Note: Descriptions are shown in the official language in which they were submitted.
~24~369
-- 2 --
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to a process for convert-
ing a heavy hydrocarbon, particularly a heavy oil such as
an atmospheric residue or a vacuum residue of crude oils,
highly into lighter and more valuable product, and a
process for further hydrotreating the lighter hydrocarbon
oil, and also to a process for producing gaseous olefins
and monocyclic aromatics from a heavy hydrocarbon as the
~eedstock by using these processes.
Description of the Prior Art
In recent years, in addition to the trend of
converting crude oils to heavy oils, unbalance between
the demand and the supply of petroleum products accom-
panied by the increase in demand of lighter oils is
arousing social problems, and effective utilization of
~xcessive heavy oils is nowadays an issue of crucial
importance in the field of petroleum industries.
On the other hand, in production of gaseous
olefins such as ethylene, propylene, butadiene, etc. and
monocyclic aromatics such as benzene, toluene, xylene~
etc., light hydrocarbons such as oil field gases or
petroleum refinery by-products such as naphtha have been
primarily employedO These are now suffering from short-
age of supply with their costs being increased, and
economical advantages to obtain gaseous olefins or mono-
cyclic aromatics are becoming markedly lowered. ~ccord-
ingly, in order to solve such a problem related to the
structure of industries, various attempts have recen-tly
been made to produce petrochemical starting materials by
hydrotreating lighter oils such as ~erosenes, gas oils,
vacuum gas oils, etc. followed by steam pyrolysis.
369
-- 3 --
~owever, in these methods, various kinds of oils employed
as the feedstock are available as petroleum products,
and the situation of starting material supply is the
same as .in the case of the light hydrocarbon such as
naphtha.
Thus, in either petroleum industries or petro-
chemical industries, it is now an important task to con-
~ert a heavy oil into lighter and more valuable product
for effective utilization as light petroleum products or
starting materials for petroleum chemistry. Accordingly,
a number of processes have been proposed for hydrocrack-
ing or thermal cracking of heavy oils, but none of these
processes are not necessarily satisfactory for converting
a heavy oil such as a vacuum residue into lighter pro-
ductl since some drawbacks are involved.
For example, in a fixed-bed or fluidized-bed
hydrocracking process in which the reaction is conducted
in a reactor packed with a granular or powderly catalyst,
when high conversion to lighter product is effected, by-
produced carbon and metal components contained i.n the
feedstock oil will be gradually deposited on the catalyst
layer, whereby depletion in activity of the catalyst or
plugging of the catalyst layer may be brought about.
On the other hand, when it is desired to accom-
plish high conversion of a heavy hydrocarbon to lighter
product according to thermal cracking, so called coking
phenomenon will be caused, which will lead to stopping of
-the operation. Therefore, this process is generally
applicable only to conversion to lighter product to an
e~tent such that coking poses no problem. For improvement
of this point, the so called hydrobisbreaking process has
been proposed. This process, however, cannot give suffi~
cient coking inhibition effect even if the hydrogen
pressure is increased to a high pressure of 300 kg/cm20
~Z4~3~9
-- 4
The coker process is also proposed, in which conversion
to lighter product is conducted while forming positively
cokes. This process, in addition to the disposal of
cokes by-produced in a large amount, cannot be free from
the problem of lowered yield of light oil. Besides, the
light oil obtained is enriched in aromatic components and
olefin components, thus involving the drawback of poor
quality.
Thus, in the prior art, even when attempted to
convert a high boiling material into lighter product by
catalytic processing of a heavy oil, impurities contained
in the oil such as sulfur or heavy metals as a matter of
course, particularly the presence of basic polymer com-
pounds will markedly lower the acidic ability of the
catalyst. As the result, there is involved the problem
that the cracking activity due to acidity of the catalyst
cannot persist. Also, in thermal cracking of a hydro-
carbon in absence of catalyst, the reaction rate is known
to be greater as its molecular weight is greater. How-
ever, since the reaction rates of side reactions such as
cokes formation and polycondensation are also great, it
is very difficult in reaction operations to increase the
degree of cracking.
On the other hand, various techniques have been
reported for hydrotreating heavy hydrocarbons by the re-
action in a dispersed state with addition of solid
materials. U.S. Patent 3,131,142, U.S. Patent 4,134,825
U.SO Patent 4,172,814 and U.S. Patent 4,285,804 disclose
hydrotreatments by adding an oil-soluble metal compound
or an emulsion of an aqueous solution of a water-soluble
metal compound. U.S. Patent 3,161,585 and U.S. Patent
3,657,111 disclose hydrotreatments by using a thermally
~racked colloidal material of an oil-soluble metal com-
pound or vanadium sulfide colloid particles. Canadian
Ratent 1,073,389, Canadian Patent 1,076,983, U.S. Patent
~LZ~43~
4l176,051, U.S. Patent 4,214,977 and U.S. Patent
4,376,695 disclose hydrocracking by using pulverized coal
or pulverized coal coated with a metal salt. U.S. Patent
3,707,461 and U.S. Patent 4,299,685 disclose hydrotreat-
ments by use of pulverized coal ash. U.S. Patent
4,169,038, U.S. Patent 4,178,227, U.S. Patent 4,204,943,
~apanese Laid-open Patent Publication No. 20768a/1982 and
Japanese Laid-open Patent Publication No. 69289/1983 dis-
close hydrotreatments by using cokes by-produced or
petroleum ash by-produced. Japanese Laid-open Patent
Publication No. 40806/1979 and Japanese Laid-open Patent
Publication No. 141388/1981 disclose hydrocracking by
using a desulfurized catalyst or a pulverized waste cata-
lyst thereof. U.S. Patent 4,066,530 and U.S. Patent
4,067,799 disclose hydrotreatment by use of a combination
of an oil-soluble metal compound and an iron component
particle, Japanese Laid-open Patent Publication No.
108294/1983 by use of a combination of a metal compound
and a metal-containing dust by-produced, and U.S. Patent
3,331,769 and U.S. Patent 4,376,037 by use of a combina-
tion of a metal compound and a porous solid catalyst or a
porous carrier, respectively. However, most of these
techniques employ the reactions approximate to desulfur-
ization conditions, and they are proposals aiming at
primarily metal removal, hetero-atom removal such as sul-
fur or nitrogen removal or residual carbon removal from
heavy hydrocarbons. A part of these techniques employ a
heavy hydrocarbon which can be cracked with relative ease
as the feedstock and attempt to apply an appropriate
degree of hydrocracking by utili~ing a waste catalyst,
cokes by-produced or a natural product. Thus, according
to any of these techniques, when applied for high conver-
sion of heavy hydrocarbons such as atmospheric residue or
vacuum residue into lighter products, the technical
problems frompractical aspect such plugging of equipments
and economical problems remain to be solved.
lZ4~36~3
SUMM~R~ OF THE INYE~TION
The present inventors have made extensive studies
to overcome -the drawbacks possessed by the processes of the
prior art and to develop a process for converting highly a
heavy hydrocarbon as the feedstock into ligh-ter and more
valuable product economically and at high yield. As a
consequence, it has now been found tha-t by adding at leas-t
two kinds of components of an oil-soluble or water-soluble
transition metal compound and a ultra-fine powder having an
average particle size within -the range from 5 to 1000 m~
which can be suspended in a hydrocarbon to -the feedstock of
a heavy hydrocarbon and carrying out thermal cracking in the
presence of hydrogen gas or hydrogen sulfide-containing
hydrogen gas, side reactions of polycondensation reaction
and cokes forming reaction can be suppressed and scaling
(cokillg) in the equipmen-t, particularly in the reaction
zones, can be inhibi-ted, whereby valuable light oils can be
obtained economically, stable and at high yield from a heavy
hydrocarbon, and at the same time deteriora-tion of the
residue can be suppressed to reduce its amount remarkable.
The present invention has been accomplished on the basis of
such a finding.
More specifically, the present invention provides
a process for conver-ting a heavy hydrocarbon containing a
fraction having a boiling point higher than 520C into
lighter hydrocarbon oil which comprises: adding an oil-
soluble transition metal compound or an aqueous solution of
mls/LCM
~Z~1~3~
,,
water-soluble transition metal compound -to the heavy
hydrocarbon; and separa-tely adding an ultra-fine powder of a
fine ceramic or carbonaceious substance which can be
suspended in a hydrocarbon and has an average particle size
within the range from 5 to 1000 m,u, to the above heavy
hydrocarbon; cracking -the heavy hydrocarbon in -the presence
of hydrogen gas or hydrogen sulfide-containing hydrogen gas;
and recovering the resulting ligh-ter hydrocarbon oil.
- 6a -
mls/LCM
~Z~36g
J _
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. l and Fig. 2 show flow charts for practic-
ing the different embodiments of the process for produc-
ing gaseous olefins and monocyclic aromatics, respective-
ly, in which 3 is a cracking heater unit, 5 is a high
pressure gas-liquid separator, 8 is an atmospheric flusher,
10 is a vacuum flusher, 17 is a liquid-solid separator,
20 is a`hydrotreating units, 23 is a high pressure gas-
liquid separator, 26 is a gas-liquid separator and 29 is
a steam pyrolysis unit.
DESCRIPTION OF PREFERRED EMBODIMENTS
The heavy hydrocarbon to be used in the present
in~ention is a crude oil or an atmospheric residue or a
vacuum residue of a crude oil, including also shale oil,
tar sand extract and liquefied coal oil. A heavy hydro-
carbon containing a large amount of a fraction worthwhile
giving high conversion of heavy oil into lighter, more
valuable product, for example, a fraction having b.p. of
5~0 C or higher under atmospheric pressure, has greater
2conomical effects.
In the process for converting a heavy oil into
lighter/ more valuable product according to the present
invention, a synergetic effect can be brought about by
using at least two kinds of substances in combination.
This may be considered to be exhibited due to the action
as described below.
