U.S. patent number 3,617,513 [Application Number 04/788,830] was granted by the patent office on 1971-11-02 for coking of heavy feedstocks.
This patent grant is currently assigned to Esso Research and Engineering Company. Invention is credited to Jacob B. Angelo, Edward L. Wilson, Jr..
United States Patent |
3,617,513 |
Wilson, Jr. , et
al. |
November 2, 1971 |
COKING OF HEAVY FEEDSTOCKS
Abstract
The formation of char in fluid coking is inhibited by the
presence of hydrogen-donor compounds in the fluid coking zone,
increasing the yield of desirable liquid products. A hydrogen-donor
solvent is admixed with a heavy fluid coker feedstock in amounts
sufficient to provide at least 10 weight percent of hydrogen-donor
compounds, based on total feed to the fluid coker. Preferable
compounds for use as hydrogen donors are the partially saturated
hydroaromatic compounds such as indane, C.sub.10 -C.sub.12
tetralins, C.sub.12 and C.sub.13 acenaphthenes, di-, tetra-, and
octahydroanthracene, and tetrahydroacenaphthene. The process is
particularly useful in the production of liquid hydrocarbon
products from solid coal wherein the coal is subjected to solvent
liquefaction and the resulting liquid slurry is fed into a
fluid-coking zone. Where hydrogen-donor solvent is used for the
liquefaction step, and it does not become completely
hydrogen-depleted, no additional solvent need be added prior to
fluid coking. However, additional hydrogen-donor solvent may be
added (and if not nondonor solvent was used in liquefaction, must
be added) prior to such coking. The use of additional
hydrogen-donor solvent further enhances the yield of liquid
products and inhibits char yield. Preferably, the fluid-coking step
will be used in conjunction with an external burner, and a portion
of the product coke will be removed for use in generating hydrogen
by contact with steam, with such hydrogen being used to satisfy at
least in part the demands for hydrogen in the hydrogenation of the
recycle solvent.
Inventors: |
Wilson, Jr.; Edward L.
(Baytown, TX), Angelo; Jacob B. (Houston, TX) |
Assignee: |
Esso Research and Engineering
Company (N/A)
|
Family
ID: |
25145697 |
Appl.
No.: |
04/788,830 |
Filed: |
January 3, 1969 |
Current U.S.
Class: |
208/127; 208/53;
208/413; 208/425; 208/56; 208/416; 208/427 |
Current CPC
Class: |
C10B
49/22 (20130101); C10B 55/00 (20130101); C10G
1/002 (20130101); C10B 55/10 (20130101) |
Current International
Class: |
C10B
49/22 (20060101); C10B 55/00 (20060101); C10B
49/00 (20060101); C10G 1/00 (20060101); C10B
55/10 (20060101); C10g 009/32 () |
Field of
Search: |
;208/8,56,127 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levine; Herbert
Claims
We claim:
1. In the fluid coking of an admixture of liquids and solids
obtained by solvent liquefaction of coal containing less than 5
weight percent of compounds capable of hydrogen-transfer donation
under coking conditions,
the improvement of concurrently coking in admixture with said
feedstock a hydrogen-donor solvent boiling within the range from
300.degree. F. to 900.degree. F. and containing hydrogen-donor
compounds chosen from the group consisting of C.sub.10 to C.sub.12
tetralins, indane, C.sub.12 and C.sub.13 acenaphthenes, di-,
tetra-, and octahydroanthracene and tetrahydroacenaphthene, and
mixtures of two or more thereof,
said hydrogen-donor compounds constituting at least 30 weight
percent of said solvent and at least 10 weight percent of the
admixture of liquid, solids, and solvent.
2. A process in accordance with claim 1 wherein by solvent
liquefaction of coal, and the hydrogen-donor solvent is at least in
part supplied by unreacted solvent from said liquefaction.
3. A process in accordance with claim 2 wherein fluid coking
conditions include
a temperature from about 1,000.degree. F. to about 1,500.degree. F.
and
a pressure from about zero p.s.i.g. to about 30 p.s.i.g.
