Expansion
chungs
Point benzene
unsolvable
liche com
component quinoline
insoluble
component bound
ner
Coals
material 30 / 3O ⁰ O ⁰ O 56 96 96 O 1.229 34.4 9.53 0.40 38.38 1 1.243 37.2 17.56 0.39 40.43 CVJ 1.249 40.4 21.66 2.15 42.56 3 1.278 44.1 25.13 2.40 42.60 5 1.291 45.2 34.37 2.76 42.73 example 10

In this example, leonocentrated sulfuric acid and Waste sulfuric acid added to coke oven tar and the mixtures held at 50, 80 or 120 ° 0 and stirred for 30 minutes.

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Table 13

Adding concentrated sulfuric acid to 2ieer

O * analysis Temperature 50 ⁰ G 80 ° G 120 ⁰ C added
lot benzene-insoluble
component 4.5 Jt 4.5 4.5 ■ quinolinunlö sli marriage 1.8 Jt 1.8 1.8 !Component 30.4 # 30.4 30.4 0.5 Jt bound
Sole 200 ep 200 200 Viscosity (50 ° G) 8.5 Jt 8.2 9.1 benzene-insoluble
component 1.3 Jt 1.9 1.4 quinoline-insoluble
component 31.4 mill 32.5 32.3 1.0 Jt bound
carbon 280 ep 360 580 Viscosity (50 ° G) 9.9 mill 12.2 13.6 beneolunlusliche
component 1.6 Jt 1.2 1.5 quinoline-insoluble
component 32.7 t 32.8 34.0 3.0 Jt bound
carbon 380 ep 740 1960 Viscosity (50 ° C) 18.7 mill 23.5 25.2 benaol-insoluble
component 1.5 1.5 1.2 quinoline-insoluble
component 33.4 mill 33.9 35.5 bound
carbon 720 ep 1520 - Viscosity (50 ° V)

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- 16 Table 14

Addition of waste sulfuric acid to tar

analysis Stirring emp erature 50 ⁰ C 80 ⁰ C 120 ° C added
lot benzene-insoluble
component 4.5 * 4.5 4.5 quinoline-insoluble
component $ 1.8> 1.8 1.8 a # bound
carbon 30.4 # 30.4 30.4 Viscosity (50 ⁰ C) 200 cp 200 200 benzene-insoluble
component 8.9 % 9.6 9th! quinoline-insoluble
component 1.4 # 1.8 1.8 1.0 J6 bound
carbon 32.0 i> 33.1 34.6 Viscosity (50 ⁰ C) 300 cp 420 930

The properties of waste sulfuric acid and concentrated sulfuric acid are shown in Table 15.

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- 17 Table 15

density

Organic sulfur, tar-like water-acid-con-sulphurised high-polymer content concentration compound re substance of the sulfone

acid

Waste sulfuric acid

15/4 ° C 1.48

concentrated sulfuric acid 1.84

37

31

28

The yields of pitch when adding waste sulfuric acid or concentrated sulfuric acid to! Deer are shown in the table specified,

• Table 16

Added concentrated sulfuric acid

Yield softening Addition of yield softening Waste-

point of sulfur point

Pitch acid

O * 60.4 & 85.0 ° C o i> 60.4 85.0 ⁰ C 1 66.6 86.1 1 71.0 85.4 3 82.9 85.6 3 79.0 85.1 VJt 88.7 85.9 5 88.9 85.7

