DE3100366A1 - Process for the preparation of boiler fuel oil, bitumen and asphaltite - Google Patents

Abstract

The invention relates to a process for the preparation of boiler fuel oil, bitumen and asphaltite by mixing products, such as acid tars and sulphuric acid (black acid), with a hydrocarbon fraction. According to the invention, the hydrocarbon fraction is brought to a temperature of 10 to 450 DEG C before mixing, the stated products at 30 to 90 DEG C are then introduced, the components of the resulting reaction mixture are then brought into contact with the catalyst, and the vapour/gas phase formed in the course of the process is separated off at a temperature between 102 and 360 DEG C.

Description

ZWEIBRÜCKENSTR. 15 - 3 -

Belorussky Technologichesky January 8, 1981

Institute imeni S.M. Kirowa P 79 597

Minsk / USSR AS / fr

VEEFAHEEN ZÜE MANUFACTURING BOILER OIL, BITUMEN AND ASPHALTITE

The invention relates to the chemical technology of processing various acid products, in particular on a process for the production of boiler oil, bitumen, asphaltite from acid goudronen (acid refined oil sludge), spent sulfuric acid (Schwnr / .r.äurf!) unri a Knh] enwn: -.: -'- r, ", t.offVnkt.ion.

The present invention can be used in petroleum-processing, petrochemical, coke-chemical and other operations, where there is sulfuric acid waste, with great success

use.

A process is known for utilizing acid goudrons as fuel by burning them in various ways Firings; (Caye T. Forsyth E., Mills A.L. Lectures by V.

International Petroleum Congress Volume III, Petroleum Processing

Moscow,

and Gas "Erdölchemie-Verlag, / published 19Γ · 1, p. 127).

This process is associated with the technological combustion of goudron because of its high level of difficulty Viscosity and coking capacity in production stresses

BAD ORIGfNAc

3100356

and nozzles when heated, a low calorific value that is between I5OO and 35OO kcal / kg lies, and the corrosion of equipment own.

When acid goudrons are burned, large amounts of SOg-containing smoke gases are produced, which affect the environment and the destruction of buildings, facilities that cause corrosion of steel structures and equipment.

Losses of valuable mineral raw material, namely sulfur dioxide, are also characteristic of the known process, its recovery from smoke gases is technically difficult is to be carried out »

It is also a process for the utilization of acid goudrons with the production of boiler heating oil (USSR-tlrheberschein No. 268578) known.

The essence of this process consists in the neutralization of acid goudrons with aqueous suspensions of iron (TI) - and Iron (ITI) hydroxide.

However, the known method is of little use its complexity, energy intensity, consumption one large amount of reactants, difficulty in carrying out a continuous process production of inferior Boiler heating oil as well as incurring waste products that are difficult to recycle, i.e. a mixture of gypsum with organic Fabrics.

Ee is also a process for the production of road bitumen, and building bitumen from the oxidation of petroleum goudrons with sulfuric acid (USSR copyright no. 165975/1

known.

The essence of the process lies in the fact that a mixture

Consisting of 1.5 to 2.4 parts by mass of petroleum goudron or shark belly: long backlog

goudron / and 1 part by mass of acid goudron, based on the calculation of 5 Ms 10 parts by mass of petroleum goudron or half goudron per 1 part by mass of acid in the acid goudron, ^{oxidized at a temperature between 90 and 210 0} C by increasing the temperature by around 70 C hourly and representing The mixture is closed / held at a temperature of 300 to 400 ° C. for 40 to 90 minutes.

This procedure takes place periodically, has a long holding times and creates difficulties in the technological design of large-scale production.

A process for the production of as-dhaltite is also known from sulfuric acid waste through its heat treatment (Parchomenko W.E. "Acid goudron as a technological raw material".

Gostoptechisdat, 194-7, p. 57) · In this process, however

from the starting materials from the main acid mass beforehand / I to wash. the Inadequate effectiveness of the process consists in the complicated washing of the acid goudron, which increases the energy intensity of the

one

Process that formation / contaminated with organic compounds dilute sulfuric acid, the utilization of which is even more difficult than that of the starting material, i.e. the Päuregoudron is to be carried out.

Better boiler oils, bitumen and asphaltite are produced

Wash out

in a known process by / the acid goudrone of sulfuric acid with water, this procedure here

next state of

serves as / technology (Chernozhukov N.T. "Technology of petroleum

and gas processing ", part 3, Chimija-Verlag, Moscow, P. 341).

BATH ORIGINAL

The essence of this procedure is as follows: Tn a

pumps, inaii one

Lead agitator / on / layer of 80 to 90 C warm water in an amount of 20 to 40% of the acid goudron while stirring the goudron by stirring through

directs this direct steam. The weak sulfuric acid, obtained in the bottom of the agitator, is abgelas% n, while the top layer is mixed with one-captured substances obtained in such a manner boiler fuel oils, bitumens and asphaltite with 1 to 1.5 ¹ ^ pivot feIsauregehaIt.

shows
This method / however has the following disadvantages:

- production of boiler oil, bitumen and asphaltite of low quality,

- imperfect technology, laborious scrubbing of sulfuric acid to produce a large amount

dilute sulfuric acid, which is difficult to use because it is contaminated with organic compounds,

- Impossibility of using high viscosity acid gudrons as raw materials for the production of boiler fuel oil,

- difficulties in carrying out a continuous process,

- high metal and energy intensity of the system for carrying out this process.

The purpose of the present invention is to avoid the disadvantages mentioned.

The invention is based on the object of a highly productive and economical process for the production of To develop boiler oil, bitumen and asphaltite, in which the process of thermochemical conversions of the reaction mixture

310036

- 7 through improvement: the exchange of heat and substances is intensified.

This object is achieved in that in the proposed method for the production of boiler oil, bitumen and asphaltite by mixing products, taken from a grump,

used or black _# <.

consisting of acid goudronen and / sulfuric acid, with a hydrocarbon According to the invention, the reaction is the hydrocarbon fraction gel to a temperature of 10 to 450 ° C before mixing

in these
is and / products taken from a group consisting of

from acid goudronen and sulfuric acid, at a ^{temperature between 30 and 90 0} C, are then introduced, then the products

become one

of the resulting mixture brought into contact with / contact / and the vapor-gas phase formed in the course of mixing is separated off ^{at a temperature of 102 to 360 ° C.} Such a process allows the process to be intensified and good boiler heating oils, bitumen and asphaltite to be produced.

The process according to the invention is expediently carried out in stages under 0.1 to 20 Kr N / m pressure: up the first stage is introduced and dispersed at the same time 1

one
Part by mass of products from / group, consisting of acid goudronen and sulfuric acid, in 0.5 to 80 parts by mass of hydrocarbon fraction, heated to a ^{temperature between 10 and 260 0} C, then brings the products of the reaction mixture obtained at this stage in contact with the contact during on the second stage 1 part by mass of the mixture obtained in the first stage with. separated vapor-gas phase and at the same time in 0.4 to 90 parts by mass of Kohlenwasser ™ *) hereinafter referred to as "sulfuric acid"

material fraction whose temperature is between 120 and 450 ° C, then disperses the products in contact with the contact brings and separates the vapor-gas phase.

This reduces the formation of foam and shortens the time it takes for the foam to break.

It is also advisable to bring the products of the mixture into contact in the first stage for 1 to 150 seconds and in the second stage for 2 to 700 seconds 9, whereby the desired degree of decomposition of sulfuric acid and its derivatives is achieved ₃

When separating the vapor-gas phase is also one

dense rays

Sprinkling at / a linear speed

to recommend

which is between 0.01 and 10.5 m / sec ⁷ .

This shortens the time it takes for the foam to break.

It is also appropriate to use a carrier gas in an amount of

0.02 to 1.6 nr / m .sec, reducing the time for the Removal of SOg traces is shortened and the product quality is improved. It is recommended to use nitrogen, carbon dioxide gas, To use water vapor, air or mixtures thereof, as a result of which the formation of explosive concentrations avoided and a shortening of the time for the removal of SOg traces ensured.

It should be emphasized that the process according to the invention for the production of boiler oil, bitumen and asphaltite readily also in three, four and even more levels below

appropriate operating conditions can be carried out.