4. A process for obtaining liquid hydrocarbon products from solid
coal which comprises
1. in a liquefaction zone contacting said coal with a
hydrogen-donor solvent under liquefaction conditions chosen to
obtain a liquefaction zone slurry product containing partially
hydrogen-depleted donor solvent, liquefied coal, undissolved coal
and mineral matter,
said partially hydrogen-depleted donor solvent retaining sufficient
hydrogen-donor constituents so that such constituents constitute at
least 10 weight percent of the total slurry product,
2. coking the entire slurry product in a fluid coking zone under
coking conditions including a temperature within the range from
1,000 to 1,500.degree. F.,
whereby a coker distillate stream and a coke stream are
obtained,
3. separating said coker distillate stream into at least a recycle
solvent fraction and another fraction,
said recycle solvent fraction boiling within the range from
350.degree. F. to 900.degree. F.,
4. hydrogenating said recycle solvent fraction, and
5. using at least a portion of said hydrogenated recycle solvent
fraction as the hydrogen-donor solvent in step (1).
5. A process in accordance with claim 4 further comprising the
steps of:
6. burning at least a portion of the coke stream in a burning zone
to generate heat for the coking reaction and to obtain a recycle
coke stream and a product coke stream,
7. contacting at least a portion of said product coke stream with
steam under hydrogen-producing conditions, and
8. returning said recycle coke stream to said coking zone.
6. A process in accordance with claim 4 wherein the liquefaction
conditions include
a temperature from 700.degree. F. to 1,000.degree. F.,
a pressure from 350 p.s.i.g. to 3,000 p.s.i.g., and
an average oil residence time from 5 to 60 minutes, and
wherein the coal particle size range is about 8-mesh and
smaller.
7. A process in accordance with claim 6 wherein the recycle solvent
contains at least about 50 weight percent hydrogen-donor compounds,
and has a boiling range from about 372.degree. F. (at about 8.4
percent over) to about 785.degree. F. (at about 94.4 percent over),
and where the solvent-to-coal ratio is about 1.2/1, by weight.
8. A process for obtaining liquid hydrocarbon products from solid
coal which comprises
1. in a liquefaction zone contacting said coal with a
hydrogen-donor solvent under liquefaction conditions chosen to
obtain a liquefaction zone slurry product containing partially
hydrogen-depleted donor solvent, liquefied coal, undissolved coal
and mineral matter,
said partially hydrogen-depleted donor solvent retaining sufficient
hydrogen-donor constituents so that such constituents constitute at
least 10 weight percent of the total slurry product,
2. adding to said slurry product fresh hydrogen-donor solvent,
3. coking the mixture of slurry and fresh hydrogen-donor solvent
under fluid coking conditions including a temperature within the
range from 1,000.degree. F. to 1,500.degree. F.,
whereby a coker distillate stream and a coke steam are obtained,
and the yield of coke is reduced.
9. A process in accordance with claim 8 wherein at least a portion
of the liquid portion of the slurry is removed prior to addition of
fresh hydrogen-donor solvent.
10. A process in accordance with claim 9 wherein at least 50 weight
percent of the liquid feed to the coker is fresh hydrogen-donor
solvent and at least 30 weight percent of the fresh hydrogen-donor
solvent is constituted of hydrogen-donor compounds.
Description
DISCUSSION OF PRIOR ART
The search for a commercially attractive process for making liquid
products from coal began long ago. The coking (pyrolysis) of coal
has long been a well-established industry, with liquid byproducts
being recovered along with the primary product, coke. Solvation of
coal, with or without the addition of molecular hydrogen, has also
long been known as a feasible but not an economically attractive
process for obtaining liquid products from coal (as exemplified by
U.S. Pat. No. 1,342,790 ). The Pott-Broche process (e.g., U.S. Pat.
No. 1,881,927), with modifications, was capable of producing
high-cost gasoline from coal. During World War II Germany produced
large quantities of synthetic fuels using coal as a feedstock, but
at a prohibitively high cost. After the cessation of hostilities,
when crude oil again became available to Germany, the more
economical process of refining petroleum supplanted synthetic fuels
production.
With the possible dwindling of supplies of crude oils, however, the
search for an economically attractive coal liquefaction process has
continued. Gorin has suggested several process schemes utilizing a
hydrogen-donor solvent in the liquefaction zone, and limiting the
conversion so as to selectively liquefy only those materials most
susceptible to hydrotreating. In this scheme, however, the need for
separating undissolved solids from the liquid extract phase adds
greatly to investment and operating costs. (See U.S. Pat. Nos.