Table 17
Making pitch from tar

Attempt addition Yerhalt- degree of temp, the yield properties of the pitch

No. of waste tar / heavy oil heavy oil-an pitch jBrwei-benzene-quinoline-bonded sulfur-heavy oil action chungs-unsolver- unsolver

acid point borrowed carbon

Compo- Eompo- material
nente nente

ISJ 1 96 0 1/1 σ ⁰ O 80 $ 6 ⁰ O * * sulfuric acid % I. fs) ο
to 2 1.5 1/1 0 80 25th 88 29.3 9.2 57.8 H
OD cn α »
fs * 3 1.5 1 / 0.5 σ 80 30th 95 34.5 9.5 59.9 I. cn
cn 4th 1.5 1 / 0.5 A. 80 28 88 36.5 9.6 59.6 ** v
O 5 1.5 1 / 0.5 B. 80 30th 91 36.9 9.4 62.7 0 » 6th 5.0 1/1 C. 120 28 88 35.2 8.8 58.6 46- 7th 5.0 1/1 C. 150 46 83 * 58.2 * 8.6 * 51.0 * 8th 2.0 1/1 C. 50 35 103 * 61.7 * 8.9 * 55.0 * 9 0.5 ** 1/1 C. 80 32 111 39.0 8.7 59.6 10 1.0 ** 1/1 C. 80 28 87 30.5 9.5 58.8 # Values for the 28 89 32.0 9.4 58.0 separated substances after heavy oil treatment ** without distillation to adjust the softening point concentrated

Example 11

In this example, waste sulfuric acid or concentrated sulfuric acid is added to a tar formed in the coke oven and after sufficient agitation, petroleum heavy oil is added to form pitch or a high molecular weight aromatic bituminous substance precipitate and separate. Distillation is then carried out to adjust the softening point.

The data of this example are shown in Tables 17 and 18.

Table 18 Manufacture of road construction tar from tar

Ver
search
No. additive
at departure
case-
heavy
fic acid Ver
ratio
Tar/
Heavy fuel oil Degree temp,
of the
Heavy-heavy
oil oil
handlg. ⁰ C
70
70 From _s
prey -
at -
Stras- ^h
senbau-
tar ig «
tr £ ißenbuildi ser 1
2 O
10 1/1
1/1 G
C. 35 60
38 63 VT density Acid-
Oil-
salary G
A.
, 2 25/25 ⁰ C
1.182
1.185 0.5
0.4

Properties of road construction tar

Ver- 4 -, ^^ ^ i,

~ v naphtha "Coluol- flame foam fractional book _nerds _ insoluble spot test distillation

^holding com- ¹⁷⁰ ° ^{C 270} ° ^{C 500} ° component ^G

0 4.7 9.1 0 3.5 10.0

* 16.3 ⁰ G Well 1 2.8 23.4 140 Well 2 2.7 145

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Note: The substance separated after the heavy oil treatment (Deposition,) was analyzed as a road construction tar. There was no distillation or oil addition to adjust the viscosity.

As can be seen from Tables 17 and 18, the amount of waste sulfuric acid added or concentrated is shown Sulfuric acid directly related to the increase and decrease in the amount of the benzene-insoluble component, and the proportion of heavy oil and the treatment temperature regulate the softening point and the bound carbon content and influence the separation of the heavy oil.

The addition of heavy oil is preferably $ 30 to $ 200, based on the tar, so that the separated pitch component can be separated and recovered effectively. The temperature is preferably 50 to 150 ⁰ G for tar and from 100 to 25O ⁰ C in medium pitch.

Example 12

In this example, concentrated sulfuric acid is added instead of waste sulfuric acid.

The properties of coal tar used as raw material, waste sulfuric acid and concentrated sulfuric acid, as well the properties of pitch and pavement tar obtained in this example are given in Tables 19, 20, 21 and 22 shown.