An oil-soluble or water-soluble transition metal
compound may be considered to be converted by thermal
treatment in the present of hydrogen and/or hydrogen sul-
Eide in the reaction zone of a heavy hydrocarbon or in
the stage prior thereto into a substance having a hydro-
treating catalytic activity in a hydrocarbon thereby
t ~ 3G9
inhibiting polycondensation reaction or cokes precursor
cr cokes forming reaction which are inevitable side reac-
tion in high conversion of a heavy hydrocarbon into
lighter, more valuable hydrocarbon. In addition, other
advantages are also exhibited such as suppression of the
amount of the gases generated as by-product, prevention
of deterioration of the properties of the oil produced by
thermal cracking, etc.
On the other hand, a ultra~~ine po~der hav-
ing an average particle size within the range from about
5 to 1000 m~ which can be suspended in a hydrocarbon may
also be considered to prevent the scaling (coking) phe-
nomenon in the reaction zone, which is also inevitable
in high conversion of a heavy hydrocarbon into lighter,
more valuable hydrocarbons, by ensuring floating state of
cokes precursor, cokes or the like or through its ability
to transport and migrate these materials. In addition,
when a transition metal compound is converted to a sub-
stance having a hydrotreating catalytic activity, it may
be considered to serve in forming high dispersibility and
high surface area. As the result, there are additional
advantages such that the effect can be exhibited with a
small amount of the transition metal compound and that
khe effect can be exhibited even with a transition metal
having weak hydrogenating function.
In practicing the process for high conversion of
a heavy hydrocarbon into lighter, more valuable hydro-
carbons of the present invention, it is essentially
required that at least two kinds of substances of an oil-
soluble or water-soluble transition metal compound or a
substance having hydrotreating catalytic activity con-
verted from such a compound and a ultra-fine powder
having an average particle size within the range from
about 5 to 1000 m~ should be simultaneously present in a
heavy hydrocarbon. However, it is not necessary to
369
g
prepare a specifically compounded mixture beforehand, but
it is only sufficient to add separately these substances
into a feedstock of a heavy hydrocarbon. Even when the
respective components may be added separatelyl it may be
considered that the transition metal compound interacts
with the ultra-fine powder to be changed
automatically into a substance system exhlbiting a desired
function in the reaction zone or at the stage prior to
the reaction zone. The ultra-fine powder is required
to be suspended in a heavy hydrocarbon. The "suspended"
herein mentioned refers to the state where solid particles
exist substantially in a liquid or the state where solid
phases are distributed incontinuously through the liquid
phase which is continuous phase, including those called
as colloid, slurry or paste.
Of course, it is also possible to prepare a sub-
stance system capable of exhibiting a desired function
with at least two kinds of substances beforehand and use
this substance system for addition into the feedstock of
a heavy hydrocarbon. For e~ample, an oil-soluble transi-
tion metal compound is dissolved or an aqueous solution of
a water-soluble transition metal compound is emulsified in
an oil such as gas oil or vacuum gas oil, a ultra-fine
powder having an average particle size
within the range from about 5 to 1000 m~ is dispersed in
the solution or emulsion. The resultant dispersion is
subjected to the thermal treatment at a temperature at
~hich the transition metal compound is decomposed in the
presence of hydrogen gas or hydrogen sulfide-containing
hydrogen gas to prepare a solid, which is separated or
concentrated by a known solid-liquid separating method and
added to a heavy hydrocarbon. The heavy hydrocarbon is
then provided for use in a process for converting the
heavy hydrocarbon into lighter, more valuable product by
thermal cracking in the presence of hydrogen gas or hydro~
gen sulfide-containing hydrogen gas. As another example,
~24~369
-- lO_t
a gaseous phase of hydrogen gas or hydrogen sulfide-
containing hydrogen gas having a ultra-fine powder ~
with an average particle size of about 5 to 1000 m~ is
heated and into its atmosphere is sprayed an oil solution
having an oil-soluble transition metal compound dissolved
therein or an aqueous solution having a water-soluble
transition metal compound dissolved therein to decompose
the transition metal compound, followed by drying. The
resultant solid is added to a heavy hydrocarbon, which is
then subjected to thermal cracking in the presence of
hydrogen gas or hydrogen sulfide-containing hydrogen gas
to convert the heavy hydrocarbon into lighter, more valu-
able hydrocarbons. However, in the impregnation method
or the precipitation method, in which the transition metal
compound is supported on a ultra-fine powder, it is not
desirable to use a preparation method in which agglomera-
tion or sintering will occur between mutual transition
metal compounds, between mutual ultra-fine powders or
between the transition metal compound and the ultra-fine
powder.
i
As another substance system having a desired
function, it is also possible to reuse a thermally cracked
product obtained by the present process for converting a
heavy hydrocarbon into lighter, more valuable hydrocarbons
or a heav~ residue fractionated by distillation of the
thermally cracked product as such, or alternatively to use
a solid separated and recovered from these dispersed oils.
In the oil-soluble or water-soluble transition
metal compound, the transition metal is inclusive of all
the transition elements in the Periodic Table of ~lements,
and selected particularly from the group consisting of
vanadium, chromium, iron, cobalt, nickel, copper, molybde-
num~ tungsten and mixtures thereof,
Examples of the oil-soluble compounds containing
:~;Z 4~3~9
desired transition metals are 50 called ~-complexes con-
taining cyclopentadienyl group or allyl group as the
ligand, organic carboxylic acid compounds, organic alkoxy
compounds, diketone compounds such as acetylacetonate
complex, carbonyl compounds, organic sulfonic acid or
organic sulfinic acid compounds, xanthinic acid compounds
such as dithiocarbamate, amine compounds such as organic
diamine complexes, phthalocyanine complexes, nitrile or
isonitrile compounds, phosphine compounds and others.
Particularly preferable oil-soluble compounds are salts of
aliphatic carboxylic acids such as stearic acid,
octylic acid, etc., since they have high solubilities in
oill contain no hetero atom such as nitrogen or sulfur
and can be converted with relative ease to a substance
having hydrotreating catalytic activityO Compounds of
smaller molecular weights are preferred, because less
amounts may be used for the necessary amounts of the
transition metal.
Examples of water-soluble compounds are carbon-
ates, carboxylates, sulfates, nitrates, hydroxides,, ,"~-
l1alogenide and ammonium or alkali metal'salts of transi
ti,on metal acids such as:ammonium heptamolybenate.
In the case of an oil-soluble transition metal
compound, it can be used as a solution by additing
directly into the feedstock of a heavy hydrocarbon.
However, in the case of a water-soluble transition metal
compound, it is necessary to form an emulsion by adding
an aqueous solution thereof into the feedstock of a heavy
hydrocarbon. In this case, including the method employing
an emulsifier, any of the known methods for emulsification
may be applicable.
The ultra-fine powder having an average
particle size within the range from about 5 to 1000 m~
which can be suspended in a hydrocarbon can exhibit
3~9
- 12 -
excellent effects as described below as compared with
solid catalysts, carriers employed for solid catalysts
and merely crushed products of these known in the prior
art of this field. That is to say, ~1) it can ensure
high dispersibility and great free movement in the re-
action zone and can give a site for uniform reaction
without localization; (2) it will reside scarcely in the
reaction zone, but discharge easily adhered or deposited
polycondensed products such as asphaltenes, cokes pre-
cursors, cokes, etc. under highly dispersed, floated
state out of the reaction zone, thereby avoiding plugging
in the reaction zone; and ~3) it can prevent agglomera-
tion of substances having hydrotreating catalytic activi-
ty formed from transition metal compound to effect high
dispersion, thereby enhancing the activity of the sub-
stance having hydrotreating catalytic activity. In
addition, the greatest feature of the ultra-fine powder
is an extremely great outer surface area as compared with
substantially porous solid catalysts and carriers. The
solid catalysts and carriers of the prior art, even when
crushed, will be broadly distributed generally in the
range from several microns to some ten microns, having
a very small outer surface. The effect expected is
derived mostly from the inner surfaces within the poresO
~Iowever, in the case when the reaction occurs within the
pores, the diffusion rate of the reactants poses a
problem, and there is created a concentration gradient of
the reactants between the center portion of the particle
and the vicinity of the surface, whereby the site for the
reaction becomes ununiform. Accordingly, the effective
coefficient is always the problem, and physical structures
such as pore distribution or crushed particle size dis-
tribution may have effects greatly on the resultant per-
formance. Besides, when employing a heavy hydrocarbon as
the feedstock, substances having large molecular weights
contained therein such as asphaltenes, porphyrin-like
substances containing heavy metals and cokes precursors or
12;~L~3~9
-- l~ t--
cokes formed cannot enter to the inner portions of the
pores but will readily plug the pores in the vicinity of
the surface, whereby the inner surfaces depending sub-
stantially on the pores can function little to give no
expected effect. In contrast, the ultra-fine powder
is a substance system which is not substantially porous
or not expected to be porous and can exhibit a desired
effect through the effective action of only the large
outer surface. The outer surface area will be dramati-
cally increased as the particle sizes are smaller. For
example, in the case of the particle sizes of 10 to 50
m~, the surface area can be about 300 to 60 m2/g to give
an extremely excellent effect. The ultra-fine powder
satisfying these properties can be classified into in-
organic substances and carbonaceous subs-tances. Illustra~
tive of inorganic substances are so called fine ceramics
such as ultra-fine particulate silicic acid, silicates,
a:Lumina, titania, etc. and ultra-fine metal particles such
as those obtained by the vapor deposition method. Of
these substances, to describe about ultra-fine particles
of silicic acid and silicates, these are a group of many
kinds of substances called conventionally as white carbon,
and they can be synthesized according to the vapor-phase
processes such as by thermal decomposition of silicon
halides, thermal decomposition of silicic acid-containing
compounds, thermal decomposition of organic silicic com-
pounds, etc.; and according the liquid-phase processes
such as decomposition of sodium silicate with an acid,
decomposition of sodium silicate with an ammonia salt or
an alkali salt, formation of an alkaline earth metal sili-
cate from sodium silicate followed by decomposition with
an acid, ion-exchange by treating an aqueous sodium
silicate solution with an ion-exchange resin, pressurized
decomposition of an organogel, decomposition of silicon
halide with water, decomposition of sodium silicate solu-
tion with silicofluoric acid by-produced in the manufac-
turing step of calcium superphosphate, production
4'~369
- 14 -
utilizing natural silicic acid or silicates, the reaction
of sodium silicate with a hydroxide such as calcium
hydroxide or calcium chloride, aluminum chloride or
sodium aluminate, the treatment of quartz or silica gel
with calcium hydroxide in an autoclave, etc. The parti-
cle size can be measured by an electron microscope, and
it may range approximately from 5 to 50 m~, although
different depending on the kind~ As to the surface area,
the outer surface area calculated from the particle size
measured by an electron microscope and the specific
surface area determined by the gas adsorption method
(BET method) coincide substantially with each other, and
it is within the range approximately from 50 to 400 m2/g.