3,018,241 and 3,117,921, for example). Johnson (Re. 25,770) and
Schuman et al. (U.S. Pat. No. 3,321,393) have suggested the
hydrogenation of coal in a three-phase system utilizing a
liquid-fluidized bed of hydrogenation catalyst. This scheme also is
burdened with the need for high-temperature solids-liquid
separation. The present invention avoids the need for a mechanical
means of solids-liquid separation at high temperatures by charging
the entire liquid-solids slurry from a liquefaction zone into a
fluidized coker. The lighter material readily vaporizes leaving the
heavier liquid components to crack and volatilize in the presence
of hydrogen-donor solvent, producing additional lighter components
and resulting in a reduced char yield.
Many patents have suggested the use of coking as a part of a coal
liquefaction process. Gorin's patents (U.S. Pat. Nos. 3,018,241 and
3,018,242) suggest the "carbonization" of the solid residue
remaining after solids-liquid separation. Pevere et al. (U.S. Pat.
No. 2,664,390) suggest carbonization of a mixture of liquids and
solids, but "oversize solid particles" must be removed, apparently
to avoid plugging the nozzles of the atomizer which is employed.
Pevere et al. do not use a hydrogen-donor solvent or fluid coking.
Frese et al. (U.S. Pat. No. 2,738,311) suggest the coking of heavy
oil and residue, but first flash off all lighter components
(including all possible hydrogen-donor solvents) and do not
contemplate fluid coking at all.
As can be seen by the foregoing discussion, the prior art has not
contemplated the combination of hydrogen-donor liquefaction and
fluid coking which forms the basis of the present invention.
DISCUSSION OF THE INVENTION
The present invention is directed to a process for converting coal
into liquid products. Basically, the invention depends upon the
combination of a hydrogen-donor liquefaction step with a succeeding
fluid coking of the liquid products from the liquefaction zone in
the presence of unconsumed hydrogen-donor solvent. As a
modification, however, it should be understood that any type of
coal liquefaction (e.g., nonhydrogen-donor solvation) can be
carried out and a hydrogen-donor solvent added to the liquid
products from the liquefaction zone, with or without first having
flashed off a substantial amount of the lighter materials.
In order better to understand the present invention, each of the
sections of the complete overall process scheme will be separately
discussed. It should be clearly understood, however, that the
overall scheme, which envisions the production of hydrogen from
withdrawn coke from the burner, is exemplary only and that the
production of hydrogen need not be carried out in order to enjoy
the benefits of the present invention.
Mixer
Solid Feed. The basic feedstock to the process of the present
invention is a solid, particulate carbonaceous material, such as
bituminous coal, subbituminous coal, lignite, brown coal, etc.
Although it is desirable to grind the coal to a particle size
distribution from about 8-mesh and finer, it has been found that
the solvation reaction will result in a size reduction even if
particles as large as one-fourth inch on the major dimension have
been introduced into the liquefaction zone. Thus, it is possible to
charge large chunks of coal rather than the preferred finely
divided coal. A typical inspection of the feed coal thus far
experimented with is given in table I, below.
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TABLE I
Typical Feed Coal Inspections
Moisture, saturated 13.0 Ash, Dry 10.6 Mineral matter, dry 12.8
Vol. Matter, DMF* 45.1 Fixed Carbon, DMF 54.9 Carbon, DMF 79.1
Hydrogen, DMF 5.59 Oxygen, DMF 10.6 Nitrogen, DMF 1.24 Sulfur,
Total, dry 4.70 Sulfur, Pyritic, dry 1.71 Sulfur, Organic, DMF 3.42
B.t.u./lb., Dry 12,610 B.t.u./lb., DMF 14,360
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*dry, mineral-free.
The carbonaceous material preferably is dried to remove excess
water, although it is feasible to charge the "wet" coal if the
liquefaction facilities have been sized to allow the withdrawal of
evolved steam. The coal can be dried by conventional techniques
prior to introduction into the mixer used to establish the slurry
feed for liquefaction. Preferably, however, the wet coal is mixed
with hot hydrogen-donor oil which is charged tO the mixer and water
is volatilized in the mixer, thereby reducing the feed slurry
moisture content to less than about 2 weight percent. Thus, the
mixer also serves the function of a drier.