For the production of bitumen, it is advisable to use high molecular weight organic compounds or their mixtures such as distillation goudrone, deasphalting asphalt, extracts of the Selective refining of oils and their mixtures as hydrocarbon fraction to use. As a result, road construction bitumen and construction bitumen with improved plasticity properties are obtained.

expediently

For the preparation of asphaltite the reaction mixture / a 10 to 12O ⁰ G warm hydrocarbon fraction in a Wenge from 1 to 60 parts by mass per 1 part by weight of reaction mixture is to be added in the process, followed by separation of asphaltite and recycling the hydrocarbon fraction. This reduces the duration of the process, improves the conditions for the coagulation and separation of asphaltite and improves the quality of the asohaltite.

, wet

The process according to the invention for the production of boiler oil, bitumen and asphaltite by mixing products,

Consumed taken from a group consisting of acid goudronen and / sulfuric acid, with a hydrocarbon fraction is carried out as follows.

Mixing 1 part by mass Säuregoudron or sulfuric acid at a temperature between 30 and 90 ⁰ C temperature with 0.3 to 5 parts by mass of hydrocarbon fraction. The resulting mixture

better

has a lower viscosity, which means that it is pumped through technological lines. The mixture obtained is an emulsion which contains sulfuric acid, water, sulfonic acids, carboxylic acids, resin and oil-containing and resin and asphaltene-containing substances, esters and acidic esters.

'· ■ ■ 3100368' - ίο -

The emulsion obtained is thermally stable and decomposed easily in layers.

Then the decomposition of sulfuric acid and its derivatives under a pressure of 0.1 to 20.10 N / m is gradual carried out.

The decomposition of sulfuric acid and its derivatives in a hydrocarbon fraction is a complicated process, that of a change in the composition of the reaction mixture and the partial pressure of vapors and gases, the viscosity, Molecular mass, density and refractive index of organic Connections is accompanied.

In realizing the process is the big one

connected

Number of inner bonds with many parameters / whose change causes a disruption of these bonds.

The decomposition of the sulfuric acid contained in the acid goudron at a temperature of 10 to 450 ⁰ C according to the equation

H ₂ SO ₄ T = 10-450 C ^ Q ₀ ^ ₊ U ₂ Q ₊ o ₂

represents a thermodynamically forbidden reaction. In this one One can assume that when the acid goudron is introduced into the hydrocarbon fraction, it is preheated

102 to 450 C, the sulfuric acid first with aromatic carbon
Hydrogen / interaction.

H ₂ SO ₄ + ArH * - ArSO ^ H + H ₂ O,

then / implementation of both newly formed sulfonic acids as well

- li -

Sulphonic acids with hydrocarbons contained in the acid goudron he follows

ArSO ^ H + ArH - Ar - Ar + SO ₂ +

2ArSOoH 2ArH + 0
ArH + 20

Ar - Ar + 2SO ₂ + I Ar - Ar + H ₂ O Ar ¹ H + Ar "H + GO,

+ 0

The reduction-oxidation reactions take place in the volume of the hydrocarbon fraction.

When the acid goudron is introduced into the preheated hydrocarbon fraction, the model of the conversions of the Hydrocarbon fraction under the action of sulfuric acid and their derivatives are presented as follows:

iMonozykloaro- | jBicycloaromatic Hydrocarbons

! matic hydrocarbons

51

Polycycloaro; -H resins . matic coal ι

Hydrogens

Naphthenic paraffin fish '·

Hydrocarbons i

The amount of time required to complete the process The hydrocarbon fraction was obtained from the equation

^G kwf = ^ß

vSs

kgvS _S

Oil

vSs

H _n FlO,

determined what mean

of ß coefficient, determined on the basis / tests,

in this case it is assumed to be in a range from 1 to 25Ο;

^G kwf Amount of hydrocarbon residues in barrel parts;

Gw "c _rf Amount of acid goudron, consumed sulfur

KgVlA ^{1 year}

acid in parts by mass;

^H 2 ^S0 4 ' ^C H ₂ 0, content of sulfuric acid, water or C _Ss sulfonic acids in the acid goudron in percent by mass;

M _on M ₀ Molecular mass of sulfuric acid or sulfone-2 4 *

acid

The specified process implies the formation of highly condensate

Structures predicted carbene and carbide / not.

The paraffinic-naphthenic compounds arise from mono- and bicyclic compounds and can be used as a source at the Resin synthesis are used. As the change in concentration from paraffinic-naphthenic Compounds is relatively small, so the proportion is at the expense of the paraffinic naphthenic compounds Asphaltenes obtained are also low.

The proposed process thus excludes the formation of coke structures, which affect the quality of boiler oil and bitumen and asphaltite can deteriorate.

In the first stage is 1 part by mass of the mixture obtained in 0.5 to 80 parts by weight hydrocarbon fraction, preheated to a temperature 10-260 ⁰ C introduced, and the components of the reaction mixture was at a temperature

door from IO to 260 ⁰ C for 1 to 150 seconds. koniaktiort.

As a result, the partial decomposition of the
Sulfuric acid and its derivatives with simultaneous oxidation of the hydrocarbon fraction and formation of a vapor gas
Liquid mixture, its separation from / foam formation

is accompanied. To break the foam, you sprinkle it

with the hydrocarbon fraction in shape

of dense rays whose outflow velocity is 0.01
up to 10.5 m / sec. To remove the traces of
SOp and other gases are supplied with a carrier gas in an amount of 0.02 to 1.6 nr / m sec. One uses as carrier gas
Nitrogen, carbon dioxide, water vapor, air or their spirits. In the second stage, 1 part by mass of the reaction mixture obtained in the first stage with separated vapor-gas phase is then dispersed in 0.4 to 90 parts by mass of hydrocarbon fraction which has a temperature of 120 to 450.degree. That
Reaction mixture is at 120 to 450 ⁰ C for 2 to 700 seconds.
held.

The result is the final decomposition of sulfuric acid and its derivatives with simultaneous oxidation of the carbon

of a -liquid-

hydrogen fraction and formation / vapor-gas mixture, des-

one

sen separation of / foaming is accompanied. In order to destroy the foam, the foam is sprinkled with the hydrocarbon fraction in the form of dense jets whose outflow velocity is between 0.01 and 10.5 m / sec. To remove traces of Γ> 0 ₂ and other gases produced by the reduction of sulfuric acid and its derivatives

3 2 is a carrier gas in an amount of 0.02 to 1.5 nr / m sec.

fed. The carrier gas used is the same as in the first stage Nitrogen, carbon dioxide, water vapor, air or mixtures thereof.

For the production of bitumen, high molecular organic compounds or their mixtures, distillation goudrone, entasphal are used using asphalts, extracts from the selective refining of petroleum products and their mixtures as hydrocarbon fractions.

Thanks to the use of these products, it is possible to produce plastic bitumen with a high softening point.

A special feature of the production of asphaltite is considered

one _o

the fact that the reaction mixture / 10 to 120 C warm hydrocarbon fraction is added in an amount of 1 to 60 parts by mass per 1 part by mass of reaction mixture, then asphaltite separates and returns the hydrocarbon fraction to the process.

This produces a high polymer product, i.e. asphaltite, which is used for the synthesis of molecular sieves, resins and mastic can serve.

The process according to the invention thus solves an important economic problem, namely the recycling of sulfuric acid waste of companies producing boiler heating

these forward

tar, bitumen and asphaltite, whereby / for their part technically / can be turned. The method according to the invention also enables the task of protecting the environment from contaminants to solve and favors an improvement in working conditions.

"3100365

In order to better understand the present invention Characteristic values of starting products and examples of the specific implementation of the method according to the invention are given.

To briefly name the starting products, the following are used Abbreviations a:

A highly aromatic hydrocarbon fractions, in which "n" is the serial number of the hydrocarbon fraction in Table 1 means;

B Straigthrun hydrocarbon fraction of petroleum, where "n" is the serial number of the hydrocarbon fraction in Table 2 means;

C residual petroleum hydrocarbon fractions, wherein

η *

"η" means the hydrocarbon fraction number in Table 3;

D Acid goudrone or spent sulfuric acid4 in which "n" means the serial number in Table 4.