Table 19

Coal tar used as a raw material

density
15/4 ⁰ C viscosity
(5O ⁰ C) bound
carbon 9.8 benzene insoluble
liche compo
nent quinolinun
soluble
component 1.18 cp
200 >
30.4 4.5 0.4 Tar acid content Eaphthalene content fractionated
distillation 260 ⁰ C 35O ⁰ C 2.1 24 37

Table 20

Properties of waste sulfuric acid and more concentrated sulfuric acid

Dense sulfur sulphonic tar-like acidic acid, high polymer centra-organic re noun sulfonated zen substances

Water content

Waste sulfur
acid

15/4 ° C 1.48

concentrated sulfuric acid 1.84

31

28

4 5

Table 21

Properties of pitch obtained after the conventional method

Softening benzene quinoline bonded point insoluble insoluble carbon Component component

Medium pitch 66.9 12o1 1.2 46.5

Hard pitch 88.0 27.2 3.6 53 * 4

Hard pitch 87.1 36.2 10.0 57 * 1 (heat-modified)

Table 22

Properties of road construction tar, obtained after the conventional one method

HVT density Acid oil
salary ETaphthalene
salary toluolun
soluble
component Flame
Point 59.7 15/4 ⁰ C
1.23 0.2 traces 11.7 ⁰ C
174

fractional distillation the form of 27O C Test 170 ° C 300 ⁰ C.

good 0 1.4 4.2

Example 13

Extraction with the help of petroleum-light oil by itself or with mixed oil.

Light oil, heavy oil or mixed oil from petroleum was used in

- 23

2098 ?? / 0874

215553Q

given different proportions to 10 kg of coal tar. The mixtures were heated with stirring, allowed to stand and the pitch component deposited as the lower layer was analyzed.

The results obtained in this example are shown in Table 23. The data of the starting material used Coal tar and the petroleum light oil and heavy oil used as solvents are given in Table 24 »

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Table 23

attempt

No.

Extraction conditions Mixing ratio

Coal heavy light tar oil C oil (2)

Temp.

Properties of the separated pitch
Softening bound benzene quinoline density

temp. ⁰ C

ner Koh
fuel .1 unsolvable
liche
Compo
nent unsolvable
liche
Compo- ^
nente fo 30/30
⁰ C .34 .2 1 .30 63 .7 37.4 11.8 1 .28 64 35.4 11.0 1 58 32.3 7o7

2 3

0.8 1

0.2

120

95.0
93o7
91.8

The separated pitch was distilled to adjust the softening point «,

quinoline-bound insoluble carbon
component

density Table 24 200
⁰ G 230
⁰ C 15th 300
⁰ C 360
⁰ G Dry
Point aniline benzolun 15/4 ° G Fractional distillation % % 65 % Point soluble
Compo
nent Boil
beginning 21st 34 «Atf ⁰ C % 1,200 ⁰ C 12th 87 - 34.2 7.6 Coals
tar 0.811 192 - 4th 25th - 68 - Light oil 0.864 178 79 - Heavy fuel oil
C.
(2) 238

3.4

33.5

It is also clear from the results given that a pitch with a high carbon bound content can be obtained when light oil is added together with grade C heavy oil as compared with the Addition of grade C heavy oil * Further, the properties of the solvent and the extraction conditions a great influence on the separability and properties of the pitch ©

Example 14

Properties of the solvent in the solvent extraction of coal tar and separability of the pitch component

Experiments similar to those in Example 13 were carried out with various solvents. The results achieved are shown in Table 25

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density - 26 -
Table 25 Solvent 215553Q Boil
beginning 200
⁰ C 360
⁰ O Dry
Point 15/4 ° C ⁰ C % % ⁰ C 232 - 21st - Oo921 Properties of the Aniline Fractional Distillation Il Il M. Il Il Point 238 25th _ 0.864 ⁰ C It It It Il Heavy oil C
(D Il 52 180 13th 56 - t! • 0.910 It 212 12th 93 364 Heavy oil G
(2) 0.839 79 178 12th - 342 ti 0.811 ti 170 46 - 233 Heavy oil B 0.788 61 48 _- 197 Heavy oil A Oo736 72 72 20th 53 - light oil 0.853 68 60 18th 50 - Kerosene 0.826 42 64 30th 64 • mm petrol
(Gasoline) 0.866 10 crude oil 54 Mixed oil (1) 77 Mixed oil (2) 19th

20982 2/087 '.