Hydrogen-Donor Solvent.
In the mixer, the coal feedstock at ambient temperature is admixed
with a liquid solvent, preferably a hydrogen-donor solvent, which
is at a temperature from 500.degree. to 700.degree. F. The
solvent/coal weight ratio is within the range from 1/1 to 2/1,
resulting in a slurry temperature within the range from 300.degree.
to 350.degree. F. A mechanical propeller or other agitating device
may suitably be provided in the mixing zone so as to obtain a
uniform slurry concentration.
The solvent stream will boil within the range from 350.degree. to
900.degree. F. (preferably from about 375.degree. to about
800.degree. F.) so as to remain in the liquid phase after the
slurry has been formed. Preferably, the solvent will contain at
least 30 weight percent (preferably at least 50 weight percent) of
compounds which are known to be hydrogen donors under the
liquefaction conditions and (as has now been discovered) under
coking conditions.
Hydrocarbon streams containing one or more of the hydrogen-donor
compounds, in admixture with nondonor compounds or with each other,
will be suitable. Compounds such as indane, C.sub.10 to C.sub.12
tetralins, C.sub.12 and C.sub.13 acenaphthenes, di-, tetra-, and
octahydroanthracene, and tetrahydroacenaphthene are preferred as
hydrogen-donor compounds, as are other derivatives of the partially
saturated hydroaromatic compounds.
Where the solvent stream is a hydrogenated recycle solvent fraction
(as is preferred), the composition of the equilibrium solvent will
vary somewhat, depending upon the source of the coal used as a
feedstock to the system and the operating conditions in the
liquefaction, coking and solvent hydrogenating sections. However, a
typical description of the hydrogenated recycle solvent fraction
will be similar to that shown in table II. ##SPC1##
Liquefaction Zone
The slurry of coal in solvent is passed into a liquefaction zone,
where the convertible portion of the coal is allowed to dissolve
and depolymerize to form free radicals. At the temperature
maintained within the liquefaction zone (e.g., about 750.degree.
F.), the coal softens almost instantaneously and the expanding
gases trapped within the coal particles cause vesiculation and
swelling of the particles. Where, as is preferred, the slurry is
preheated in a furnace-type heater before introduction into the
liquefaction zone, the softening begins while the coal particles
are in the furnace-type heater. Within approximately 5 minutes, the
coal particles disintegrate to produce some low molecular weight,
benzene-soluble materials. Little hydrogen transfer is involved in
this disintegration phase, even if donor-type solvents are used,
but nondonor solvents such as dodecane do not disperse the
fragments of coal as well as do tetralin and naphthalene. The
dispersed fragments (not necessarily liquefied) are cracked to
produce free radicals which can recombine to form material which is
not soluble even in pyridine. If a hydrogen-donor solvent is
present, however, the tendency to recombine is substantially
inhibited, both in the liquefaction zone and in the coking zone.
Since the depolymerized (cracked) coal molecules can either
recombine with each other or be stabilized by accepting hydrogen
from the donor solvent, the degree of inhibition will depend on the
amount of donor solvent which is present. Where the donor solvent
contains about 50 weight percent of hydrogen-donor constituents,
and the solvent/coal ratio is from 1/1 to 2/1, the concentration of
hydrogen-donor constituents in the liquefaction zone can be seen to
range initially from 25 weight percent to 331/3 weight percent and
will be depleted by the liquefaction reaction. However, molecular
hydrogen can be added to the liquefaction zone to partially
replenish the hydrogen-donor solvent by in situ hydrogenation of
the depleted molecules (e.g., naphthalenes may be hydrogenated to
tetralins).
Liquefaction conditions which are suitable may include a
temperature from 650.degree. to 1,000.degree. F., a pressure from
300 p.s.i.g. to 3,000 p.s.i.g., a solvent/coal weight ratio from
1/1 to 2/1, a molecular hydrogen input rate from zero to 4 weight
percent (based on m.a.f. coal charged into the liquefaction zone in
the slurry), and an oil residence time of 5 to 60 minutes, all so
combined as to obtain a MEK conversion in the range from 60 to 90
weight percent, preferably about 85 weight percent. The conversion
is expressed as the percent of moisture and ash free (m.a.f.) coal
that is converted to materials which are soluble in methylethyl
ketone (MEK). It is calculated by the equation:
wherein
a=percent ash in the moisture-free coal feedstock,
S.sub.f =percent solids in the feed slurry,
S.sub.p =percent solids in the product slurry.
