FR2473536A1 - PROCESS FOR THE MANUFACTURE OF HIGH QUALITY RAW MATERIALS FOR THE PREPARATION OF BLACKS - Google Patents

Abstract

According to the invention, the raw materials for black are obtained from a carbonaceous intermediate product, obtained by the disintegration of crushed coal, or similar carbon-containing materials, by a mixture of solvents obtained from petroleum and coal products, to Up to 5% volatile constituents are quenched at high temperature and pressure, where appropriate, and a fraction with a boiling point of 220-480 degrees C which can be used as raw material for black is distilled off.

Description

FRENCH REPUBLIC

NATIONAL INSTITUTE

INDUSTRIAL PROPERTY

  PARIS Y N of publication: (Use only for

reproduction orders).

2,473,536

A1

REQUEST

OF PATENT INVENTION

No 81 00228

  (R) Process for manufacturing high quality raw materials for the preparation of blacks.

(51) International classification (Int CI. 3). C 09 C 1/48.

  Filing date ........................ January 8, 1981.

  Priority claimed: RFA, 10 January 1980, no P 30 00 658.7.

Date of provision of

request public ............ B.O.P.I. - "Lists" n 29 from 17-7-1981.

Applicant: Company known as: RUTGERSWERKE AG, residing in Germany.

  @ Invention by: Helmut Kôhler, Heinz-Gerhard Franck and Jûrgen Stadelhofer.

Holder: Idem Mandatory: Cabinet Plasseraud,

84. rue d'Amsterdam, 75009 Paris.

  D Sale of booklets at IMPRIMERIE NATIONALE, 27. rue de la Convention - 75732 PARIS CEDEX 15 Process for manufacturing high quality raw materials for

preparation of blacks.

The subject of the present invention is the manufacture of

tion of a high quality raw material for the production of blacks, in particular according to the

oven from oil. Black is an important material

  aunt for the rubber and dye industry. By far the most important process for making black is the oil oven process. In this process, an appropriate mixture of black hydrocarbons is decomposed in an oven and

in hydroqene.

  It turned out that all of the hydrocarbon mixtures

bures are also not suitable for manufacturing

  black; however, it has been found that pre-

Especially advantageous materials were mixtures of liquid hydrocarbons having a high degree of aromaticity. Today, such blends based on products from coal and petroleum are used for the

  manufacture of blacks. As raw materials

  oil, we use in particular the residues of

  catalytic cracking (aromatic concentrates) and oil

those from the steam cracking of petrol; as pro-

  of coal, suitable fractions obtained in the treatment of coal tar are used. Important conditions for the suitability of a mixture of aromatic hydrocarbons to serve as

nour raw material for blacks is the domain of

  lition, density (or Correlations-Index des Bu-

reaux of Mines, based on these two quantities), the report

atomic port C / H as a measure of aromaticity as well as a maximum sulfur content of 2% (see K. Zim.mer, Erdôl und Kohle, Erdgas, Petrochem. 22, 1969, 742). According to this memo, a raw material for black having a correlation index> 120 is a

  good starting material for making black.

  A corresponding classification of the quality of raw materials for blacks is given in the published German application DE-OS 25 47 697 and can be

  taken from Table I of this request.

  Unfortunately, large raw materials

  of the quality indicated above are only available in limited quantities. This is true for both

raw materials based on coal tar used

  so far that should be considered the best

their raw materials for black due to their higher aromaticity than for the raw materials from petroleum which are formed in the form of a product, in the manufacture of olefins

or in the catalytic cracking process.

Because of this insufficiency, one often tried to widen the base in raw material for starting products for the blacks. For example, the published German application DE-OS 25 47 679 describes a process in which coal tar pitch is mixed with pyrolysis oil from the decomposition of benzene in suitable ratios

  court adjust the viscosity required.

  The drawback of this process, however, is that coal tar pitch is only available for this purpose to a limited extent, since it is used as a high-quality raw material.

  quality for the manufacture of other hydro-

  carbonaceous in particular as a binder. In addition, separate

remove harmful pitch suspension oil and pyrolysis oil (ash, etc.) by processes

requiring mechanical expenses.

  This situation causes an urgent need for processes for manufacturing raw materials

  for black on an assured raw material basis.

  The present invention therefore aims to develop

  per a raw material for black which rests as regards the base of raw material especially on the coal resources assured for a long time. According to the invention, this problem is solved by the fact that from a carbonaceous intermediate product of the pitch tar which can be obtained by disintegration of

  ground coal, and / or other semi-raw materials

  carbon containing, with a material content of

  higher or lower volatile res, by a combination

flavored solvents from petroleum and petroleum

  good with an average boiling temperature> 3500C,

using temperature and pressure conditions

  high ion, if necessary up to 5 X of volatile constituents until a distillation end of 2600C and which is obtained from the residue, by

  distillation, 10 to 40% of a fraction of the boiling point

  lition from 220 to 4800C, as a raw material

for black.