On the other hand, the carbonaceous substances
are a group of substances obtained by formation of carbon,
namely carbonization, which can be classified into liquid
phase or solid phase carbonized substances such as petro-
leum cokes, coal cokes, pitch cokes, activated charcoal,
charcoal, etc. and gas phase carbonized substances such
as carbon blacks. Carbonaceous substances, as compared
with inorganic substances, are combustible and therefore
advantageous when the heavy residue which is a product
after the reaction of converting a heavy hydrocarbon into
lighter, more valuable hydrocarbons is utilized as boiler
fuel.
Liquid phase or solid phase carbonized sub-
stances are generally great in particle sizes formed, and
most of them are required to be subjected to micro-
pulverization operation and classification operation in
order to have desired particle sizes. On the other hand,
most of the gas phase carbonized substances have particle
sizes falling within the particle size range of the pre-
sent lnvention, and therefore they are available as sucho
~mong them, carbon blacks include a variety of kinds
formed as the gas phase carbonized substances, which can
` ~Z~36~
- 15 -
be prepared according to the methods such as oil furnace
method, gas furnace method, channel method, thermal
method, acetylene black method, by-produced carbon black
method, lamp black method and others. The particle size
can be measured by an electron microscope and it is
approximately 9 to 500 m~, although different depending
on the kind, approximately 9 to 100 m~ except for those
produced by the thermal method. As to the surface area,
the outer surface area calculated from the particle size
measured by an electron microscope and the specific sur-
face area determined by the gas adsorption method (BET
method) coincide substantially with each other, and it is
within the range of approximately from 5 to 400 m2/g.
When the ultra-fine powder of the present
invention is added to the feedstock of a heavy hydro-
carbon, it may be added directly as such or as a con-
centrated dispersion in a different medium. The
dispersion containing the ultra-fine powder may be
subjected to mechanical operation such as by a stirrer,
ultra~sonic wave or a mill, or alternatively or in com-
bination admixed with dispersants such as a neutral or
basic phosphonate, a metal salt such as sulfonic acid
salt of calcium or barium, succinimide and succinate,
benzylamine or a polypolar type polymeric compound.
In practicing the process for converting a
heavy hydrocarbon into lighter, more valuable product,
the amounts of at least two kinds of substances to be
added may be within the range from 10 to 1000 ppm,
more preferably from 5Q to 500 ppm, for the transition
metal compound calculated as metal based on the weight
of the feedstock of a heavy hydrocarbon, and within the
range of from 0.05 to 10 % by weightr more preferably
from 0.1 to 3 % by weight, for the ultra-find powder
based on the weight of the feedstock of a heavy hydro-
carbonO In the case of preparing a substance system
~t ~ 36~
- 16 -
capable of exhibiting the desired function of at least
two kinds of substances beforehand, it is desirable to
prepare a formulation having a composition so as to fall
within the ranges as specified above. At a level of less
than 10 ppm of the transition metal of the transition
metal compound based on the heavy hydrocarbon or at a
level of less than 0.05 wt. % of the ultra-fine powder,
no sufficient effect of inhibiting the side reactions of
polycondensation reaction and cokes forming reaction, and
also no sufficient effect of preventing scaling (coking)
can be obtained. On the other hand, in excess of 1000
ppm of the transition metal of the transition compound
or in excess of 10 wt. % o~ the ultra-fine powder, no
~urther improvement corresponding to such amounts can be
recognized, but rather unfavorable side reactions or
solid-liquid separation in the reaction zone and plugging
accompanied thereby may occur.
In practicing the process for converting a
heavy hydrocarbon into lighter, more valuable product,
the thermal cracking conditions depend on the heavy hydro-
carbon employed as the feedstock and the properties and
amounts added of at least two kinds of substances~ but,
in general, the reaction temperature employed may range
from 4ao to 550 C, pre~erably from 430 to 520 ~C. At
a higher temperature region exceeding this temperature
range, thermal cracking will pxoceed so far that forma-
tion of cokes and generation of gases will become marked
until there is substantially no feedstock to be converted
into lighter oil. On the other hand, at a lower tem-
perature region lower than this temperature xange, the
thermal cracking rate tends to become markedly slow.
The reaction pressure may be 30 Kg/cm2 to 300
Kg/cm2 preferably 50 Kg/cm2 to 250 Kg/cm2.
369
- 17 ~-
The thermal cracking may be operable by either
batchwise or continuous system, and the reaction time or
the time for residence of the heavy hydrocarbon within
the reactor may be l minute to 2 hours, desirably 3
minutes to one hour. These processing conditions do not
take individually optimum values, but they are related
-to each other, and therefore the optimum ranges may be
changed depending on the situation. Further, the amount
of hydrogen to be fed in practicing thermal cracking may
be lO0 to 5,000 Nm3/kQ, more preferably 500 to 2,000
Nm3/kQ, in terms of the volume ratio relative to the
feedstock and it is generally desirable to continue run-
ning with supplement of hydrogen gas in an amount corre-
sponding to the amount of hydrogen gas consumed. As the
hydrogen to be fed, either high purity hydrogen gas or a
gas mixture containing a large amount of hydrog~n gas
may be employed. Even when employing hydrogen sulfide-
containing hydrogen gas, the amount to be used may be
such as amount as corresponding to that as mentioned
above as the total amount, but the content of hydrogen
sulfide may preferably about l to lO mole %.
The type of the reaction equipment when carry-
ing out the reaction continuously may be either a tubular
reactor, a tower reactor or a soaker type reactor, but in
any of these reactors, it is desirable to perform sus-
pension reaction while maintaining a ultra~fine powder
under suspended state without forming a fixed-bed,
fluidized-bed or ebullating-bed. The reactor structure
can be simpler for suspension reaction~ and the reaction
temperature can be controlled more easily without change
in performance with lapse of time and plugging by coking
will hardly occur. In addition, a high temperature and
short time reaction can be practiced with relative ease
and therefore a great space velocity can be taken to
afford a large amount of unit treatment, with additional
advantage of making chemical consumption amount of
~z~ 9
- 18 -
hydrogen gas smaller while suppressing hydrogenating
activity such as hydrogenation of aromatic nuclei.
Of the product oils obtained by practicing the
process for converting a heavy hydrocarbon into lighter,
more valuable product of the present invention, the des-
tillates may be available as a whole or after fractiona-
tion as substitute for naphtha in petroleum chemistry, or
can be separated into fractions having respective boiling
ranges for use as intermediate starting materials for
petroleum products such as gasoline, jet fuel oil, kero-
sene, gas oil, diesel fuel, lubricant and others.
In the process for further hydrotreating the
hydrocarbon oil obtained as the lighter, more valuable
product according to the process of the present invention~
the hydrocarbon oil obtained may be subjected to hydro-
treatment as such or after removal by separation of the
high boiling fraction from the hydrocarbon oil obtained~
Hydrotreating-may advantageously be carried out after
removal of the high boiling fraction, since substances
such as asphaltenes or metals can be removed thereby. In
addition, the high boiling fraction removed by separation
can be handled substantially similarly as the liquid fuel
oil, which can be utilized as the fuel source in the pro-
cess practiced in the present invention or otherwise for
use in boilers in general. As the method for separation
of high boiling fraction, there may be employed conven-
tionally used high pressure gas separation, atmospheric
distillation, vacuum distillation and further solvent
deasphalting.
The catalyst to be used in practicing the
hydrotreating process may be any of the catalysts known
or hydrotreating of petroleum fractions and heavy oils;
preferably a catalyst containing each at least one kind
o metals selected from the group VIb metals and the
~2~436~
-- 19 --
group VIII metals of the Periodic Table such as metal
species of nickel-molybdenum, cobalt-molybdenum,
nickel-tungsten and the like, supported on an inorganic
porous carrier. These metal species are used generally
as oxides or sulfides, and the inorganic porous carrier
may include, for example, alumina, silica, silica-
alumina, zeolite, zeolite-containing alumina, alumina-
boria, silica-alumina-titania and others. The hydro-
treating conditions may be selected as desired depending
on the heavy hydrocarbon oil employed as the feedstock
and the properties of the catalyst, but the reaction
temperature may be 250 to 480 C, preferably 300 to
450 C. If the reaction temperature exceeds 480 C,
thermal cracking of the side reaction proceeds too much,
whereby increase of the carbon deposited on the catalyst,
increase of the hydrogen consumed accompanied with in-
crease of gas generation and reduction of liquid yield
are recognized. On the other hand, at a temperature
lower than 250 C, the reaction rate will become markedly
smaller. The reaction pressure may be 3 to 300 Kg/cm2,
preferably 50 to 250 Kg/cm2, which is related greatly to
the hydrotreating capacity of the catalyst. Further, the
liquid hourly space velocity (~HSV) may be 0.1 to 5.0
-1 --1
hr , preferably 0.2 to 3.0 hr , and the amount of
hydrogen to be fed is within the range from 200 to
2000 Nm3/kQ in terms of the volume ratio relative to the
feedstock oil to be hydrotreated. These conditions are
not selected so as to take individually optimum values,
but they are related to each other and optimum ranges
are to be selected in correspondence to the requirements,
including of course the properties of the feedstock oil
and the catalyst activity, and also the purpose of use
of the hydrotreated product oil.