Before measuring S.sub.p, MEK is added to the product slurry as a
solvent, in the ratio of 1 volume of MEK for each volume of product
slurry. The results so obtained are referred to as "MEK
conversion."
As aforesaid, in the liquefaction zone the hydrogen-donor solvent
reacts with the free radicals resulting from depolymerization. As a
result, even though hydrogen may be charged into the liquefaction
zone to replenish the donor solvent, a portion of the
hydrogen-donor solvent becomes hydrogen-depleted. The degree of
depletion is a function of the specific solvent and of the
conditions employed. A typical recycle solvent will contain about
50 weight percent of compounds which will donate hydrogen and,
during about 1 hour within the liquefaction zone with molecular
hydrogen being added, will be depleted to the extent that only 25
weight percent of the solvent is made up of hydrogen-donor
compounds.
A gaseous phase product is removed from the liquefaction zone as
well as the liquid slurry. Exemplary compositions of the gas
product and liquid product (without separation from solids in the
slurry) are given below in table III.
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TABLE III
Exemplary Gas and Liquid Products
Gas Product Liquid Product Comp. Wt. % Temp. .degree.F. Cum. Wt. %
Sp.Gr. 60/60.degree. F.
__________________________________________________________________________
Co 1.2 337 IBP CO.sub.2 21.8 437 7.4 0.9014 H.sub.2 S 17.7 485 14.7
0.9496 CH.sub.3 SH 5.2 549 22.6 0.9667 H.sub.2 4.7 596 31.4 1.0089
C.sub.1 20.1 658 40.2 1.0370 C.sub.2 15.8 732 49.0 1.0560 C.sub.2
.sup. 0.4 786 53.4 1.0791 C.sub.3 7.3 835 59.1 Solid C.sub.3 .sup.
0.5 [Btms 30.9] Solid C.sub.4 2.9 100.0 C.sub.4 .sup. 1.1 C.sub.5
1.3 100.0
__________________________________________________________________________
operating conditions in the liquefaction zone are shown in table IV
in comparison with operating conditions in the other zones.
Since the amount of hydrogen-donor components in hydrogen-donor
solvents is substantially reduced by the liquefaction step, it may
be desirable to add more of such components to the slurry effluent
from the liquefaction zone. This is easily accomplished by adding
hydrogenated recycle solvent to the slurry before it is introduced
into the coking zone. Suitably, the slurry may first be passed
through a flash zone to partially remove the lower boiling
materials, including the materials boiling in the range of the
solvent. Thus, at least a portion of the partially
hydrogen-depleted donor solvent is removed, to be replaced by fresh
hydrogenated recycle solvent. If such a flash zone is used, the
slurry (at a temperature of about 800.degree. F. and a pressure of
about 350 p.s.i.g.) is dropped to a pressure of about 100 p.s.i.g.,
and the liquid volume reduced by flashing (e.g., to about one-half
the original volume). Additional recycle solvent may be added in
amounts from one-half the volume of the removed solvent (which
would effectively replace the donor constituents removed by
flashing) to twice the volume (or more) of the removed solvent. As
shown later, the donor solvent is not substantially cracked in the
coking zone, so the additional volume is limited only by the heat
load required to vaporize the solvent in the coker. The addition of
fresh hydrogen-donor solvent reduces char make in the coker.
Coking
Preferably, a fluid coking zone is employed, whereby volatile
matter is driven off and heavier materials are cracked to produce
distillable products. A fluid coking zone is operated at elevated
temperatures which promote the further depolymerization and
cracking of the coal (as well as of liquefied components thereof
which are in the slurry). As aforesaid, the cracking and
depolymerization reactions form free radicals which may recombine
and polymerize, resulting in the production of char. However, by
providing a substantial amount of hydrogen-donor compounds as part
of the coker feedstock, the tendency toward polymerization is
inhibited and char yield is reduced, with a concomitant increase in
the yield of liquid products.