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Table 25 (continued)

Extraction conditions 1 Temp.
⁰ C Detach salary Quantity ratio
Coal tar solution
middle 0.5 80 availability
of the ab
divorced
Bad luck to ge
bound
Coals
fabric in
from
happened
those
Bad luck, % Heavy oil 0
(D 1 1
0.5
1 80 some
bad 53.8 η 1 1 O O O
CO 00 00 bad - Heavy oil 0
(2)
Il
Heavy oil B 1
1
1 1 80 Well
some
bad
Well 58o7
52.4
56.8 Heavy oil A 1 1
1 80 Well 62.1 Light oil 1 1 100
30th Well 63.1 Kerosene
petrol
(Gasoline) 1
1 1 80 some
bad
bad 50.4 crude oil 1 1 80 Well 60.9 Mixed oil (1) 1 80 Well 62.9 Miseh Oil (2) 1 bad

Remarks:

The aniline point was measured on distilled oil up to 360 ° C.

The blended oil is a mixture of grade C oil, light oil, kerosene and gasoline.

As can be understood from the results shown above, it is a prerequisite for increasing the content of bonded carbon in the deposited pitch that the aniline point is high and that a suitable proportion of a Component with a low boiling point is added.

- 27 -

209822 / Ö874

In the solvent extraction carried out according to the invention If the bound carbon content of the pitch is increased, the content of benzene-insoluble components is increased and resin component, however, depends on the properties of the coal tar used as the raw material because there is no modifying one Process stage of polycondensation by thermal treatment, as in the conventional method, is carried out.

In order to circumvent these difficulties, according to one embodiment of the invention, a polycondensation after the addition of a small amount of waste sulfuric acid or concentrated sulfuric acid to coal tar at a low temperature in order to achieve very good quality pitch. An example of this embodiment is shown below given.

Example 15

Perform the extraction after the treatment by adding waste sulfuric acid.
10 kg of coal tar were heated to a temperature between 50 and

O 2C /

80 G were heated, 0.5 to 1 _o 06 $ and it was completely mixed. Then crude oil or mixed oil was added in a quantity ratio of 0.5 to 1.0: 1, based on tar, the mixture was kept between 80 and 120 ° 0, stirred and then allowed to stand "The properties of the pitch thus separated are shown in Table 26 (the softening point was adjusted by distillation)"

x) Waste sulfuric acid added

S. Addition of
waste f
9 T IS Crude oil or
Mixed oil Extraction
temperature [Continuation) bound
dener
Coals
material 80 % % .8th yj sulfur
acid label 26 1 Properties of bad luck % 80 11.0 22nd .3 1 Expansion
chungs
Point 61.0 120 8.5 27 .5 0.5 1" ⁰ C 59.6 80 11.5 30th .8th 0o5 0.5 90 62.3 80 11.0 25th .7 solvent 0.5 M _e ngenverhältnis
of the solvent 0.5 87 61.0 80 8.3 22nd .4 - Coals
tar 0.5 93 58.1 80 8.1 29 .5 crude oil 0.5 1 0o5 92 59.0 80 6o6 28, .9 It 1.0 1 1 89 56.5 120 8.2 27 »6 Il 0.5 1 0.5 88 59.8 10.0 29 It 0.5 1 85 62.0 Mixed oil 1 96 benzolunquinoline- ß-
soluble insoluble resin
Component borrowed com
component ti 1 93 % bad luck
the end
prey,
re.
on
tar Il 1 33.8 % It 1 35.8 34 It 1 42.0 48 abelle 26 ( 36.8 30th 31.0 36 Solution 37.5 47 middle 35.1 51 36.1 55 crude oil 39.6 49 ti 41 It Il Mixed oil M. It It It

Note: The mixed oil is a mixture of grade C heavy oil, light oil, kerosene and gasoline.

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209822/0874

As can be seen from the addition of waste sulfuric acid not only an improvement in terms of the proportion of benzene-insoluble component and ß-resin component achieved, but the pitch yield is also improved.