The process for producing gaseous olefins and
monocyclic aromatic hydrocarbons by use of a heavy hydro-
carbon as the feedstock comprises as a first embodiment:
~L~44369
- 20 -
(A) adding to a heavy hydrocarbon
(i) at least two kinds of substances comprising
an oil-soluble or water-soluble transition
metal compound and an ultra-fine powder which
can be suspended in a hydrocarbon and has an
average particle size within the range from 5
to lQ00 m~; or
(ii) a solid prepared by dissolviny an oil-
soluble transition metal compound in an oil or
emulsifying an aqueous solution of a water-
soluble transition metal in an oil; dispersing
an ultra-fine powder having an average particle
size within the range from 5 to 1000 m~ in
the oil solution or in the oil/aqueous emul~
sion; and heating the dispersion at the decom-
position temperature of the transition metal
compound in the presence of a hydrogen gas or
a hydrogen sulfide-containing hydroyen gas; or
(iii) a solid prepared by dissolving an oil-
soluble transition metal compound in an oil or
dissolving a water-soluble transition metal
compound in water and converting the solution to
a dry solid by spray.ing the solution ~n a hydro~
gen gas or a hydrogen sulfide-containing
hydrogen gas in which an ultra-fine powder
having an average particle size within the
range from 5 to 1000 m~ is dispersed and by
simultaneously heating the gas to decompose the
transition metal compound and to dry the solid;
(B) thermally cracking the hèavy hydrocarbon in the
presence of a hydrogen gas or a hydrogen
~- sulfide-containing hydrogen gas and recovering
the resulting lighter hydrocarbon oil;
(C) removing a fraction having a high boiling
point from the lighter hydrocaxbon oil; and
(D) pyrolying a fraction having a low boiling
point or a mixture of the fraction and a
~Z~36~
- 21~i
petroleum fraction with steam, and recovering
a gaseous olefins product and a monocyclic
aromatics product.
Alternatively, according to a second embodiment,
the process comprises:
(A) adding to a heavy hydrocarbon
(i) at least two kinds of substance comprising
an oil-soluble or water-soluble transition
metal compound and an ultra-find powder which
can be suspended in a hydrocarbon and has an
average particle size within the range from
- 5 to 1000 m~; or
(ii) a solid prepared by dissolving an oil-
soluble transition metal compound in an oil or
emulsifying an aqueous solution of a water-
soluble transition metal compound in an oil;
dispersing an ultra-fine particle having an
average particle size within the range of from
5 to 1000 m~ in the oil solution or in the oil/
aqueous emulsion; and converting the dispersion
to a solid by heating the dispersion at the
decomposition temperature of the transition
metal compound in the presence of a hydrogen
gas or a hydrogen sulfide-containing hydrogen
gas; or
(iii) a solid prepared by dissolving an oil-
soluble transition metal compound in an oil or
dissolving a water-soluble transition metal
compound in water; and converting the solution
to a dry solid by spraying the solution in a
hydrogen gas or a hydrogen sulfide-containing
hydrogen gas in which an ultra-fine particle
having an average particle size within the
range from 5 to 1000 m~ is dispersed and by
simultaneously heating the gas to decompose the
transition metal compound and to dry the solid;
369
~ 22~-
(B) thermally cracking the heavy hydrocarbon in the
presence of a hydrogen gas or a hydrogen
sulfide-containing hydrogen gas and recovering
the resulting lighter hydrocarbon oil;
(C) removing a fraction having a high boiling point
from the lighter hydrocarbon oil;
(D) hydrotreating a fraction having a low boiling
point under hydrogenation conditions and re-
covering the resulting hydrotreated oil; and
(E) pyrolyzing the hydrotreated oil or a mixture of
the hydrotreated oil and a petroleum fraction
with steam, and recovering a gase~us olefins
product and a monocyclic aromatics product
According to a third embodiment of the process,
in the process according to the first or second embodi-
ment as defined above, the whole or a part of a solid
which is separated and recovered from the lighter hydro-
carbon oil obtained in step (B) or the fraction having a
high boiling point removed in step (C) is recycled to
step (B).
Accroding to a fourth embodiment of the process,
in the prooess according to the first or second embodiment
as defined above, the whole or a part of the fraction
having a high boiling point removed in step (C) is recycled
to step (B).
Thus, the process for producing gaseous olefins
and monocyclic aromatics according to the present inven-
tion comprises as the basic steps four or five steps.
In the case of the four steps, it is consisted of the
step of adding to a heavy hydrocarbon at least two
kinds of substances, the thermal cracking step, the
step of removing a high boiling fraction and the steam
pyrolysis s-tepO In the case of the five steps, it has
the hydrotreating step between the step of removing a
lZ~L4~
- 23~1~
high boiling fraction and the steam pyrolysis step.
The thermal cracking step employs the process
for converting a heavy hydrocarbon into lighter, more
~aluable product as described above. Accordingly,
through the effect of at least two kinds of substances
to be added to the feedstock of a heavy hydrocarbon in
the presence of hydrogen gas or hydrogen sulfide-contain-
ing hydrogen gas, the side reactions of polycondensation
reaction and cokes formation reaction can be inhibited,
and also scaling (coking) in the equipment particularly
in the reaction zone can be prevented, whereby useful
lighter oil can be obtained from a heavy hydrocarbon
economically, stably and at high yield, with additional
great advantage that deterioration of properties of the
lighter oil as well as the high boiling residue can be
prevented. This can be exhibited particularly in the
case of using an atmospheric residue or a vacuum residue
of a paraffin-based crude oil such as Minus crudes,
Taching crudes, etc. known as the heavy oil crudes.
More specifically, these heavy residues are heavy oils
which have been deemed to be relatively difficult in
high conversion to lighter, valuable product by phase
separation of product. According to the present inven
tion, by taking advantage of the excellent feature of
paraffinic properties of these heavy oils, it is rendered
possible to effect high conversion thereof into lighter,
more valuable product. Accordingly, the fraction having
the low boiling point of lighter product obtained by
atmospheric or vacuum distillation can be provided for
use directly in steam pyrolysis without f~lrther passing
through the hydrotreating step to give starting materials
for petroleum chemistry. As a consequence, equipments
such as hydrotreating equipment axe nc more necessary,
and there is also a great effect of decreased amount of
hydrogen consumption. Moreover, the high boiling
12~36~
- 24 -
residue removed by distillation can sufficiently be
utilized as the liquid fuel substantially similarly
as the straight heavy oils for the fuel source in
practicing the present process or boilers in general.
The steps of removing a high boiling fraction
is required for feeding a fraction having a low boiling
point to the subsequent steam pyrolysis steps or hydro-
-treating step. As the method for removing a high
boiling fraction, there may employed high pressure gas
separation, atmospheric distillation or vacuum dis-
tillation conventionally used, and further solvent
deasphalting. It is also possible to effect fractiona-
tion into naphtha fraction (boiling point lower than
200 C), kerosene gas oil fraction (boiling point of
200 - 343 C) and vacuum gas oil fraction (boiling
point of 343 - 545 C). Various kinds of these lighter
fractions may be subjected to steam pyrolysis as such
or after hydrotreatment.
In subjecting the thermally cracked oil af~er
removal of the high boiling fraction to be hydro-
treating step, the method for hydrotreatment as described
above can be employed as such. However, since the feed~
stock oil employed is the thermally cracked oil from
which the toxic materials for the catalyst such as
asphaltenes and metals have been removed, the catalyst
employed has greater activity as the surface area as the
physical property of porous carrier is greater, whereby
it is not particularly required to increase the pore
volume of large pore si~es as in the case of the
catalyst for treatment of an oil with a high level
content of asphaltenes or metals.
9L3~
- 25 -
The thermally cracked oil from which the high
boiling fraction has been separated and removed in the
separating step or the hydrotreated oil recovered from
the hydrotreating step may be used as the feedstock oil
in the steam pyrolysis step, and it is also possible to
carry out steam pyrolysis of each fraction fractionated
separately or as a mixture with other petroleum frac~
tions depending on the purpose.
The mode of steam pyrolysis to be used in the
steam pyrolysis step in the process of the present
invention is not particularly limited, but various modes
can be employed, and it is also possible to use a
tubular heater which is an existing naphtha cracking
heater as such or with a slight modification.
The reaction conditions in the steam pyrolyz-
ing step may be a steam oil weight ratio of 0.2 to
200, preferably 0.4 to 1.5, a pyrolysis temperature of
700 to 900 C, preferably 750 to 900 ~C, and a
residence time of 0.05 to 2.0 seconds, preferably 0.]
to 0.6 seconds.
The product obtained by the steam pyrolysis
reaction is led from the heater to a quenching heat
exchanger for heat recovery, followed by separation and
purification, to give gaseous olefins and monocyclic
aromatics, by-produced fuel oils and other by-produced
hydrogen and hydrocarbons.
In practicing the process of the present in-
vention, hydrogen gas to be used in the thermal cracking
step, and the hydrotreating step may be supplied by
circulation from the hydrogen gases separated from the
respective steps, sometimes after removal of hydrogen
sulfide and ammonia contained therein, and it is generally
~Z~36~3
-t
- 26 -
desirable to supplement hydrogen gas in an amount corre-
sponding to the hydrogen gas consumed. In this case,
as hydrogen source, the hydrogen gas by-produced in
steam pyrolysis or hydrogen gas obtained in steam
modification of by-produced hydrocarbon gas or by-produced
fuel oil may also be available.
Referring now to the accompanying drawings, the
embodiments of the process for producing gaseous olefins
and monocyclic aromatics by use of a heavy hydrocarbon as
the feedstock in the present invention is described in
detail, but the present invention is not limited thereby.