Tabel

Physico-chemical characteristics of (highly aromatic) hydrocarbon fractions

^A l A ₂ A3 Thermal
gas
oil ^A 5 ^A 6 Characteristic values Anthra-
Zen-
oil Coke-
of-
til-
Ia t kata
lyti
sches
easily
tes Extracts of
Selective raffi
nation of oils
with a boil
range ( ⁰ C) from Gas oil 5 320-485 35Ο-5ΟΟ 1 2 3 4th 6 7

Density at
20 ° C, p; / cm ³

1.1165 0.9500 0.8735 0.9831 ■ 0.0551 o, 967i

1 2 3 4th 5 6th 7th Refractive index π «) 1.6083 1.5570 1.4356 1.5839 1.5528 1.5718 conventional viscosity at 5O ° C, X 2.4 3.2 0.1 1.0 6.7 10.12 Molelcularmas- 276 19 '! 264 332 353 se Faction tog composition, ⁰ C Start of boiling 323 248 183 202 326 349 50% boils the end 442 365 258 375 420 382 End of boiling 530 442 348 509 485 498 Sulfur hold on, mas sel 0.25 1.25 0.98 1.38 1.63 1.85 Group togetherness composition, Pig methane ^ naphthe- 0.2 31.6 41, 4 9.5 12, 1 11, 8 niche cyclical aroma tables

1 9 2 7th 3 4th 5 6th 7th monocyclic 30th ,8th 16 , 59 13.1 8.7 10.9 io, 9 bicyclic 55 , 3 39 , 5 15.6 25.9 34.2 30.2 poly cyclic ^4th , 6 2 , 3 29.2 53.3 41.0 40.4 Resins , 2 0.7 2.6 1.8 6.7 Table 2

Physico-chemical parameters of hydrocarbon fractions (Straigthrun petroleum fractions)

B.

B ₁

Characteristic fractions with a boiling range ( ⁰ C) of

200-340 250-480 300-460 350-550> 35O

12 3 4 5 6

Density at

2O ⁰ C, g / cm ³ 0.8612

Refractive

number p ⁰ 1.3912

conventional viscosity at 50 ° C, ° \ 0.1

Molecular mass

Fractional composition, ° C

0.9054 0.9486 0.9703 0.9695 1.5292 1.5519 1.5691 1.5727

6.3

265

10.4

376

11.00

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1 2 3 4th 5 6th Start of boiling 179 247 299 353 353 50% evaporates 261 395 372 464 465 End of boiling 354 482 464 552 - Sulfur content, Dimensions% 0.23 1.39 1.58 1.58 1.73 Group get-together ingot, ingot methane naphthenic 73.4 52.6 13.4 36.1. 40.2 Cyclic aromatic monocyclic 7.8 10.8 11.7 10.4 2.9 bicyclic 8.2 14.2 35.1 24.1 15.4 polycyclic 10.3 21.5 38.3 16.2 32.9 Resins 0.1 0.9 1.5 11.2 8.6 table 3

Physico-chemical characteristics of (remaining petroleum) hydrocarbon fractions

C ₁

Characteristic values

Distillation Ent asphaltie goudron rungs asphalt

Density at 20 ⁰ C, g / cm ³ 0.9861 1.0192

conventional viscosity

at 80 ⁰ C according to Redwood

Viscometer sec. 42 63

COPY

1 2 3 Softening point after the ring and ball method, ⁰ C 36 47 Rankine flash point, ⁰ C 227 259 Sulfur content, mass% 2.7 2.9 Coking number, mass% 13.9 21.3 Group composition, pig paraffinic-naphthenic 22.6 3.2 cyclic aromatic monocyclic 12.2 5.1 bicyclic 11.5 6.3 poly cyclic 15.8 32.9 Resins 29.5 36.4 Asphaltenes 8.4 16.1

Table 4 Physico-chemical characteristics of acid goudrons

and used sulfuric acid (black acid)

Characteristic values

D-

Acid goudrone, obtained from

Refining
from

Cylin-Trans-In-Kon-Paderöl forma-dust- den- raffi-

gates-rieöl sator-nen

oil oil

Production of
Su lfonate supplements

consumed sulfuric acid accruing from sulfuric acid alkylation

Density at 20 ° C, g / cm ³ l, 3O ^r .fi 1, PG «? J, 7! F> 9

1.Ί77Β l, '»7 () ·) J,

1, RnO7

31ÖÖ366

1 23 ^ 5678

Viscosity at 80 ° C, measured in a viscometer a Opening, from 5 mm 0 sec 1296 14.5 587 129 15 926 3.2

Component composition, Ingot:

- sulfuric acid 40.5 58.3 35.9 58.1 79.1 24.6 88.6

- water 6.1 3.8 3.7 2.7 7.4 3.9 5.3

- organic

Mass 57.4 37.9 60.4 39.2 13.5 71.5 6.1

Group composition of the organic matter, ingot:

3Ί00366

resinous and oily

Fabrics 47.7 67.5 69.6 62.4 72.1 20.5 24.3

containing resin and asphalt

Fabrics 7.3 3.3 4.1 7.9 1.2 0.9 0.2

Carboxylic acids 1.5 3.1 1.5 3.5 2.2 0.8 0.9 acid

Ester 0.9 0.4 0.9 0.4 0.7 0.3 0.4

Sulfonic acids; 24.1 25.7 23.9 9.8 23.8 44.7 2.0

of that 25.2 21.8 waterun soluble 21.7 insoluble ch in one Petroleum frac tion of 0.5 2.1 250 to 350 ° C 2.4

7.7 9.6 4.3 0.1

2.1 14.2 40.4 1.9

Table 5

Physico-chemical parameters of substances containing resin and oil, isolated from acid goudrons and used sulfuric acid (black acid)

^D 1 ^D 2 ^D 3 ^D 1 ^D 5 ^D 6 ^D 7

Resin and oily substances, isolated

from acid eg oudronen, obtained with "ο *, l" i

Characteristic values ^Η ^ ^Γ Γ Sulfur refining of acidic to-cylinder-Transf-Tndust-Condens- ^Parafiuns ϊ · el deröl formarier- finen ™ "SfJofSSf toren- oil oil Sulphoffelsaure-52_Natzu- alkylier -

sentences approx

1 234 56 7 8

Density at
20 ⁰ C,
g / cm ³ 0.9841 0.8948 0.9418 0.8992 0.8785 0.9651 0.8794

Refractive index Πρ ° 1.5885 1.4984 1.5576 1.4996 1.4792 1.5685 1.4958

Molecular mass 441 306 352 321 283 387 295

Elemental composition,
Dimensions%:

- Carbon 87.43 87.49 87.63 87.54 87.38 87.42 87.65

- hydrogen 10.53 11.57 11.24 11.31 11.82 10.83 11.39

- sulfur 1.09 0.41 0.45 0.58 0.34 0.92 0.43

Content of
oxygen
hn It ip; on
radio 15 o-

nellen
Groups,

O CM

C ^ it ·. - O

O O O -

Cr \ - & O

r-1 O O

S25 53 UTN fe

o Lf ^ u) c ^ t

te O O ~ O

So rf O _:

, -T "CD C ° r-,

, 2 it m ω °

Oo O C) f '\

■ H O O O

ο * «Λ 'Λ ea c>

• λ ^ H LTN

ΙΓ \

U) cn cn im

^ cd ca ffi w

tr! CN O cm O

cn CM CN it ή

Ί CNi .0 »ο O

CM CM OvJ Ol OJ

^ O O O ϋ

O ·

- Sour-

fabric 0.53 0.26 0.28 0.30 0.2 ₅ 0.48 0.41

- nitrogen 0.42 0.27 0.40 0.27 0.21 0.35 0.12

H: C-Ver MW. 1.5869 1, ^ 387 ι // ·, ο8 ι, 6; <. _;; .> ι, / ι «<γ., .. ^

ratio
empirical
formula

0>
O CM
O O O CM
t-i £
O 11O0, O
σ
O • 0
cr> O
m.
O
VO it
W.
o> cn
LP,
LPv OO «Ft C-! .
O ^ J
O