In the fluidized coking zone, a bed of heated coke particles is
maintained in the fluid state. The slurry feed is directed into the
bed of coke for vaporization and cracking. The vaporous and gaseous
products are removed overhead as a coker distillate stream and
fractionally distilled. The heavier components may be recycled to
the coking zone while the lighter products may be separated into a
recycle solvent stream and at least one product stream (boiling at
temperatures lower than the boiling range of the recycle
solvent.
Heat for the coking reactions is supplied by removing a portion of
the coke in the coking zone and burning a part thereof, whereby the
remaining removed coke is highly heated before being returned to
the coking zone as the source of heat. A suitable fluid coker will
have a coke holdup of 1,522 tons and a coke circulation rate of 68
tons/minute. Steam diluent may be added at the rate of 260,000
lb./hr.
The coking reaction can also be accomplished in a delayed coker or
by other processes well known in the refining arts. The fluid
coking process is preferred for use with the present invention, and
is carried out in the manner well known to those skilled. in the
art, since the presence of the hydrogen-donor solvent does not
deleteriously affect operation of the coking unit.
Coke Burner
In the coke burner, a recirculating stream of coke from the coker
is contacted with air in order to burn off a part of the coke and
generate heat to support the coking reactions and vaporization
taking place within the fluidized coker. The coke burner will
operate generally under conditions including a temperature from
1,000.degree. to 1,500.degree. F., a pressure from zero to 30
p.s.i.g., a superficial gas velocity of 0.5 to 4.0 ft./sec., an air
rate sufficient to provide the amount of heat required for the
coking zone and/or hydrogen production zone, and an average coke
residence time from 5 to 10 minutes. If withdrawn excess coke is to
be used for the generation of hydrogen, a hydrogen generator will
be placed downstream of the coke burner. For most efficient
operation, a second burner will be provided for the hydrogen
generator. This second burner would operate at a higher temperature
(e.g., 2,000.degree. F.) in order to provide heat for the
high-temperature hydrogen production zone. Where only one burner is
employed, air or oxygen must be introduced into the hydrogen
generator to burn additional coke and raise the temperature to the
desired level.
Hydrogen Generator
The hydrogen generator receives hot coke from the burner and
contacts it with steam in order to carry out the water-gas
reaction:
C+H.sub.2 O CO +H.sub.2
Unreacted steam is carried from the hydrogen generator along with
the carbon monoxide and hydrogen and is suitably contacted in a
shift reactor with further steam and a shift catalyst in order to
obtain more hydrogen, following the shift reaction:
CO+H.sub.2 O CO.sub.2 +H.sub.2
Suitable catalysts for use in the shift reaction are well known,
including the old iron oxide catalysts and the newer catalysts such
as copper/zinc oxide combinations. A two-stage shift reaction
utilizing a high-temperature catalyst in the first stage and a
low-temperature catalyst in the second stage may be employed, if
desired.
The hydrogen generator operates with a fluid bed of coke, as does
the burner and the coker. The coke is maintained in a fluid bed by
the injection of the reactant steam. Air or oxygen may be introduce
to react with coke in the bed and evolve heat, there raising the
temperature of the coke to the desired level. Alternatively, a
second burner may be used, as aforesaid, which is operated at a
higher temperature (e.g., 2,000.degree. F.) in order to maintain
the 1,600.degree.-1,800.degree. F. temperature required in the
hydrogen generator. Operating conditions in the hydrogen generator
include a steam rate of 0.1 to 1.0 pound per hour per pound of coke
in inventory, a temperature from 1,600.degree. to 1,800.degree. F.,
a pressure form zero to 250 p.s.i.g., and average coke residence
time of 0.5 to 2 hours, a bed depth of 10 to 15 feet, and a
superficial gas velocity of 0.5 to 4.0 feet/second.
All of the operating conditions for the various reaction zones are
shown in table IV.
Solvent Hydrogenation Zone
The solvent hydrogenator receives the recycle solvent (boiling
generally within the range from 350.degree. to 800.degree. F.) from
the coker fractionator. It is contacted in the solvent
hydrogenation zone with hydrogen in presence of a hydrogenation
catalyst such as cobalt molybdate, and under hydrogenation
conditions such as a temperature from 650.degree. to 850.degree.