~ ig. 1 and Fig. 2 show different examples of
flow charts for practicing the process for producing
gaseous olefins and monocyclic aromatics according to the
present invention. To describe with reference to the
steps in Fig. 1, the feedstock of a heavy hydrocarbon
admixed with at least two kinds of substances according
to the present invention is elevated in pressure by means
of a feed pump and fed through a line 1, and hydrogen gas
or hydrogen sulfide-containing gas is elevated in pres-
sure by means of a compressor and fed through a line 2,
respectively, into a thermal cracking equipment 3, where~
in the heavy hydrocarbon is converted to lighter, more
valuable product. The lighter product obtained is
delivered through a line 4, to be quenched therein, to a
gas-liquid separator 5. The high pressure gas-liquid
separator consists generally of the two stages of a hot
separator and a cold separator. The hydrogen-enriched
gas from the separator is discharged through a line 6 and
after elevation to a desired pressure, if desired, cir-
culated to the thermal cracking equipment 3. The liquids
from the hot separator and the cold separator are not
required to be preheated and fed -through a line 7 to an
atmospheric flusher 8. Next, the atmospheric residue
withdrawn through a withdrawing pipe 9 from the bottom of
~2~369
27~
the atmospheric flusher 8 is further delivered to a
vacuum flusher 10 to be treated therein. The vacuum
flusher 10 is operated under vacuum with equipment of a
vacuum generating device for the purpose of lowering the
operating temperature, and sometimes it is also possible
to use steam distillation as auxiliary means in which
steam is blown from the tower bottom to lower the partial
pressure of the oil. The atmospheric fraction from the
atmospheric flusher 8 and the vacuum fraction from the
vacuum flusher 10, after removal of off-gas through lines
11 and 12, respectively, are mixed by passing through
lines 13 and 14 to be introduced into a line 15. On the
other hand, the vacuum residue withdrawn through a with-
drawing pipe 16 from the bottom of the vacuum flusher 10
may be employed as such as a liquid fuel, but it may be
introduced into a solid separator 17 to be subjected to
the solid separation operation. The solid separator 17
may comprise, for example, a centrifugal separator, a
filter, a solvent sedimentor and a combination thereof.
A part of the vacuum residue or the solid or the solid
subjected to further cleaning and drying operations (not
shown) may be recycled via the line 18 to be added to
the feedstock of heavy hydrocarbon. The liquid vacuum
residue separated from most of the solid in the solid
separator 17 is discharged through a line 19 and may be
used as liquid fuel. The distillate oil introduced into
the line 15 is elevated in pressure by a feeding pump and
fed into a hydrotreating equipment 20 to be hydrotreated
therein with hydrogen gas elevated in pressure by means of
a compressor. The hydrotreated product is cooled to a
desired temperature by means of a heat-exchangex, etcO and
delivered via a line 22 to a high pressure gas-liquid
separator 23 to be separated into gas and liquid. The
hydrogen-enriched gas separated is circulated via a line
2~, after elevation to a desired pressure if necessary, to
the hydrotreating e~uipment 20. On the other ~a~d~ the
: - -
~2~4369
- 28 ~
hydrotreated liquid product is dropped in pressure by
passing through a line 25 to be fed into a gas-liquid
separator, and, after discharging the off-gas with a high
vapor pressure through a line 27, delivered via a line 28
to a steam pyrolysis equipment 29. In this equipment,
the hydrotreated product is steam pyrolyzed and the
pyrolyzed product is withdrawn through a line 30, cooled,
separated, purified and recovered as gaseous olefins,
monocyclic aromatics, by-produced hydrogen, by-produced
fuel oil, etc.
The flow chart shown in Fig. 2 shows the case
when no hydrotreating step is required, corresponding to
the chart shown in Fig. 1 from which the symbols 20 to
28 are omitted.
The present invention is described in further
detail by referring to the following Examples, by which
the present invention is not limited.
Example 1
Using a vacuum residue of Minus crudes (100 wt
~ of a fraction having boiling point higher than 520 C~
as the feedstock oil, thermal cracking was carrled out by
means of a continuous type equipment operated with high
pressures having a reactor of a soaker type vessel of 40
mm in inner diameter and 100 mm in height equipped with
a stirrer mounted with three turbine type blades each
having three fans. As the two kinds of the components
to be added to the feedstock oil, nickel octoate was
added in an amount of 200 ppm as nickel based on the
feedstock oil, and oil furnace carbon blacks [average
particle size of 20 m~ by electron microscope (E.M.),
specific surface area of 120 m2/g by BET method] in an
amount of 2 wt. ~ based on the feedstock oil, respective-
ly~ and the feedstock oil was thoroughly stirred before
lZ~q~3~;9
- 29 -
it was fed into the reactor.
The reaction conditions employed for the ther-
mal cracking were a temperature of 495 C, a pressure of
200 kg/cm2, a residence time (based on cold liquid) of
20 minutes and a hydrogen/feedstock oil ratio of 2000
~Q/Q, with the number of revolutions of the stirrer being
1000 rpm. The continuous running time was 100 hours as
the steady state running time.
The products obtained were 5.8 wt. % of Cl - C4
gases~ 45.2 % of the GO fraction b~ atmos-
pheric distillation (b.p.: 343 C >~, 29.0 wt. % of the
~GO fraction by vacuum distillation (b.p. 343 - 520 C)
and 20.0 wt. % of the vacuum residue (VR). The content
of asphaltenes Cdefined as insoluble in hexane and solu-
ble in tetrahydrofuran) was 2,1 wt. %, and the content of
cokes (defined as insoluble in both tetrahydrofuran and
hexane) was 1.0 wt. ~. The amount of hydrogen consumed
was 110 NQ per kg of the feedstock. The conversion of
heavy feedstocks into lighter, more valuable product as
defined by the following formula:
proportion of fraction having
b.~. hiaher than 520 C in product
1 proportion of fraction having b.p. x 100
higher than 520 C in feedstock
~"as found to be 80 wt. %. The yield of the liauid frac-
tion conver-ted to lighter product of b.p lowex than
520 C was 74.2 wt. ~ as the sum of GO and VGO.
In addition, the amount of coking (scaling
amount) on the inner wall surface of the reactor after
100 hours of steady state running was extremely small as
40 ppm based on the total weight of the feedstock oil fedO
Comparative example 1
Example 1 was repeated except that the two
~Z~3~
- 30' -
kinds of components were not added into the feedstock
oil. As the result, about 2 hours after initiation of
running, the reactor was completely plugged with coking,
whereby no stable running could be practiced. Under the
conditions where stable running was possible, the yield
of the liquid fraction having b.p. lower than 520 C was
34.1 wt. %, being less than half of the yield in Example 1
Comparative example 2
Example 1 was repeated except that no ultra~
fine particle was added and only nickel octoate was
added in an amount of 500 ppm as nickelO As the result,
about 4 hours after initiation of running, the reactor
was completely plugged with coking. The yield of the
liquid fraction having b.po lower than 520 C was 75 wto %
but the amount of cokes formed was 3.5 wt. % and most of
them, namely about 3.0 wt. % was found to participate in
the coking in the reactorD
Comparative example 3
Example 1 was repeated except that no transi-
tion metal compound was added and only oil furnace carbon
blacks were added in an amount of 4 wt. %. As the result,
about 15 hours after initiation of running, the reactor
was completely plugged with coking. The yield of the
liquid fraction having b.p. lower than 520 C was 74 wto %,
but the amount of the cokes formed was as much as 6.1 wto
%, with the amount of coking in the reactor being about
0.8 wt~ %.
Comparative example 4
Example 1 was repeated except that 3 wto % of
pulverized delayed cokes uniformized to have a particle
size distribution within the range from about 10 to 6
~Z~3~9
t
were employed instead of carbon blacks. As the result,
about 3 hours after initiation of running, the reactor
was completely plugged with coking. The yield of the
liquid fraction having b.p. lower than 520 C was 73 wt.
%, but the amount of cokes formed was 3.1 wt. %, of
which about 2.2 wt. % was found to have undergone coking
together with the pulverized delayed cokes added in the
reactor.
Comparative example 5
Example 1 was repeated except that 3 wt. % of
nickel-tungsten catalyst supported on porous y-alumina
with a specific surface area of 220 m2/g ~BET method)
containing 4 wt. % of nickel oxide and 15 wt. % of tungs-
ten oxide, pulverized to particles sizes of 60 ~ or less,
was employed instead of nickel octoate and carbon blacks.
As the result, after running for about 7 hours, the
reactor was completely plugged and stable running could
be continued no longer. The yield of the liquid fraction
having b.p. lower than 520 C was 72 wt. % and the amount
of cokes formed was 1.8 wt. %, but within the reactor,
about 1.2 wt. % of the cokes was found to have undergone
coking in the forrn containing partially the catalyst
added.
Comparative example 6
Example 1 was repeated excep-t that an aqueous
solution of ammonium molybdenate dissolved in water was
added in an amount of S00 ppm as molybdenum into the
feedstock oil to form an emulsion, to which were further
added 3 wt. % of pulverized particles of about 10 ~ to
30 ~ of a complex oxide of silica-alumina (silica 60 %,
alumina 40 %) which was a porous material with a speciic
surface area of 400 m2/g (BET method) instead of nickel
octoate and carbon blacks. As the result, after running
~4369
- 32 -
~or about lO hours, the reactor was completely plugged
and stable running could be continued no longer. The
~ield of the liquid fraction having b.p. lower than
520 C was 75 wt. % and the amount of cokes formed was
305 wt. %, but within the reactor, about 1.2 wt. % of the
cokes was found to have undergone coking in the form con
taining partially the particulate material added.
As apparently seen from the results of Example
l and Comparative examples 1 through 6, the present in-
vention can be appreciated to be excellent as the method
for obtaining a high yield of lighter oil by cracking of
a heavy hydrocarbon. Moreover, the residual oil having
b~po higher than 520 C obtained in the present inven-
tion has a viscosity as low as 22 cst at 150 ~C, and its
combustibility by thermogravimetric analysis is similar
to the vacuum residue of the feedstock Minus crudes, and
thus it was sufficiently available as fuel oil.
Examples 2 - 10
Using a vacuum residue of Minus crudes llOO wto
% of the fraction having b,p. higher than 520 ~C~ as the
feedstock oil, various combinations of two kinds of com-
ponents were added thereto in predetermined amounts as
mentioned below to carry out thermal cracking by means of
the same reaction apparatus as in Example 1.
That is, in the case of Example 2, vanadium
octoate was added in an amount of 300 ppm as vanadium
and channel carbon black [average particle size: 14 m~
(EoM. method), specific surface area: 300 m2/g (BET
method)] was added in an amount of 2 wt. ~, respectively~
In the case of Example 3, copper octoate was
added in an amount of 500 ppm as copper and silicas
produced by liquid-phase process [average particle si~e~
36~
- 33 -
20 m~ (E.M. method), specific surface area: 150 m2/g (BET
method)] was added in an amount of 2 wt. %, respectively.
In the case of Example 4, molybdenum naphthenate
was added in an amount of 100 ppm as molybdenum and sili-
cas produced b~ vapor-phase processes [average particle
size: 8 m~ (E.M. method), specific surface area: 350 m2/g
(BET method)] was added in an amount of l wt. %, respec-
tively.