Carbonyl groups,

) -C = O 0.15 0.08 0.06 0.06 0.07 0.13 0.04

Ester group- ^ ~~

pen, -COÖR 5.96 2.12 2.12 2.51 2.14 4.32 1.47 Hydroxy1 groups,

-OH 0.49 0.36 0.16 0.35 0.28 0.59 0.28

Carboxyl groups,
-COOH 1.34 0.43 0.45 0.76 0.63 0.71 0.53

Tabel

Physico-chemical characteristics of hydrocarbon groups, isolated according to the adsorption luminescence method made of substances containing resin and oil

Hydrocarbon groups paraffi- monocyclic bicyclic polycyclic aromatic oils naphthe- aromatic- aromatic-

niche see see

from resin and oil-containing substances from acid goudrons, accruing from the refining of cylinder oil

Density at 20 ⁰ C, g / cm ³ 0.8694 0.8851 0.9776 1.0658 Refractive index ΠJJ ⁰ Ι, ΊΒΩΙ 1, Ί9Ο7 1.5 ^ 98 l _for 5? 4

Molecular mass 446 428 395 373

__ from resinous and oily substances from acid goudrons, accruing from the refining of transformer oil

Density at 20 ⁰ C, g / cm ³ 0.8368 0.8531 0.9357 0 / ^"1 SOl

Refractive index Π ^ ° 1.4580 1.4842 1.5404 1, ^Γ 782

Molecular mass 332 325 276? <"> 6

from resinous and oily substances from acid goudrons, accruing from the refining of industrial oil

Density at 20 ° C, g / cm ³ 0.8462 0.8750 0.9574 0.9867

Refractive index H ^ ⁰ 1.4643 1.4970 1.5447 1.5831

Molecular mass 373 360 325 346

from resin and oil-containing substances from acid goudrons, accruing from the refining of condenser oil

Density at 20 ⁰ C, g / cm ³ 0.8393 0.8431 0.9389 0.986?

Refractive index Π ρ 1.4595 1.4694 1.5706 1.6535

Molecular mass 349 325 298 281

from resin and oil-containing substances from acid goudrons, accruing from the refining of paraffins

Density at 20 ⁰ C, g / cm ³ 0.8326 0.8570 0.9283 0.9791

20th
Refractive index IL ■ 1 , 4569 1 , 4816 1 , 5401 1.5750 Molecular mass 312 294 264 280

from resin and oil-containing substances from acid goudrons, accruing during the production of rulfonate additives

Density at 20 ⁰ C, g / cm ³ 0.8437. 0.8501 0.9425 0.9901

Refractive index ¹¹ J "1.4612 1.4702 1.5794 1.6605

Molecular mass 362 328 309 296

from resin and oil-containing substances of the used sulfuric acid, accruing at the Sulfuric acid alkylation

Density at 20 ⁰ C, g / cm ³ 0.8304 0.8421 0.9306 0.9835

Refractive index ΐζ ° 1.4572 1.4538 1.5685 1.6502

Molecular mass 315 297 275 264

example 1

The mixture is heated 1 part by mass Säuregoudron, accruing in the refining of cylinder oil, at a temperature of 90 ⁰ C and converted into 43 parts by mass Koksdestillat, preheated to 280 ⁰ C, a, and then the components brings the obtained-G-emisches in contact with the contact for 150 sec. and separating the resulting during the process vapor-gas phase from at a temperature of 200 ⁰ C.

The boiler heating oil obtained has the following characteristics: Density at 20 ° C., g / cm ^{3 0.9510}

conventional viscosity at 50 ° C, ° V _k 3.89 content, mass%, of:

- sulfur 1.24

COPY j "

31Ö0366

. - 27 -

- mechanical admixtures 0.05

- water-soluble acids, alkalis none

Pour point, ⁰ C -5

Flash point (in closed cup), ⁰ C 90

lower calorific value (based on dry fuel), kcal [kg 9895

Example 2

Mixing 1 part by mass Säuregoudron, accruing in the manufacture of SuIfonatzusätzen, at a temperature of 68 ⁰ C and 1 part by mass hydrocarbon fraction, that is 68 ⁰ C warm thermal gas oil. Then, 1 part by mass of 68 ⁰ C hot mixture obtained in 8 Masseriteile thermal gas oil, heated to a temperature of 296 C, introduced with simultaneous dispersion and the components of the reaction mixture obtained will be at 273 ° C and a pressure of 3> 9 * Hr N / m for 32 sec, followed by separation of the steam gas phase at a temperature of 174 ⁰ C with the contact brought into contact.

The boiler fuel oil obtained has the following characteristics: density at 20 ⁰ C, g / cm ³ 0.9856

conventional viscosity at 50 ° C,

X 2.1

Content, mass%, of:

-Sulfur 1.39

- mechanical admixtures 0.05

- water-soluble acids, alkalis no pour point, ⁰ C. +1

Flash point (in closed cup) 143 lower calorific value (based on dry

Fuel), kcal / kg 9974

Example 3

It leads 1 part by mass Säuregoudron, accruing in the refining of cylinder oil, having a temperature of 54 ⁰ C in 18.9 parts by mass of hydrocarbon fraction of the heated to a temperature of 268 ⁰ C extract the selective refining of 61 with a boiling range of 320-485 ° C under simultaneous dispersion and brings the mixture obtained at a temperature of 246 ⁰ C and a pressure of 1.4.1 Cr N / m for 42 seconds with the contact with separation of the vapor-gas phase at 148 ° C and 0, 94.1Cr N / m pressure with subsequent supply of nitrogen as a carrier gas in an amount of

3 2
0.1 no / m. Sec.

The Kesselheiz ^ l obtained has the following characteristics: density at 20 ⁰ C, g / cm ³ 0.9683

conventional viscosity at 50 ⁰ C,

° V _k 10.14 content, mass%, of:

- sulfur 1.86

- mechanical admixtures 0.04

- water-soluble acids, alkalis no pour point, C +3 flash point (in a closed cup) 136 lower calorific value (based on dry fuel, kcal / kg 9931

Examples 4 to 9

for the production of boiler fuel oil according to the invention Procedure in the same order of operations as in Example 3 are given in Table 7.

Tabel

Process conditions and characteristics of boiler heating oils

Characteristic values 4th Examples. 7th 8th Q 1 2 5 6 5 6th 7th 3 4

Hydrocarbon fraction Ag A, - B, - A, - A, - A ₂ acid goudron, consumed

Sulfuric acid D-, Pp D ~ D "Dg D"

Ratio of acid goudron, spent sulfuric acid to hydrocarbon fraction, in parts by mass 1: 2 1: 24.7 1: 12.3 1:80 1: 10.6 1: 26.7 temperature, ⁰ C, of: acid goudron, consumed

Sulfuric acid 45 56 38 44 90

Hydrocarbon

parliamentary group 125 203 420 254 267

Contacting the reaction mixture 105 176 400 250 240 Separation of the vapor-gas phase 105 127 243 128 122 Pressure at which the components are in contact N / m ² .10 ⁵ 1.0 1.4 ^r J, 7 1, 8 1.2 1.3

2 3 4 5

Carrier gas Stick- _{Stick- f} Koh- Was- Stick

fabric fabric- ^ i ^len - ^ser - ^fabric

Coal £!

Dioxyd- * S .ff

■ H.d S

ο ·, -P O Q)

Mixture cn μ cj

Amount of supplied

Carrier gas, m - '/ m .sec 0.6 1.6 1.3 0.02 1.5 1.2

Pressure at which the vapor-gas phase is separated
becomes, N / m ² .10 ⁵ 0.1 0.93 0.94 0.91 0.94 0.92

Characteristic of boiler heating ^{oil density at 20 0} C, g / cm ³ 0.9521 0.9673 0.9698 0.9675 0.9678 0.949 ^

Conventional viscosity at 50 ⁰ C, ° V _k 1.3 10.00 10.85 10.00 10.2 4.3

Content, mass%, of:

-Sulfur 1.34 1.82 1.7 1.8 1.83 1.3

- mechanical

Admixtures 0.06 0.03 0.08 0.04 0.03 0.04

-water soluble

Acids, alkalis ;; no

Pour point, ⁰ C -4 +2 +3 +1.5 +2 -3

Flash point (in closed cup) 93 128 139 125 127 95

lower calorific value (related

on dry fuel), kcal / kg 9875 9914 9931 9902 99Ο8 9882

Example 10

Mixing 1 part by mass Säuregoudron, accruing in the manufacture of Sulfonatzusatz, at a temperature of 90 ⁰ C with 1.4 parts by mass of extract of selective refining of oil with a boiling range of 320-465 ° C (Ac), then transferred to the first stage 1 mass part of 90 ⁰ C hot mixture obtained and dispersed in 5.6 parts by weight hydrocarbon fraction a ₁ -, heated to 157 ° C, and the Reakbion.sgemisch obtained is at a temperature of 142 ⁰ C and a pressure of

5 2
2.6.Kr N / m brought into contact with the contact at 142 ° C. for 27 seconds with subsequent separation of the vapor-gas phase. In the second step, 1 part by mass of the obtained in the first stage reaction ^ emisches introduced with separate steam Gas.- phase and 6.4 parts by mass of hydrocarbon fraction A _5, heated to 309 ⁰ C, and dispersed at 283 ° C and

λ 2

1.7 Kr N / m pressure for 51 seconds with subsequent separation the vapor-gas phase at a temperature of 127 C with the Brought into contact.