The same effects are obtained when using sulfuric acid is used instead of waste sulfuric acid. The table shows the analytical values of the waste sulfuric acid, which in this example is used.

Table 27 Analysis values for waste sulfuric acid

Density Sulfur content of tar water 1S / 4- ^O G acid sulfonic acid,
'organic content

sulfonated substances

1,485 52.23 # 28o07 % 14.29 % 54.1 %

It can be seen that when the polycondensation treatment is carried out with the addition of sulfuric acid and with a suitable choice of solvent in the solvent extraction is to produce a high quality electrode pitch from a coal tar as a raw material, which is a low one Contains bound carbon and solvent-insoluble components ο

The effects of the method according to the invention on the Difference in coal tar qualities are shown in the next example.

Example 16

Differences due to the qualities of the coal tar used as raw materials "

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2Ö93? 2/087 4

S4

Table 28

Properties of the coal tar feedstock

Degree of density of coal tar

^{13/4 C}

bound benzene-quinoline-carbon soluble soluble

Component component

AWAY

I0I57 1,200

25.8%
33c5

3.0%
7.6

0.5 3o4

The experimental method is the same as in Example 15. The results obtained are shown in Table 29 » These results, shown in Table 29, show that it is more difficult to obtain a good quality pitch from coal tar A than from coal tar B. By adding light oil and the like to the solvent

/it

and further, however, by adding waste sulfuric acid, it becomes possible to obtain high quality pitch.

Just as on coal tar, the method according to the invention can also be applied to soft pitch and medium pitch. This possibility is shown in the following example.

additive
v. Away- additive
Part 1 Tabel 29 properties
Bad luck of Degree
of case-
sulfur-
acid Heavy
oil C to
tar Extrak
functional Widened
chungs-dener
point Koh
len
material benzene
unsolvable
liche
Compo
nent money
tar - 1 Easy
oil temp. 92 ⁰ C 58o7% 32.3% B. - 1 - 80 ⁰ C 97 ° C 54c3% 27.3% A. - 0.5 - 80 ⁰ C 92 ⁰ C 58.5% 32.1% If 1.0 0.25 0.5 80 ⁰ C 91 ⁰ C 56.5% 34.1% Il 1.0 0.25 0.25 80 ⁰ C 97 ⁰ C 56.5% 37.1% ti 1.0 - 0.25 100 ⁰ C 9O ⁰ C 59.1% 41.1% It 0.5 80 ⁰ C

Medium pitch and soft pitch

The experiment was carried out in the same manner as in the previous example, with the exception that 10 kg of one
Medium pitch or soft pitch was used in place of the coal tar, and that grade C heavy oil was used for it or a mixed oil containing light oil as the extraction solvent. The results obtained are shown in lamella 30.

209822/0874

Bituminous Share of the solution Extrak Table 30 46o5 severed Bad luck material means on 1 part
of the material functional
temp. , 54.5 benzolun
soluble quinoline
urine soluble Heavy oil light oil
C. Properties of the 56.8
56.4 component component Starting
material
Bad luck ⁰ C Softening bound
point carbon 57.0 12.1 1.2 ro
ο Bad luck 1.0 150 32.7 9.0 00 Bad luck
Soft pitch 0.8 0.2
1.0 150
150 ⁰ C
66.9 34.1
31.5 9.5
8o9 2/087 Soft pitch 0.8 0.2 150 88.0 33.5 9.4 89.1
78.1 80.0

cn co ο

For comparison, the properties of the invention pitch produced and the properties of the pitch produced by conventional methods are shown in Table 31 O

Table 31

Manufacturing method

Properties of pitch

At-

Erwei- bound- benzolunchino- ß- merchungsner Carbon soluble linun resin kung point carbon component soluble component

nakedness

Distillation according to the conventional method

67

46.5

12.1

1.5 10.6

As above, but modified by heating

.87

57 »5

35.2

10.7

24.5

According to the invention y use of mixed oil

89

58.1

31.0

8.3

Ex. 22.7

According to the invention j addition of waste sulfuric acid (0.3 / O

88

59.0

37.5

8.1 29.4 "