In the case of Example 5, an aqueous solution of
ammonium heptatungstate was added in an amount of 600 ppm
as tungsten and an alumina produced by vapor-phase
process [average particle size: 20 m~ (E.M. method),
specific surface area: 100 m2/g (BET method)] was added
in an amount of 3 wt. ~, respectively7
In the case of Example 6, an aqueous solution of
cobalt sulfate was added in an amount of 800 ppm as cobalt
and an anatase type titanium oxide produced by vapor-phase
process [average particle size: 30 m~ (E.M. method),
specific surface area: 50 m2/g (BET method)~ was added in
an amount of 6 wt. %, respectively.
In the case of Example 7, nickel stearate was
added in an amount of 300 ppm as nickel and calcined
cokes micropulverized by a jet crusher ~average particle
size: 400 m~ (E.M. method), specific surface area: 35 m2/g
(BET method)] was added in an amount of lO wt~ ~, respec-
tively.
In the case of Example 8, chromium resinate was
added in an amount of 700 ppm as chromium and thermal
decomposition carbon black [average particle si~e: 180 m~
(E.M~ method), specific surface area: 15 m2/g (~ET method)~
was added in an amount of 7 wt. %, respectively.
~Z~36~
- 34 -
In the case of Example 9, nickel acetylacetonate
was added in an amount of 500 ppm as nickel and fluid
cokes micropulverized by a jet crusher [average particle
size: 800 m~ (E.M~ method), specific surface area:
25 m2/g (~ET method)] was added in an amount of 10 wt. %,
respectively.
In the ca~e of Example 10, iron pentacarbonyl
was added in an amount of 1000 ppm as iron and silicates
produced by li~uid~phate processes (containing 18 % of
calcium oxide) ~average particle size: 30 m~ (E.M.
method), specific surface area: 80 m2/g (BET method)] was
added in an amount of 3 wt. %, respectively.
In Examples 7 and 9, each 1 wt. % of a dis-
persant composed primarily of calcium petroleum sulfonate
and a dispersant composed primarily of polybutenyl-
succinimide was further added to the feedstock oil,
respectively.
, The reaction conditions employed for thermal
cracking were a temperature of 495 C, a pressure of 200
kg/cm2, a residence time (based on cold liquid) of 20
minutes and the number of revolutions of the stirrer of
1000 rpm in all Examples 2 to 10, a hydrogen/~eedstock
oil ratio o~ 2000 NQ/Q in Examples 2 to 7, and a hydrogen
with 3 mol % of hydrogen sulfide/feedstock oil ratio of
2000 NQ/Q in Examples 8 to 10. The steady state running
for each Example was 30 hours.
As the result of the experiment, in all these
Examples, stable running was possible without causing
plugging of the reactor, with the con~ersion being within
the range from 75 to 85 wt. % and the yield of the li~uid
fraction boiling at lower than 520 C being within the
range from 70 to 78 wt. %. In addition, the amount of
cokes formed was within the range from 0.7 to 2 wt. ~,
36~
t
and the amount of coking on the inner wall surface in
the reactor was within the range from 40 to 200 ppm based
on the total weight of the feedstock fed.
Example 11
An Arabian light vacuum gas oil (b.p. 343 -
520 C) containing lO00 ppm as nickel of nickel stearate
and 10 wt. % of oil furnace carbon black [average particle
size: 15 m~ (E.M. method), specifid surface area 200 m2/g]
was charged in an amount of 3 kg into an autoclave of an
inner volume of lO liter, hydrogen gas containing 5 mole %
of hydrogen sulfide was pressurized into the autoclave at
a charging pressure of lO0 kg/cm2 and the reaction was
carried out under stirring at lO00 rpm at a temperature of
~20 C for one hour. After the reaction, the contents
were filtered, washed and extracted with tetrahydrofuran,
followed by drying to obtain a solid product. The solid
product was added to a vacuum residue of Minus crudes
dissolved by heating (lO0 wt % of the fraction having
b.pD higher than 520 C) to a content of lO wt. % and
dispersed highly therein by ultrasonic wave. The resul-
tant dispersion was added to the same Minus vacuum residue
as mentloned ahove to a solid content of 2 wt. %. The
mixture was thoroughly stirred and provided for use in
steady state running of the reaction conducted by the
same reaction apparatus and under the same conditions as
in Example l for 30 hours.
As the result of the experiment, running could
be accomplished stably without causing plugging of the
reactor, with the conversion being 81.6 wt. % and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 75.6 wt. %. The amount of the cokes
Eormed was 0.8 wt. % and the amount of coking on the
inner wall surface of the reactor was 40 ppm based on the
total weight of the feedstock fed.
369
- 36 -
Example 12
5ilicas produced by vapor-phase processes
[average particle size: 16 m~ (E.M. method~, specific
surface area: 200 m2/g tBET method)] (300 g) was sus-
pended in hydrogen gas containing 5 mole % of hydrogen
sulfide in a fluidized bed and, while being permitted to
fly with rotation through the gas stream, subjected to
atomizing mixing with an aqueous solution of ammonium
heptamolybdate in an amount of 15 g as molybdenum. Then,
while maintaining the temperature of the gas stream at
430 C, the reaction was carried out for one hour. The
solid product obtained by this procedure was added to the
vacuum residue of Minus crudes (lO0 wt. % of the fraction
having b.p. higher than 520 C) to a content of 2 wt. %,
and the feedstock oil was thoroughly stirred and fed to
the reactor. The reaction apparatus and the reaction
conditions were the same as in Example l, and the steady
state running conducted fox 20 hours.
As the result of the experiment, running could
be accomplished stably without causing plugging of the
reactor, with the conversion being ~0.9 wt. ~ and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 74.9 wt. %. The amount of the cokes
formed was 1.2 wt. % and the amount of coking on the
inert wall surface of the reactor was 95 ppm based on the
total weight of the feedstock fed.
Example 13
The product oil obtained in Example l was
subjected to atmospheric distillation and vacuum distil-
lation to remove the fraction boiling at lower than
520 C. The resultant residue was filtered under heat-
ing. The solid residue after extraction of the ~iltered
product with tetrahydrofuran was dried and added to a
3f~9
37
vacuum residue of Minus crudes ~100 wt. % of the frac-
tion having b.p. higher than 520 ~C) to 4 wt. %, followed
by addition of 0.5 wt. % of a dispersant composed pri-
marily of calcium petroleum sulfonate. The mixture was
thoroughly stirred and fed into the reactor. The re-
action apparatus and the reaction conditions were the
same as in Example 1, and the steady state running con-
ducted for 30 hours.
As the result of the experiment, running could
be accomplished stably without causing plugging of the
reactor, with the conversion being 81.~ wt. % and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 75.4 wt. %. The amount of the cokes
formed was 1.6 wt. % and the amount of coking on the
inner wall surface of the reactor was 1~0 ppm based on
the total weight of the feedstodk fed.
Example 14
The product oil obtained i~n Example 1 was
subjected to atmospheric distillation and vacu~un distil-
lation to remove the fraction having b.p. lower than
520 C. The resultant residue was added to a vacuum re-
sidue of Minus crudes (100 wt. % of the fraction having
hop~ higher than 520 C) to 4 wt. %, followed by addi-
tion of molybdenum naphthenate in an amount of 500 ppm
as molybdenum based on the feedstock oil and further by
addition of 0.5 wt. % of silicas produced by vapor-
phase processes [average particle size: 8 m~ (E.M. meth-
od), specific surface area: 350 m2/g (~ET method)] to
the feedstock oil. The mixture was thoroughly stirred
and fed into the reactor. The reaction apparatus and
the reaction conditions were the same as in Example 1,
and the steady state running conducted for 30 hours.
As the result of the experiment, running could
~;24~369
- 38~-
be accomplished stably without causing plugging of the
reactor, with the conversion being 74.8 wt. ~ and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 69.7 wt. ~. The amount of the cokes
formed was 2.0 wt. % and the amount of coking on the
inner wall surface of the reactor was 180 ppm based on
the total weight of the feedstock fed.
Example 15
Using a vacuum residue of Taching crudes (100
wto % of the fraction having b.p. higher than 520 QC) as
the feedstock oil, thermal cracking was conducted by
means of the same continuous type equipment operated
with high pressures as used in Example 1.
As the components to be added to the feedstock
oil~ copper naphthenate was added in an amount of 500 ppm
as copper and silicas produced by liquid-phase processes
[average particle size: 15 m~ (E.M. method), specific
surface area: 210 m2/g (BET method)] was added to a con-
tent of 2 wt. %. The feedstock was thoroughly stirred
before feeding to the reactor.
The reaction conditions employed for thermal
cracking were a temperature of 490 C, a pressure of
lS0 kg/cm2,ar-esi-dence time (based on cold liquid) of 20
minutes and a hydrogen/feedstock oil ratio of 2000 NQ/Q,
wi~ll the number of revolutions of the stirrer being
1000 rpm. The steady state running was continued for
50 hoursO
As the result of the experiment, running could
be accomplished stably without causing plugging of the
xeactor, with the conversion being ~1.4 wt. ~ and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 76.0 wt. %. The amount of the cokes
~LZ~36~
- 39 -
formed was 1.4 wt. ~ and the amount of coking on the
inner wall surface of the reactor was 20 ppm based on the
total weight of the feedstock fed. The amount of hydro-
gen consumed was found to be 100 NQ/kg-feedstock.
Example 16
Using a vacuum residue of Arabian light crudes
(100 wt~ % of the fraction having b.p. higher than
520 C) as the feedstock oil, thermal cracking was con-
ducted by means of the same continuous type equipment
operated with high pressures as used in Example 1.
As the components to be added to the eedstock
oil~ vanadium acetylacetonate was added in an amount of
500 ppm as vanadium and further silicas produced by
vapor-phase processes ~average particle size: 12 m~ (E.M.
method), specific surface area: 230 m2/g (BET method)] was
added:to a content of 3 wt. ~. T~e f,eedstock,,was,,thoroughly
stirred before feeding to the reactor.