The boiler fuel oil obtained has the following characteristics: density at 20 ⁰ C, g / cm ³ 0.9885

conventional viscosity at 50 ⁰ C,

X 5.7

Salary, ingot, to:

- sulfur · 1.68 ■ - mechanical admixtures 0.06

- water-soluble acids, alkalis no pour point, ⁰ C +3 flash point (in the closed cup) 156 lower calorific value (based on dry

non "D ■«>, ^ - r <«■> e ■ 4 - / ^ - P · P ^ Tri-« η 1 / Xrn · or> o / ■

Examples 11 to

• for the production of boiler oil according to the invention Procedures in the same order of operations as in Example 10 are shown in Table 8.

Table 8

Process conditions and characteristics of boiler fuel oil

Characteristic values 11 12th Examples 15th 16 17th 1 2 3 13 14 6th 7th 8th 4 5

A ₅ A ₅

B ^ A ₁

J 1

Hydrocarbon fraction

Acid goudron, spent sulfuric acid Dn D ₀ D _Q D

Ratio of acid goudron to consumed sulfuric acid
to coal η water
material fraction 1: 0.83 1: 0.49 1: 0.85 1: 0.94 1: 0.96 1: 0.84 1: 0.96

Mixing temperature, o,

^J C

first stage

Ratio of the mixture of acid goudron, consumed r

90

84

Sulfuric acid and hydrocarbon fraction to hydrocarbon fraction, parts by mass l: 16ß 1:80 1:30 1: 0.5 1: 2 1: 6 1: 5 temperature, ⁰ C, of:

- hydrocarbons

material fraction 260 102 260 189 142 151

- Contacting the components of the reaction mixture 260 102 260 127 128 149

- Separation of the steam

-Gas phase 260 102 260 139 128 149

Pressure at which the components are in contact N / m ² .IQ ⁵ 1.6 1.1 2.4 1.2 1.6 1.5 1.7

Contact time of the components of the reaction mixture, sec 100 150 32 1 44 43 second stage

Ratio of the reaction mixture after the first stage to hydrocarbon ract ion, parts by mass 1: 0.4 1:10 1:20 1:14 1: 5 1: 6 1:90

Temperature, ⁰ C, from:

- hydrocarbon

parliamentary group 120 320 430 300 293 275 295

- Contacting the
Components of the
Reaction mixture

sches 120 252 430 280 253 264 276

- Separation of the steam

-Gas phase 102 102 260 120 118 129 137

Pressure at which the components are in contact N / m ² . 10 ⁵ 1.1 3.6 5.4 3.2 1.6 1.8 1.9

Contact time
the components of the
Reaction mixture,
sec 700 42 2 53 57 62 80

Characteristic of boiler oil

Density at 20 ⁰ C, V

g / cm ³ 0.9681 0.9662 0.9723 0.9675 0.9694 0.9061 0gl25

convention hey

Viscosity at

50 ⁰ C, ° V _k 9.3 8.7 10.4 9.7 9.2 0.7 3.2 Content, Bfasse%, of:

-Sulfur 1.69 1.78 1.53 1.65 1.69 1.12 0.24

5 6 7 8

- mechanical * admixtures 0.05 0.05 0.09 0.07 0.08 0.05 0.06

- water soluble
Acids, alkalis none

Stick temperature,

⁰ C + 5 + 2 +8 +4 + 6-4 +9

Flash point (when closed
Crucible) 153 141 164 150 152 163 168

lower calorific value
(based on
dry fuel), kcal / kg 9916 9862 9954 9921 9918 9873 9971

Example 18

The mixture is heated 1 part by mass Säuregoudron, anfallend "in the production of SuIfonatzusätzen, to a temperature of 76 ⁰ C, introduces and dispersed in 8.9 parts by weight of hydrocarbon fraction of preheated to 256 ⁰ C Destillationsgoudron with subsequent contacting of the components of the Eeaktionsgemisches for 150 sec, at a temperature of 248 ⁰ C, stick

3 2

substance supply in an amount of 0.9 nr / m. sec with subsequent separation of the vapor-gas phase formed during the process with simultaneous sprinkling with the aid of dense jets, the linear speed of which is 0.05 m sec, at 272 ° C and 0.95.1O ^ N / m ² pressure.

31 53 - 36 - 17th The bitumen obtained has the following characteristics: 254 Softening point after the ring and 70 Ball method, ⁰ C 81 Breaking point according to Fraass, ⁰ C Flash point, ⁰ C in the Rankine apparatus 56 Plastic range, ⁰ C 21st Stretchability at 25 ^° C. ₁ cm Needle penetration depth, 0.1 mm 93 at 25 ⁰ C (100 g, 5 sec) endures at O ⁰ C (200 g, 60 sec) in the residue after 5 h, 160 ⁰ C, % the initial depth of penetration Adhere to marble

Content of water-soluble compounds,

Mass% 0.08 Group composition, ingot:

- paraffinic-naphthenic 21.8

- cyclic aromatic

- monocyclic 9.9

- Bicyclic 9.2

- polycyclic 12.4

- resins 22.0

- Asphaltenes 24.7 content of oxygen-containing radio-

functional groups, mg KOH / gs

-! Carboxyl groups - COOH 1.3

- Ester groups - OOOR 24.7

- hydroxyl groups - OH 9.3

- Carbony groups - = CO 2.4

Examples 19 to 30

for the production of bitumen by the method according to the invention in the same sequence of operations as in Example 18 are given in Tables 9 »IO.

Table 9

Process conditions and characteristics of bitumen

Characteristic values 19th 20th Examples 23 24 2 3 21 22 '6 7th 1 4 3

Process conditions ^C l ^C l ^C l Hydrocarbon fraction C ₁ C ₁ C ₁ Acid goudron, ver ^D 5 ^D 6 ^D 7 needed swine fic acid D ₁ D ₂ D, Ratio of Acid goudron, more consumed sulfuric acid

to hydrocarbon off ra.k-

■ tion 1: 9.5 1: 16.3 1: 12.6 1:80 1: 4.5 1: 8.4

Temperature, ⁰ C, from:

- Acid goudron, spent sulfuric acid 48 72 34 52 QO 30

3Ϊ00366

- Hydrocarbon fraction 142

- Contacting the components of the reaction mixture 135

- Separation of the vapor-gas phase

Carrier gas

256 238

271

Amount of added inert gas, no / m. . sec

ability of

poetry
Rays

293

224

258

200 263 carbon nitrogen water dioxide vapor 252 nitrogen nitrogen nitrogen material carbon-carbon dioxide mixture di-

xyd-

Ge

mix

0.06

0.02 0.6 1.6

0.8

0.9

"with sprinkling,

m / sec 0.01 0.08 0.08 0.03 0.05 0.08

Pressure at which the vapor-gas phase is separated off, N / m ² .10 ⁵ 0.1 0.5 0.55 1 0.35 0 »64

Quality of bitumen

Softening point according to the ring and ball method, ⁰ C 59 47 50 38 109

Breaking point after

-18 -25 +3 -6

Praass, C. rl6 -2 Flash point, ⁰ C in the Rankine -Apparatus 241 23 Plasticity rich, ⁰ C. 74 67 Extensibility at 25 ⁰ C, cm 48 89