From the above examples it can be seen that according to the invention it is possible to produce a high grade pitch, which has a high content of bound carbon and of benzene-insoluble components (a high content

-

209822/0874

the ß-resin component) without any high temperature treatment What is required is ο the method according to the invention can therefore be carried out with a simplified and inexpensive device and thus shows very large economic and technical advantages "

Further, by using petroleum crude oil as a solvent, it is possible to produce pitch at a very low cost. After extraction, the solvent is a mixture of crude oil and low molecular weight aromatic oil Part of the coal tar and can therefore be used in a simple manner to produce petroleum products (gasoline, light oil, Heavy oil and asphalt) can be used by distillation.

! Furthermore, the properties of these petroleum products are improved, when mixed with aromatic ingredients. For example, gasoline (gasoline) shows an increased Cetane number and asphalt shows improved miscibility with aggregates and improved permeability in the Use as a road surface.

In addition, the addition of waste sulfuric acid or is used Sulfuric acid, the color of distilled oil and the formation of resin substances during distillation purification of the separated extraction solvent and contributes to desulfurization. In this way the quality of the distilled products is improved.

It is true that the object of the invention is to provide a method for producing and improving coal tar; however, it is also possible to obtain certain improved petroleum products and low-sulfur heating oil to make when coal tar is used as fuel, or when the process of the invention is applied to refining of petroleum is applied without the conventionally performed heat decomposition and contact decomposition.

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209872/0874

Claims (1)

Claims ■ -. I.) Method of making a bituminous substance by Heating or optionally distillation, characterized in that that one by dry high-temperature distillation of coal tar produced or one from this Bituminous substance obtained from coal tar treated with sulfuric acid at a temperature between 50 and 200 ° C » 2. The method according to claim 1, characterized in that the coal tar to be treated or the bituminous substance is anhydrous. 3. The method according to claim 1 or 2, characterized in that there is concentrated sulfuric acid or sulfuric acid a waste sulfuric acid used by washing crude benzene or petroleum products with concentrated sulfuric acid was obtained. 4. Process according to Claims 1 to 3> characterized in that one follows the sulfuric acid treatment Performs distillation. 5. The method according to claims 1 to 4, characterized in that the bituminous substance is tar pitch. 6. Process for producing a bituminous substance, in particular Tar pitch, characterized in that it is produced by high-temperature distillation of hard coal Coal tar or a bituminous substance obtained from this coal tar, preferably pitch, with a petroleum solvent extracted. 7. The method according to claims 1 to 6, characterized in that one by dry high-temperature distillation of coal produced coal tar or a bituminous substance obtained from this coal tar, preferably pitch, first 209872/087 4 3? treatment with sulfuric acid and then extraction Subjected with a petroleum solvent. Process according to Claim 6 or 7, characterized in that heavy oil is used for the extraction. 9. The method according to claims 6 to 8, characterized in that for the extraction of petroleum solvent to tar or bituminous substance in a ratio of 1: Ο.3 to 2.0 is added, the mixture at a temperature between:
causes. temperature between 50 and 250 C and the phase separation 10. The method according to claims 6 to 9, characterized in that a petroleum hydrocarbon oil is used which has an aniline point of more than 20 0, a distillation rate of 0 to 30 % from the start of boiling up to 200 ° C, from 20 to 98 % a temperature between 200 and 360 ° C and from 0 to 8 % at a temperature of more than 360 ° C. 11. The method according to claims 6 to 10, characterized in that the extraction with a petroleum hydrocarbon oil that contains a small amount of low-boiling, saturated hydrocarbon oil in addition to high-boiling Contains heavy oil. 2Ö9872 / 087A