The reaction conditions employed for thermal
cracking were a temperature of 480 C, a pressure of
200 kg/cm2, a residence time (based on cold liquid) of
25 minutes and a hydrogen/feedstock oil ratio of 2000
M~/Q, with the number of revolutions of the stirrer being
1000 rpm~ The steady state running was continued for
100 hours~
As the result of the experiment, running cold
be accomplished stably without causing plugging of the
reactor, with the conversion being 74.7 wt. % and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 68.9 wt. %. The amoun-t of the cokes
formed was 1.0 wt. % and the amount of coking on the
inner wall surface of the reactor was 200 ppm based on
the total weight of the feedstock fed. The amount of
249~3~9
-- ~o ~--
hydrogen consumed was found to be 170 NQ/kg-feedstockO
Example 17
Using a vacuum residue of Venezuela crudes
(100 wt. g6 of the fraction having b.p. higher than
520 C) as the feedstock oil, thermal cracking was con-
ducted by means of the same continuous type equipment
operated with high pressures as used in Example 1.
As the components to be added to the feedstock
oil, nickel naphthenate was added in an amount of 500
ppm as nickel and furthex silicas produced by liquid-
phase processes [average particle size: 15 m~ (E.M.
method), specific sufface area~ 210 m2/g (BET method)]
was added to a content of 2 wt. %. The feedstock was
thoroughly stirred before feeding to the reactor.
The reaction conditions employed for thermal
cracking were a temperature of 485 C, a pressure of
200 kg/cm2, a~residence time(based on cold liquid) of 25
minutes and a hydrogen/feedstock oil ratio of 2000 NQ/Q,
with the number of revolutions of the stirrer being 1000
rpm. The steady state running was continued for 20 hours.
As the result of the experiment, running could
be accomplished stably without causing plugging of the
reactor, with the conversion being 78.2 wt. % and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 71.9 wt. ~. The amount of the cokes
formed was 2.8 wt. % and the amount of coking on the
inner wall surface of the reactor was 2ao ppm based on
the total weight of the feedstock fed. The amount of
hydrogen consumed was found to be 190 NQ/kg-feedstockO
``` 1;Z~3~9
t
- 41 -
Example 18
Using a vacuum residue of Maya crudes (100 wt.
% of the fraction having b.p. higher than 520 C) as the
feedstock oil~ thermal cracking was conducted by means
of the same continuous type equipment operated with high
pressures as used in Example 1.
As the components to be added to the feedstock
oil, nickel naphthenate was added in an amount of 500 ppm
as nickel and further silicas produced by liquid-phase
processes [average particle size: 15 m~ ~E.M. method),
specific surface area: 210 m2/g (BET method)] was added
to a content of 2 wt. %. The feedstock was thoroughly
stirred before feeding to the reactor.
The reaction conditions employed for thermal
cracking were a temperature of 485 C, a pressure of 200
kg/cm2, a residence time (based on cold liquid) of 25
minutes and a hydrogen/feedstock oil ratio of 2000 NQ/Q,
with the number of revolutions of the stirring being 1000
rpmO The steady state running was continued for 20 hours.
As the result of the experiment, running could
be accomplished stably without causing plugging of the
reactor, with the conversion being 75.4 wt. % and the
yield of the liquid fraction obtained having b.p. lower
than 520 C being 68.1 wt. %. The amount of the cokes
formed was 2.7 wt. % and the amount of coking on the
inner wall surface of the reactor was 280 ppm based on the
total weight of the feedstock fed. The amount of hydrogen
consumed was found to be 220 NQ/kg-feedstockO
Example 19
A mixture of all the product oils of Examples 1
to 5 and 10 to 14 was used as the feedstock oilO Bv means
369
- 42 -
of a continuous type hydrotreating reaction apparatus of
18 mm ~ inner diametex in which the fixed-bed reactor was
packed with Ni-~o/A1 catalyst with a surface area of 270
m2/g and a porosity of 0.75 ml/g containing 5 wt. % of
nickel oxide and 20 wt. ~ of molybdenum oxide, after
application of presulfiding on the catalyst, hydrogena-
tion was conducted under the reaction conditions of a
hydrogen/feedstock oil ratio of 1000 NQ/Q, a temperature
of 400 C, a pressure of 180 kg/cm2 and LHSV of 0.8 hr~1.
The properties of the feedstock oil and the hydrotreated
oil recovered are shown in Table 1.
Example 20
Using a fraction obtained by removing high boil-
ing components having b.p. higher than 520 C ~rom the
product oil in Example 1 by atmospheric distillation and
vacuum distillation, as the feedstock oil, and Co-Mo/Al
catalyst with a surface area of 240 m2/g and a porosity
of 0.53 ml/g containing 4 wt. % of cobalt oxide and 14
wt. % of molybdenum oxide, applied with presulfiding,
hydrotreatment was conducted by means of the same continu-
ous type hydrotreating reaction apparatus as used in
Example 19 under the reaction conditions of a hydrogen/
feedstock oil ratio of 1000 NQ/Q, a temperature of 390 C,
a pressure of 150 kg/cm2 and LHSV of 1.0 hr~l. The
properties of the feedstock oil and the hydrotreated oil
recovered are shown in Table 1.
Example 21
Using a fraction obtained by removing high boil-
ing components ha~ing b.p. higher than 520 C from the
product in Example 16 by atmospheric distillation
and vacuum distillation, as the feedstock oil, and Ni-
~lo/Al catalyst with a surface area of 2~0 m2/g and a
porosity of 0.60 m~g containing 4 wt~ ~ of nickel oxide
~z~43~9
- 43 -
and 14 wt. % of molybdenum oxide, applied with presulfid-
ing~ hydrotreatment was conducted by means of the same
continuous type hydrotreatment reaction apparatus as used
in E~ample 19 under the reaction conditions of a hydrogen/
feedstock oil ratio of 1000 NQ/Q, a temperature of 400 C,
a pressure of 200 kg/cm2 and LHSV of 0.8 hr 1. The pro-
perties of the feedstock oil and the hydrotreated oil
recovered are shown in Table 1.
Table 1 Changes in Oil Properties by Hydrotreatment
. Exam ~le lg Exam ~le 20 Exam ~le 21
Feed- Hydro- Feed- Hydro- Feed- Hydro-
stock treated stock treated stock treated
oil oil oil
Specific gravity 0.8490 0.8100 0.8327 0.8048 0.8703 0.8358
H/C (atomic ratio) 1.79 1.951.88 1.99 1.69 1.92
Sulfur content(wt.%) 0.05 trace 0.02 trace 2.31 0.01
Nitrogen content 0.12 0.05 0.050.02 0.06 0.01
Conradson carbon 6.40 0.02 0.07~ trace 0.15 trace
residue (wt.%) .
Type analysis (column¦
chromatograplly)
Saturated comp(ne%n)t 175.o 91.579.3 93.0 55.2 91.1
Aromatic compon(ent%) 18.9 8.315.7 6.9 39.4 8.4
Polar components %) 1 6.1 0.2 5.0 0.1 5.4 0.5
Hydrogen distribution
(H-NMR)
Aromatic hydrogen(%) 3.9 1.1 3.2 1 l.0 6.1 1.3
Olefinic hydrogen(%) 1.1 trace 1.0 trace 1.4 trace
Aromatic a-position 6.0 4.8 5.8 4.8 12.8 7.2
hydrogen (%)
Methylene hydrogen 66.4 69.3 65.8 69.5 55.5 66.4
Methyl hydrogen (%) 22.6 25.0 24.2 24.7 24.2 25.1
.
~Z4~369
- 4~ -
Example 22
From the thermally cracked product removed of
~he gaseous components obtained in Example 1 using the
vacuum residue of Minus crudes as the feedstock, the high
boiling components having b.p. higher than 520 C were re-
moved according to atmospheric and vacuum distillation.
The fraction boiling at lower than 520 C was
steam pyrolyzed by means of a tubular heater type pyro-
lyzer under the conditions of an inlet temperature of
550 ~C, an outlet temperature of 830 C, an outlet pres-
sure of 0.~ kg/cm2G, a steam oil weight ratio
of 1.0 and a residence time of 0.2 seconds to ob-tain
olefins and monocyclic aromatics.
The results of the steam pyrolysis are given
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
per feedstock of the vacuum residue of Minus crudes in
Table 2.
Example 23
The hydrotreated oil removed of the gaseous
components obtained in Example 20 using the Minus vacuum
residue as the starting material was subjected to steam
pyrolysis similarly as in Example 22 under the conditions
of an inlet temperature of 550 C, an outlet temperature
of 830 C, an outlet pressure of 0.8 kg/cm2G, a steam/
hydrotreated oil weight ratio of 1.0 and a residence time
of 0O2 seconds to obtain olefins and monocyclic aromaticsO
The results of the steam pyrolysis are given
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
per feedstock in Table 20
1~ 69
- 45 -
Comparative example 7
The thermally cracked product obtained in stable
running in Comparative example 1, from which the gaseous
components were removed r was subjected to atmospheric and
vacuum distillation in the separation step, and the frac-
tion boilincJ at lower than 520 C was applied with the
procedure of hydrotreating step and steam pyrolysis step
similarly as in Example in 20 and 23, respectively.
The results of the steam pyrolysis are shown
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
in Table 2.
Comparative example 8
The thermal cracking step was practiced by us-
ing a vacuum residue of Minus crudes as the feedstock oil,
the same hydrotreating apparatus as in Example l9, Ni-W
catalyst on 70 wt. % silica/30 wt. % alumina with a sur-
face area of 230 m2/g and a porosity of 0.37 ml/g contain-
ing 6 wto % of nickel oxide and 19 wt. % of tungsten
oxide, and also employing the conditions under which the
catalyst activity deterioration is not marked in initia-
tion of running, namely a temperature of 380 C, a re-
action pressure of 200 kg/cm2G, LHSV of 0.5 hr l and a
hydrogen/feedstock oil ratio of 2000 NQ/Q. The yield of
the liquid fraction boiling at lower than 520 ~C was
only 16.5 wt. %. The resultant liquid fraction was
subjected to the same steam pyrolysis as in Example 220
The results of the steam pyrolysis are given together
with the yields of the main chemical starting materials
(main gaseous olefins and monocyclic aromatics) per
feedstock in Table 2.