233 227 68 63

62 needle penetration depth at 25 ⁰ C (100 g,

273 259 107 89 2.5 4.5

5 sec) 57 124 83 284 18

at O ⁰ C (200 g,

sec) 19 41 28

3Ϊ00366

1 2 05 3 • 78 - 22.3 4th - - 89 • 21st - 5 15th 6th 0 98 , 0 7th 8th in residue , 2 after 5 h holds SUS .6 Through S. , 6 heat, 160 ° C, 10.7 10 , 2 , 4 % of the beginning 9.8 9 , 3 equaled one f.7 0.1 13.4 Or 12th , 7 , 01 ,1 penetration depth 95 20.2 22nd 74 . ( 97 ,8th Cling to 23.6 24 , 6 marble , 7 Content of what , 9 , 9 soluble , 4 ,1 Links, , 9 , 0 19.4 Dimensions% 0, , 0 , 4. 0, , 7 Group together ,1 , 0 , 6 composition,. »3 Ingot: »0 8th, - paraffinic , 6 8th, naphthenic a, sch 20th 23 16, - cyclical 38 aromatic - monocyclic sch 0 10 - bicyclic 8th 10 - polycyclic 12th 14th - resins 23 21st 0.01 - Asphaltenes 25th 19th 20, 8th 8th 9 20th 32

Content of oxygen-containing functional groups , mg KOH / g:

- carboxyl groups - COOH 0.96 0.98 0.87 0.23 0.37 0.35

- Ester groups - COOR 22.91 22.96 21.75 14.85 19 £ 1 W9

- hydroxyl groups - OH 8.76 8.84 7.98 1.26 3.43 7.12

- Karbony! Groups - CO 3.49 3.51 3.40 4.02 3.42 2.09

Process conditions and characteristics of
bitumen

Tabel

Characteristic values 25th Examples 28 29 30th 2 26 27 5 6th 7th 1 3 4

Procedural conditions

Hydrocarbon fraction Ag Ag Ag Ag Ag Ag

Acid goudron or spent sulfuric acid -D ₁ IX, D-, D _r Dr D, ₇

1 2 3 ^r -> 6 y

Ratio of acid goudron,
spent sulfuric acid to hydrocarbon fraction 1: 0.4 1: 14.9 1: 6.5 1: 19.2 1: 4.7 1: 16.3

Temperature, ⁰ C, of: - Acid goudron or

52 78

45 64

89 36

3iÖ0366

sulfuric acid

- hydrocarbon fraction

- Contacting the components of the reaction mixture

- Separation of the vapor-gas phase

Carrier gas

Amount of breeded

3 2

Carrier gas, m / m .sec

Speed of dense jets with sprinkling, m / sec

Pressure at which the vapor-gas phase is separated, N / m ² .10 ⁵

180 257 260 298 241 269

120 212 248 280 224 251

125 267 301 360 263 284 Koh- Stick- Was- Stick-Stick-Sticklenstoff hydrogen-carbon-carbon-vapor carbon-carbon-carbon len len-

diodiodioxyd xyd xyd-

Ge Ge mixture mix mix

0.3 0.02 0.6 1.6 0.7 0.2

0.02 0.1 0.08 0.02 0.05 0.1

0.1 0.71 0.72 1.0 0.51 0.8

68 43 47 45 49 47 -10 -27 -26 -27 -25 -27 229 242 247 252 249 250 94 70 73 72 74 73 48 69 72 70 53 72 54 183 126 130 82 126 18th 49 35 37 29 34

Characteristics of bitumen

Softening point according to the ring and ball method, ⁰ C

Fraass breaking point, ⁰ C flash point, ⁰ C

Plasticity range, ⁰ C stretchability at 25 ° C, cm needle penetration depth at 25 ° C (100 g, 5 sec) at O ⁰ C (200 g, 60 sec)

in residue after heating through for 5 h, 160 ° C., % of the initial penetration depth 82 67 72 71 86 75

Adhere to marble. endures

Content of water-soluble

Compounds, mass% 0.15 0.1 0.02 0.05 0.03 0.08

Group composition, mass%:

- paraffinic naphthenic

cal 16.4 30.1 27.4 27.2 26.9 27.0

- cyclic aromatic

- monocyclic 9.8 10.2 9.4 9.7 9.6 9.4

- Bicyclic 15.7 17.3 16.8 16.3 16.1 16.3

- polycyclic 9.6 15.1 14.9 15.2 12.4 14.5

Resins 24.3 10.4 13.4 12.9 12.2 13.7

- Asphaltenes 2 *, 2 16.9 18.1 17.7 12.8 19.1

-f 44 -

Saueratoffhaltigen content functional groups »mg KOH / gi

- Xarbosqrl groups - COOH 1.12 0.87 0.72 0.51 0.96 0.73

- Ester groups - COO 23.15 22.92 20.45 14 ^ 5 22.05 19.72

- hydroxyl groups - OH 9.14 8.15 8.914.13 8.33 6 _fi 14

- Carbonyl groups = C = 0 3.59 3106 2.34 2.02 3.02 2.98

Example 31

Mixing 1 part by mass Säuregoudron, accruing in the manufacture of SuIfonatzusätzen, at a temperature of 75 ⁰ C and 1 part by mass Destillationsgoudron, then leads on the first step 1 part by mass of 75 ° C hot mixture obtained in 1.4 parts by weight of to 197 ° C heated distillation goudrons and brings the reaction mixture at this temperature with subsequent separation of the vapor-gas phase at 197 ⁰ C and with sprinkling with the aid of dense jets, the linear speed of which is 0.02 m / sec, in contact with the contact. 1 part by mass of the reaction mixture obtained in 2 parts by mass Destillationsgoudron ₉ is in the second stage then heated to 306 ⁰ C, dispersed and at this temperature, followed by separation of the vapor-gaseous phase at 259 ° C for sprinkling with dense beams whose linear velocity 0 .06 m / sec, and purging with air in an amount

3 2
of 0.2 nr / m-.sec brought into contact with the contact.

y ■ - 45 -

The bitumen obtained has the following characteristics:

Softening point after the ring and

Eugel method ⁰ C 96

Fraass breaking point, ⁰ C -3

Flash point, ⁰ C in the Hankine apparatus 264

Plasticity range, ⁰ C 99

Stretchability "at 25 ° C, cm 4.2

Needle penetration deep

at 25 ° C (100 g, 5 sec) 26 in residue after heating for 5 h, 160 ⁰ C,

% of the initial penetration depth 95

Content of water-soluble compounds, mass% 0.02 -

Group allowance, mass%:

- paraffinic-naphthenic 19.4

- cyclic aromatic

- monocyclic 8.6

- Bicyclic 8.4

- polycyclic 9.0

- Resins 21.4

- Asphaltenes 33.2

, Examples 32 to 37 for the production of bitumen according to the Processes according to the invention in the same sequence of operations as in Example 31 are given in Table 11.

'"' '" 310036.

Table 11

Process conditions and characteristics of
obtained bitumen

Characteristic values 32 33 Examples 35 36 37 2 3 34 5 6th 7th 1 4th

Procedural conditions

Hydrocarbon fraction

Acid goudron, spent sulfuric acid

Ratio of acid goudron, used sulfuric acid to coals hydrogen reaction when mixing, parts by mass

Mixing temperature, ⁰ C first stage

Ratio of the mixture of acid goudron and consumed sulfuric acid with hydrocarbon reaction to form hydrocarbon fraction β parts by mass

D ₁ -

A,

1: 0.1 1: 2 1: 0.7 1 * 0.75 1: 0.7 1: 0.75 75 90 85 82 83 8?