Examples 1 and 2 describe the preparation

  tion of the intermediate carbon product by disintegration

tion using a combination of petroleum and coal solvents and black oils which can be obtained from this intermediate product

  by distillation. Intermediate product manufacturing

  highly aromatic carbonaceous diaries as pitch pitch is the subject of the applicant's earlier patent application P 29 35 039.8. This preparation is carried out by disintegrating coals with a high or low volatile matter content by aromatic residues from the steam pyrolysis of petroleum fractions in combination with aromatic mixtures originating from coal having an average boiling temperature above 3500C as additional solvent, if necessary with the addition of other solvents. To obtain the raw materials for black according to the invention, a percentage of 10 - 40%, preferably 15 - 35%, of a fraction of distillation level 220 - 480C is distilled from the topping residue, preferably 250 - 4500C and we use

  this fraction as raw material for black.

  As the main component for the production of the raw material for black according to the invention, coal is used. Until recently, the

coal structure, despite extensive research

dies, was more widely the subject of speculation than an exact scientific basis. We were mainly in disagreement on the degree of aromaticity of the coal, that is to say on the percentage distribution between

aliphatic and aromatic carbon. We admitted before

  laughing that the coal was mainly constituted by highly aromatic heaps. Today, however, another image is obtained by the use of the

  13C nuclear resonance spectroscopy of char-

good solid. This is how we found, for char-

  vouchers especially suitable for disintegration, an aromatic content of only 60 - 65% (see S.K. Chakrabartty, The Structure and Chemistry of Coal, Conference on the occasion of the World Conference on Future Sources of Organic Raw Materials, Toronto,

Canada, 10. - 13. July 1978).

Other research has also shown that in the field of low volatile carbon constituents

molecular weight, you have to comote with a strong pro-

aliphatic portion (M. Vahrman, Chem. in Britain,

1972, 8, 16).

  By the use of a -simple mixture of frac-

  highly aromatic tar from partially aromatic pyrolysis oils and partially aromatic coal constituents

  which can be extracted by solvents in the reports

  corresponding ports, one should expect to obtain an oil of medium aromaticity and density and by

  continued with a medium Correlation Index.

  It has now surprisingly turned out

that the oils from the sources indicated above modi-

trusted by the coal decay process,

i.e. pyrolysis oil, gou-

  coal dron and the constituents of coal ex-

  milkers have undergone significant aromatization by disintegration so that a

  oil fraction with an extraordinary Correlation Index

generally high.

EXAMPLE 1.

  30 parts by weight of Westerholt carbon (volatile matter content 37 - 38%) are disintegrated by a mixture from 15% by weight of pitch distillate, 20% by weight of pitch distillate from tar pitch. oil treated with heat and pressure and 35% by weight of pyrolysis oil

from the steam cracking of crude benzene. This de-

integration is carried out at a temperature of 3700C

and with a reaction time of 3 hours. The press-

  maximum reaction is 25 bars. From this intermediate carbon product, after topping 3 parts by weight of volatile constituents by distillation, a distillate is obtained having a temperature

  initial boiling point 2550C and a boiling point

  tion (95%) of 4350C. The share of this distillate is

28%.

  We study this oil with regard to its

qualities as a raw material of black according to the specifications

  cifications shown in Table 2. A comparison

  its with the criteria taken from the published German patent application DEOS 25 47 679 shows that it is, in the case of the oil according to the invention, an excellent raw material for black. _ _

EXAMPLE 2.

We operate as in Example 1, but using

  the following solvent for disintegration: 15 parts by weight of pitch distillate, 20 parts by weight of pitch distillate from the coal tar pitch heat and pressure treatment and 35 parts by weight of pyrolysis residue the decomposition of diesel. From the carbon intermediate product thus obtained, there is obtained, after topping by distillation of the residue, a fraction in the range of boiling temperature of 270 - 4300C,

which represents 31% of the carbon intermediate product.

  The study of this fraction with regard to the criteria required for a raw material for black for the oven process shows that it is a very

good raw material for black.

\ He

BOARD

  Density, elementary analysis and for black atomic ratio C / H of advantageous raw materials. Elementary analysis in% by weight

C H S

  Atomic ratio C / H Aromatic concentrate (residue from catalytic cracking) Light steam cracking oil Heavy steam cracking oil Light anthracene oil Heavy anthracene oil

0.976

1.035 1.070 1.08585 1.136 87.2 91.1 92.1 91.0 91.4 9.2 8.4 7.0 6.2.8 1.8 0.1 0.1 0.6 0.7 0.7 0.79 0.91 1.10 1.22 1.31 I

quality believe

health of the ma-

raw material for black Density

at 20 C

(g / ml) -2 r% 9- 'one or 0%

T A B L E A U II

Elementary analysis in% by weight

C H S

Atomic ratio C / H Correlation Index Raw material for black according to Example 1, obtained

oar distillation of a ma-

middle car-

  good. Dour noir raw material according to Example 2, obtained

by distillation of a ma-

middle car-

good. 1,136 1,131

91.40 6.19 0.46

89.44

6.32 1.43

Oil for black from

tar according to the de-

order DE-OS 25 47 679.

1.136 91.0 6.20 0.60

Density

at 200C

(g / ml) 1.23 Co 1.17 1.22 rL w AU bone