As apparently seen from the results in Examples
36~3
- 46 -
22 and 23 and Comparative examples 7 and 8, the method of
the present invention can be appreciated to be excellent
as -the method for decomposing heavy hydrocarbons to give
starting materials to be supplied for steam pyrolysis,
thus providlng high yields of petrochemical starting
materialsO
Example 24
From the thermally cracked product removed of
the gaseous components obtained in Example 15 using the
vacuum residue of Taching crudes as the feedstock, the
~lgh boiling components having b.p. higher than 520 C
were removed according to atmospheric and vacuum distil-
lationO
The fraction boiling at lower than 520 C was
steam pyrolyzed by means of a tubular heater type
pyrolyzer under the conditions of an inlet temperature
of 550 C, an outlet temperature o 830 C, an outlet
pressure of 0.8 kg/cm2G, a steam oil weight
ratio of 1.0 and a residence time of 0O2 seconds to ob-
tain olefins and monocyclic aromaticsO
The results of the steam pyrolysis are given
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
per feedstock in Table 2.
Example 25
From the thermally cracked product removed of
the gaseous components obtained in Example 16 using the
vacuum residue of Arabian light crudes as the feedstock,
the high boiling components having b.po higher than
520 C were removed by separation according to atmospheric
and vacuum distillationO
~ ~Z~436~
- 47 -
The fraction boiling at lower than 520 C was
steam pyrolyzed by means of a tubular heater type pyro-
lyzer under the conditions of an inlet temperature of
550 C, an outlet temperature of 830 C, an outlet
pressure of 0.8 kg/cm2G, a steam oil weight
ratio of 1.0 and a residence time of 0.2 seconds to obtain
olefins and monocyclic aromatics.
The results of the steam pyrolysis are given
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
per feedstock in Table 2.
Example 26
The hydrotreated oil removed of the gaseous com-
ponents obtained in Example 21 using the vacuum residue of
~rabian light crudes as the feedstock was steam pyrolyzed
by means of a tubular heater type pyrolyzer under the con-
ditions of an inlet temperature of 550 C, an outlet tem-
perature of 830 C, an outlet pressure of 0.8 kg/cm2G~ a
steam/hydrogenated oil weight ratio of 1.0 and a residence
time of 0.2 seconds to obtain olefins and monocyclic
aromatics.
The results of the final step of subjecting the
hydrogenated oil to the steam pyrolysis are given together
with the yields of the main chemical starting materials
(main gaseous olefins and monocyclic aromatics) per feed~
stock in Table 20
~IL2~4369
- 48 -
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~ ~ o ,, C~ ~ ,` ~ ~ CO ~ o~ ~ ~
~q ~ ~D `D O~
a) ._ _._ _ ,~
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~ ~ o ~ ~ o ~ ~ oo ~ C~l
:n ~ ~ ~ . _ _ ~
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.~ ~ ~ O O~ D O ~ U~ ~ ~D l u~
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rd ,~ ~o. ~ ~ ~ l o ~ c~ x
r~ ~ ~ O ~ r~~ O U~ ~D ~ r~ a~ ~
~ x~ ~ ~ ,~ ,i ~ ~
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t~ t~ a~ o~) ~ co ,-1 oc~ oo co ~ u~ ~-1 u~ ~ ~
h r O O O u ) ~ OD 1~ ~ ~ ~ r-i a) U
~1 E3 ~ r-l ~ r-l r_l ~ ~) O~ t~ .r~ ~ ~
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r . ~
rOO ~ S~ ~ ~ '
5~ ~ ~3: o â~ ~:; d
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O U~~ ~ ~ ~ ,~ ~ ,C ~ ~ .~
u~ (du~ ~1 ~ ~: ~ ruC
~1 ~ , ~ U ~ 1~
o ~ ~I c ~ ~ ~ o~ v c c
~ d ~ o o v v v ~-- ,-~
,_1 h ~ ~ ~ V ~ ~,t aJ d o ~rt V r-t
E-l 1 40 wo ~ ~0 40 a) a~
~ ~ ~ ~ ~ '.L) ~ a) zo
r-l d ~ r~ r~ r~ ~) r-l
a~ ~ ~ o ~ al ~ ~d a
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Examples 27 - 30
The thermally cracked product obtained in
Examples ll~ from which the gaseous components were
removed, in the case of ~xample 27,
the thermally cracked product obtained in
Examples 12, from which the gaseous components were
removed, in the case of Example 28,
the thermally cracked product obtained in
Example 13, from which the gaseous components were
removed, in the case of Example 29,
the thermally cracked product obtained in
Examples 14, from which the gaseous components were
removed, in the case of Example 30, were each employed
as the hydrocarbon oil converted to lighter products in
~he respective thermal cracking steps, and each oil was
subjected to atmospheric and vacuum distillations in the
respective separation steps for removal of the components
having b.p. higher than 520 C.
Each of the hydrocarbon oils stripped of the
high boiling cornponents with b.p. higher than 520 C was
subjected to hydrotreatment simi~arly as in Exa~ple 20.
Each of the hydrotreated oil removed
of gaseous components was subjected to steam pyrolysis
similarly as in Example 22~
The results of the steam pyrolysis are given
together with the yields of the main chemical starting
materials (main gaseous olefins and monocyclic aromatics)
per vacuum residue of Minus crudes which is the starting
material in Table 3.
~2~3~9
- s~ I
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+
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o ~ u~ ~ ~ oo co ~D u~ ~ O ~ ~ _
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3 ~ o~ ~ ~ ~ ~ ~o ~
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__ _ --Q.~- I L~ +
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td ~ o o hd ~ u td h
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bO ~ a ~ O ~~ ~ ~ ~, ~0 40
o ~ ~ ~ ~~ ~ V t)
(~ ~ rV ~ P' v ~ ~; d~ d ~ a
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E-l v ~o ~o~l ~oJ 4-ol o ~ ~
n ~ ~ 1 r~ ~J
d ~ ~ r~ d r 1 r~l ~1 (U
a~ o-,-~ o v ~:U tl~ C'd ~ aJ ~U V
.~ .~.~ rl ,C rl Tl ~ O
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. 5~ _ ~LZ49~36g
Examples 31 and 32
Using an atmospheric residue of Minus crudes
(100 wt. % of fraction having b~p. higher than 343 C,
45 wt. % of fraction having b.p. higher than 520 C) as
the feedstock, thermal cracking was conducted by means of
the same continuous type equipment operated with high
pressures as in Example 1.
As the two kinds of the components to be added
to the feedstock oil in thermal cracking, there were added
molybdenum naphthenate in an amount of 100 ppm as molyb-
denum and oil furnace carbon black ~average particle sizeO
15 m,u (E.M. method), specific surface area: 200 m2/g (BET
method)] in an amount of 2 wt. %, respectively, in the
case of Example 31; and an aqueous solution of ammonium
molybdenate dissolved in water in an amount of 500 ppm
as molybdenum to form an emulsion, to which was further
added an alumina produced by the vapor-phase processes
[average particle size: 20 m~ (E.M. method), specific
surface area: 100 m2/g (BET method)] in an amount of 3 wt.
% in the case of Example 32.
The thermal cracking conditions were, in each
c:ase, a temperature of ~90 C, a presence of 150 kg/cm2,
a residence time (based on cold liquid) of 18 minutes and
a hydrogen/feedstock rat:io of 1500 ~Q/Q, with the number
of revolutions of the stirrer of 1000 rpm.
The thermally cracked products freed of gaseous
components were each subjected to atmospheric and vacuum
distillations in the respective separation step similarly
as in Example 20 for removal of high boiling components
with b.p. higher than 520 C, and the fraction boiling at
lower than 520 C was steam pyrolyzed to obtain olefins
and monocyclic aromatics.
1~4a~3~
~ 52 -
The results of steam pyrolysis of Example 31 and
32 are set forth in Table 4~ together with the yields of
the main chemical starting materials (main gaseous olefins
and monocyclic aromatics).
Examples 33 and 34
Using an atmospheric residue of Arabian light
crudes (100 wt. % of fraction having b.p. higher than
343 C, 46 wt. % of fraction having b.p. higher than
520 C) as the feedstock, thermal cracking was conducted
by means of the same continuous type equipment operated
with high pressures as in Example 1.
As the two kinds of the components to be added
to the feedstock oil in thermal cracking, there were
added iron pentacarbonyl in an amount of 800 ppm as iron
and channel carbon black [average particle size: 14 m~
(E.M. method), specific surface area- 300 m2/g (BET
method)] in an amount of 2 wt. %, respectively, in the
case of Example 33; and cobalt resinat~ in an amount of
300 ppm as cobalt and thermal carbon black [average
paxticle size: 80 m~ (E.M. method), specific surface
area. 15 m2/g (BET method)] in an amount of 6 wt. % in
the case of Example 34.
The thermal cracking conditions were, in each
case, a temperature of 470 C, a pressure of 200 kg/cm2,
a residence time (based on cold liquid) of 30 minutes and
a hydrogen/feedstock oil ratio of 2000 NQ/Q, with the
number of revolutions of the stirrer of 1000 rpm.
The thermally cracked products freed of gaseous
components were each sub~ected to atmospheric and vacuum
distillations in the respective separation step for re-
moval of high boiling components with b.p. higher than
520 C.
3~
- 53 -
Using the fraction boiling at lower than 520 C
obtained as the feedstock oil, hydrotreatment was con-
ducted by means of the same continuous type hydrotreat-
ing reaction apparatus and fixed-bed catalyst as in
Example 19 under the conditions of a hydrogen/feedstock
oil ratio of 1000 NQ/Q, a temperature of 395 C, a
pressure of 180 kg/cm2 and LHSV of 0.8 hr
The hydrotreated oil recovered was steam
pyrolyzed by means of a tubular heater type pyrolyzer
under the conditions of an inlet temperature of 550 C,
an outlet temperature of 830 C, an outlet pressure of
0O8 kg/cm2G, a steam/hydrogenated oil weight ratio of
loO and a residence time of 0.2 seconds to obtain olefins
and monocyclic aromatics.
The results of steam pyrolysis of Examples 33
and 34 are set forth in Table 4, together with the yields
of the main chemical starting materials (main gaseous
olefins and monocyclic aromatics).
lZ~g~3~
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