1:49 1: 0.7 1: 4 1: 2 1: 1.4 1: 1.4

Temperature, ⁰ C, of i

- hydrocarbon

parliamentary group 105 215 210 176 194 192

- Contacting the

Reaction mixture 102 215 208 168 176 172

- Separation of the steam

Gas phase 105 215 208 159 173 171

Speed of dense jets when sprinkled, m / sec 0.01 10.5 0.08 0.06 0.07 0.04 second step

Reaction mixture hydrocarbon tract ion ratio,

Parts by mass 1: 0.5 1:45 1: 0.9 1: 0.9 1: 1 1: 1

Temperature, ⁰ C, from:

- hydrocarbon

parliamentary group 250 380 294 271 254 265

- Contacting the

Reaction mixture 240 370 305 270 252 255

- Separation of the vapor-gas phase 230 350 340 258 240 254

Speed of densities
Rays when sprinkled,
m / sec 0.01 10.5 0.3 0.04 0.03 0.05

* 3ί0036

Carrier gas air water-air stick-carbon-stic

vapor substance dioxide stcd

Kob] dioa

^: Gemi

Amount of supplied carrier

gergas, no / m .sec 0.02 1.6 0.7 0.03 0.05 0.04

Characteristics of bitumen

Softening point after
Single and ball method,

~ c * 52 58 85 the end 82 79 84 Breaking point according to Fraass, ⁰ C -18 -16 -4 -8th -10 -6 Flash point, ⁰ C in the bankine 0.02 -apparatus 232 250 271 269 265 268 Plastic range, ⁰ C 70 74 89 90 89 89 Stretchability at 25 ° C, cm 57 52 4.7 5 8th 4th Needle penetration depth at 25 ⁰ C (100 g, 5 sec) 72 59 25th 34 37 26th at 0 ° C (200 g, 60 sec) 24 18th - - - - Adhere to marble holds Content of water-soluble Connections, mass% 0.09 0.07 0.01 0.02 0.0 Group composition, Mass% s -

- paraffinic naphthenic

ce, 21.2 20.9 20.1 20.5 20.9 20.2

COPY

- cyclic aromatic:

single cycle 10.1 9.8 8.2 9.0 9.6 8.3

bicyclic 9.3 8.7 8.0 8.4 8 _? 7 8.4

polycyclic 12.4 13.1 8.9 10.9 1115 9.3

Resins 22.2 22.5 21.5 19.1 17.9 20.6

- Asphaltenes 24.8 25.0 33.3 32.1 31.4 33.2

Example 38

1 part by mass of spent sulfuric acid, obtained in the sulfuric acid alkylation, the temperature of which is 30 ° C., Is dispersed in 7 parts by mass of hydrocarbon fraction, ie distillation goudron, preheated to a temperature of 260 C, with subsequent contacting of the reaction mixture for 25 seconds at 20.Kr N / m pressure and subsequent separation of the vapor-gas phase formed in the course of the process at 246 ^° C.

The bitumen obtained has the following characteristics: Softening point according to the ring and

Ball method, ⁰ C 96

Breaking point according to Fraass, C +2

Flash point, ⁰ C in the Rankine apparatus 254 plasticity range, ⁰ C 94

Stretchability at 25 ° C, cm 2

Needle penetration depth, 0.1 mm

at 25 ⁰ C (100 g, 5 sec) 21

at O ⁰ C (200 g, 60 sec) 5

3 *? 0σ366

- 5ο -

Sticking to marble lasts

Content of water-soluble compounds, mass% 0.1

Group composition,
Dimensions%:

- paraffinic-naphthenic 19.6

- cyclic aromatic
monocyclic 8.2 bicyclic 8.9 polycyclic 9.7

- Resins 19.1

- Asphaltenes 34.5

Example 39

It leads 1 part by mass Säuregoudron whose temperature is 3O ⁰ C, with simultaneous dispersion in 6 parts by mass hydrocarbon fraction B ,, heated to 246 ⁰ C, and brings the components of the reaction mixture at 240 ⁰ C and 1,2.10 ^ N / m ² for 32 sec. in contact with the contact. Then the reaction mixture is 32 parts by mass of hydrocarbon fraction B ^, the temperature of 45 ° C, gas phase vapor added with subsequent separation of at 102 ⁰ C. The asphaltite obtained is separated off at 50 ^° C. and the hydrocarbon fraction is returned for repeated use.

The asphaltite obtained has the following characteristics: Softening point according to the ring

and ball method, ⁰ C 154

Solubility, mass%, in:

- carbon disulfide 99.9

- chloroform 99.9 "··" · ^: · 3'fbö Trichlorethylene 99.7 - 51 - Salary, ingot, to: - Water no - Water soluble acids, alkalis no Molecular mass 1594 Group composition, mass%: - paraffinic-naphthenic 5.6 - cyclic aromatic monocyclic 0.7 bicyclic 2.6 polycyclic 12.1 - resins 19.8 - Asphaltenes 60.1

Density at 20 ° C, g / cm ³ 1.0976

Elemental composition, ingot:

- carbon 84.53

- hydrogen 9.93

- nitrogen 0.91

- oxygen 0.78

- sulfur 3.85

Examples 40 to 53

for the production of asphaltite by the method according to the invention in the same sequence of operations as in Examples 39 are given in Tables 12,13,14.

Table 12

Characteristic values

40

Examples

41 42

44

hydrogen fraction
ο.

1:12 1:80 ^D 6

1:10

450 252 90
249

430 250 248

102

^D 7

1:13

Procedural conditions

Hydrocarbon fraction B, B, B,

Acid goudron or spent sulfuric acid ^D 3 ^D 2 · ^D 5

Ratio of acid goudron, used sulfuric acid to hydrocarbon

1: 1

Temperature, ^V C, from:

- Acid goudron, spent sulfuric acid 76 82 38

- hydrocarbon fraction 150

- Contacting the
Components of the
Reaction mixture I50

- Separation of the steam

-Gas phase 120 140 120

- hydrocarbon fraction, introduced

261

255

107

into the reaction mixture 10 120 36 42 34

- Separation of

Asphaltite IO 120 36 42 34

Contact pressure,

N / m ² .10 ⁵ 1.0 4.7 2.3 2.2 3.0

Contact time
of the reaction mixture, sec 240 2 29 36 41

Amount of that introduced into the reaction mixture
Hydrocarbon fraction in parts by mass,
based on 1 part by mass
Acid goudron 1 5 60 7 6

Characteristics of asphaltite

Softening point according to the ring and ball

-Method, ⁰ C 141 194 168 179 182 Solubility, mass%, in:

- carbon disulfide 99.9

- chloroform 99.9

- Trichlorethylene 99.9 content, mass%, of:

- no water

99.8 99.9 99.9 99.8 99.7 99.9 99.8 99.8 99.4 99.7 99.6 99.7

- water-soluble acids, alkalis

Molecular mass 1207 Group composition,
Ingot:

- paraffinic-naphthenic 8.1

- cyclic aromatic
monocyclic 1.8 bicyclic 3.5 polycyclic 7 | 8

- resins 20.3

- Asphaltene 58.5 density at 20 ⁰ C, O ⁰ C,

g / cm- "

Elemental composition, Dimensions%:

- carbon 84.79

- hydrogen 10.29

- sulfur 2.78

- nitrogen 0.96

- oxygen 1.18

no
1885 1652 1723

2.0 4.3 3.7

0.2 0.5 0.4

1.4 2.2 2.0

5.9 6.8 6.3

18.6 19.4 19.0

71.9 66.8 68.6

1761

18.9

69.5

1.0918 1.1425 1.1139 1.1254 1.1315

97.46 86.15 86.30 86.92

8.35 '9.51 9.48 9.01

2.62 2.73 2.65 2.64

0.85 0.87 0.88 0.86

0.52 0.74 0.69 0.57

β * O *

31G0366

- 55 -

Table 13

Process conditions and characteristics of asphalt it

Examples of characteristic values

45 46 47 48

Procedural conditions

Hydrocarbon fraction B ₂ B ₂ B ₂ B ₂ acid goudron, consumed

Sulfuric acid ^D 3% ^D 6 ^D 7

Ratio of acid goudron,
spent sulfuric acid to hydrocarbon fraction, parts by mass 1: 1 1:12 1: 6 1: 8

Temperature, ⁰ C, from:

- Acid goudron, spent sulfuric acid 52 34 86 32

- Hydrocarbon fraction 206 242 246 251

- Contacting the components of the reaction mixture 200 226 240 246

- Separation of the steam

Gas phase 128 121 102 174

- hydrocarbon fraction,
introduced into the reaction mixture 10 34 40 120

- Separation of asphaltite 10 34 40 120

Contact pressure,

N / m ² .10 ⁵ 1.1 1.2 1.3 1.3

Contact duration of the

Reaction mixture, sec. 240 42 38 26

Amount of hydrocarbon fraction introduced into the reaction mixture in parts by mass, based on 1 part by mass of acid goudron 1 8 60 6

Characteristics of asphaltite

Softening point according to the ring and ball method,

⁰ C 139 172 179 188

Solubility, ingot, in:

- carbon disulfide

- chloroform

- Trichlorethylene content% by mass, of:

- no water

- Water-soluble acids, no alkalis

Molecular mass 1218 1674 1743 1796

Group composition, ingot:

- paraffinic naphthenic

cal 6.4 5.8 5.3 5.0

99 , 9 99 , 9 99 ,8th 99 ,8th 99 , 9 99 .8th 99 , 7 99 , 7 99 ,8th 99 , 7 99 , 6 99 , 6

1 2 3 4th 5 - cyclic aromatic monocyclic 1.4 0.8 0.8 0.6 "bi cyclical 5.2 4.5 4.3 4.2 poly cyclic 7.6 6.4 6.0 9.9 - resins 22.8 16.4 15.2 14.5 - Asphaltenes 56.6 66.1 68.4 69.8 Density at 2O ⁰ C, g / cm ³ 1.1123 1.1225 1.1278 1.1296

Elemental composition, mass%:

- carbon 85.02 86.10 86.33 86.52

- hydrogen 10.41 9.84 9.73 9.65

- sulfur 2.65 2.41 2.36 2.31

- nitrogen 0.95 0.86 0.84 0.85

- oxygen 0.97 0.79 0.74 0.67

Tabel

Process conditions and characteristics
of asphalt it

49 Examples 51 52 53 2 50 4th VJl 6th 1 3 ^B 3 ^B 3 H Procedural conditions
Hydrocarbons
tion Β-, Bo

1 2 Acid goudron, consumption ^D 3 3 4th 5 6th te sulfuric acid Ratio of acid ^D 2 ^D 5 ^D 6 ^D 7 goudron, consumption ter sulfuric acid to hydrocarbons material fraction, Mas 1: 5 parts Temperature, ⁰ C, from: 1: 8 1:12 1:14 1:18 - acid goudron, more consumed 58 sulfuric acid - hydrocarbons 150 89 48 67 30th st of faction - Contacting 220 232 241 291 of the components of the reaction 150 mixed - Separation of the 210 224 237 286 Steam gas 102 phase - hydrocarbon 167 201 210 243 faction, incorporated leads to the Eeak 10 tion mixture - Separation of 10. 38 50 25th 120 Asphaltite 38 50 25th 120

O ·

• * β * ·

Contact pressure, N / m ² .10 ⁵

Contact time of the reaction mixture s, sec

Amount of hydrocarbon fraction introduced into the reaction mixture, in parts by mass, based on 1 part of the foot acid goudron

1.0 1.1

240

63 1.2

1.2

32

161

Characteristics of asphaltite

Softening point according to the ring and ball method, ⁰ C

Solubility, mass%, in:

- carbon disulfide

- chloroform

- Trichlorethylene content, mass%, of:

- no water

- water-soluble acids, alkalis none

169 178

99.9 99 , 9 99 , 9 99 ,8th 99.9 99.8 99 , 9 99 ,8th 99 ,8th 99.8 99.9 99 , 7 99 ,8th 99 , 7 99.6

1 2 3 4th 5 6th Group composition Ingot: - paraffinic -naphthenic 3.9 3.2 3.0 2.7 2.6 - cyclic aromati sch monocyclic 2.3 2.1 1.9 1.8 1.5 bicyclic 4.8 4.6 4.2 4.0 3.9 ροIcyclic 8.5 7.9 7.5 7.3 7.2 - resins 23.2 ' 16.4 16.0 14.9 14.7 - Asphaltenes 57.3 65.8 67.4 69.3 70.1 Density at 20 ⁰ C, g / cnr 1.1167 1.1254 1.1305 1.1349 1.1376 Elementary together settlement, mass%: - carbon 84.74 85.99 86.20 86.32 16.47 - hydrogen 9.94 9.06 8.95 8.94 8.90 - sulfur 3.09 2.95 2.91 2.92 2.84 - nitrogen 1.17 1.06 1.01 0.97 0.95 - oxygen 1.06 0.94 0.93 0.85 0.84 Example 54

Mix 1 part by mass of acid goudron, which arises from the refining of condenser?) 1, with 1 part by mass of consumed sulfuric acid and leads 1 part by mass of the 55 ° C obtained Mixture with simultaneous dispersion in 10

310036G

Parts by mass of hydrocarbon fraction, ie light catalytic gas oil, heated to 235 ° C and brings the components of the reaction mixture obtained "at 231 ⁰ C and 1.2.10 N / m pressure for 85 seconds in contact. Then the reaction mixture 14 Parts by mass of hydrocarbon fraction, ie light catalytic gas oil at 31 ^° C., with subsequent separation of the vapor-gas phase at a temperature of HO ^° C. The asphalt obtained is separated at 32 ^° C. The hydrocarbon fraction is returned to the process for repeated use .

The asphaltite obtained has the following characteristics: Softening point after the ring and

Kuge 1 method, ⁰ C 162

Solubility, ingot in: 99.9 - carbon disulfide 99.9 - chloroform 99.7 - trichlorethylene Salary, ingot, to: no - Water no - water-soluble acids, alkalis 1625 Molecular mass Group composition, ingot: 6.1 - paraffinic-naphthenic - cyclic aromatic 1.1 monocyclic 4.8 bicyclic 7.0 ροIcyclic 17.3 - resins

- Asphaltenes . 3100366 - 62 - Density at 20 ^° C., g / cm ³ Elemental composition, mass%: 63.7 - carbon 1.1195 - hydrogen - sulfur 85.74 - nitrogen 9.96 - oxygen 2.58 0.89 0.83

Claims (8)

COOO MUNICH 2 P 79 597 PATENT CLAIMS fly process for the production of boiler oil, bitumen
and asphaltite by mixing products, taken from a group consisting of acid goudrones and sulfuric acid, with a hydrocarbon fraction, thereby identified <the draws that before mixing the Hydrocarbon fraction, and bring to a temperature of 10 to 45O ⁰ C in the components warm, the 30 to 90 ⁰ C mentioned products introduced, then the resulting reaction mixture with the contact in touch brings
and the resulting during the process vapor-gas phase is separated off at a temperature between 102 and 36O ⁰ C temperature. 2. Process for the production of boiler oil, bitumen and Asphaltite according to claim 1, characterized S net that the process is carried out in stages under a pressure of 0.1 to 20.Kr N / m, with the first stage
1 part by mass of products from a group consisting of acid goudronen and sulfuric acid in 0.5 to 80 parts by mass of hydrocarbon fraction at a temperature of 10 to 260 ⁰ C and at the same time dispersed, then the components of the reaction mixture obtained from the first stage with
the contact while one is on the second
Stage 1 Part by mass of the reaction mixture of the first stage with the separated vapor-gas phase in 0.4 to 90 parts by mass of hydrocarbon fraction at a temperature between 120 and 450.degree introduces and disperses at the same time, then brings the products into contact and the bainpf gas phase
separates .. 1 or J or P 3. The method according to claim /, characterized that the contacting of products of the mixture on the first stage for 1 "to 150 seconds and on the second stage lasted for 2 to 700 seconds 4 «, method according to claim 1 _s, characterized 9 that when separating the vapor-gas phase, sprinkling with dense jets? the linear speed of which is O ₈ Ol to 10.5 m / sec 5 «method according to claim 1, characterized in that in the course of the process and after the separation the vapor-gas phase a carrier gas in an amount of 0.02 to 1.6 r / m .sec is fed. 6 ο method according to claim 5j characterized s that nitrogen, carbon dioxide, water vapor, Air or mixtures thereof serve as the carrier gas. one of the 7 «method according to / claims 1 to 6, characterized $ that for the production of bitumen high molecular © organic compounds or their mixtures such as distillation goudrone, Asphalt removal asphalt, extracts from selective refining of petroleum oils and mixtures thereof as hydrocarbons tof fraction come to use. one of the 8. The method according to / claims 1 to 7 »characterized that for the production of asphaltite the reaction mixture is 10 to 120 ° C warm hydrocarbon fraction in an amount of 1 to 60 parts by mass per 1 part by mass Reaction mixture is added with subsequent separation of asphaltite and recycling of the hydrocarbon fraction into the process.