F., a pressure from 650 to 2,000 p.s.i.g., and a space velocity
from one to six weights of liquid per hour per weight of catalyst.
The hydrogenated oil is then fractionated to the desired boiling
point range in a stripping tower before being sent back to the
mixer. Table II shows the analysis of a typical hydrogenated
solvent.
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TABLE IV
Operating Conditions
Liquefaction Zone Minimum Maximum Preferred
__________________________________________________________________________
Temperature, .degree.F. 700 1,000 800 Pressure, p.s.i.g. 350 3,000
1,000 Solvent/coal wt. ratio 1/1 2/1 1.2/1 Wt. % H.sub.2 (on MAF
coal) 0 4 2 Oil residence time, min 5 60 30 MEK Conversion, wt. %
60 90 85
Fluid Coker Temperature, .degree.F. 900 1,300 1,100 Pressure,
p.s.i.g. 0 30 12 Superficial gas velocity, ft./sec. 0.5 4 2 Coke
particle size, microns 10 1,000 20-500 Bed Density, 1b./cu.ft. 15
60 40 Space velocity, w./hr./w. 0.1 1.0 0.3
Coke Burner Temperature, .degree.F. 1,000 1,500 1,200 Pressure
p.s.i.g. 0 30 15 Superficial Gas Velocity, ft./sec. 0.5 4 3.0
Hydrogen Generator Temperature, .degree.F. 1,700 1,900 1,800
Pressure, p.s.i.g. 20 300 150 Superficial gas velocity, ft./sec.
0.5 4.0 2.5 % Coke gasified/hr. 20 40 30 Ash concentration, wt. %
50 70 60 Steam conversion, wt. % 40 80 60
Solvent Hydrogenation Temperature, .degree.F. 650 850 700 Pressure,
p.s.i.g. 650 2,000 1,350 Space Velocity, w./hr./w. 1 6 2 SCF
H.sub.2 /bbl. feed 1,000 10,000 5,000
__________________________________________________________________________
EXAMPLES
The following examples show the effect of hydrogen-donor solvent on
char yield in various coking operations. All char yields are weight
percent, based on coal feed.
Example 1
A nondonor solvent oil (boiling at 450.degree. to 750.degree. F.)
was mixed with finely divided coal at a solvent/coal weight ratio
of 2/1. The mixture was subjected to a temperature of 1,100.degree.
F. at ambient pressure to coke the mixture (equivalent to delayed
coking). The char yield was 61.0 weight percent, not quite as high
as the char yield obtained by coking coal at 1,100.degree. F. in
the absence of a solvent (78 weight percent).
Example2
Finely divided coal was well dispersed in naphthalene (a nondonor
oil) at a solvent/coal ratio of 2/1 and subjected to liquefaction
conditions of 750.degree. F. for 20 minutes. From an analysis of
benzene insoluble materials in liquid product, correlations
indicated that a char yield of 77 weight percent would have been
obtained if the product had been coked.
Example 3
Example 2 was repeated with the coal dispersed in dodecane (a
nondonor solvent at a solvent/coal ratio of 2/1, and subjected to
liquefaction at 750.degree. F. for 43 minutes. Correlations
indicated a char yield of 77 weight percent.
Example 4
Illinois coal, ground to a particle size distribution of about
100-mesh and finer was first dried and then contacted in a mixer
with a hydrogen-donor solvent similar to that described in table II
at a solvent/coal weight ratio of 1.2/1. The the resultant
admixture was passed through a liquefaction zone at 775.degree. F.
and a pressure of 350 p.s.i.g. for a residence time of about 60
minutes, and the total liquid slurry effluent from the liquefaction
zone was charged to a fluid coker at a temperature of 1,000.degree.
F. and a pressure of 10 p.s.i.g. The car yield was 45.4 weight
percent.
Example 5
Example 4 was repeated with a solvent/coal ratio of 2/1 and under
liquefaction conditions of 850.degree. F. and 980 p.s.i.g. Char
yield was 35.0 weight percent, showing a reduction in char yield
due to additional donor solvent in the coker feed.
Example 6
Example 4 was repeated except that the slurry effluent from the
liquefaction zone was centrifuged to obtain a residual solids
product which contained about 50 weight percent solids and 50
weight percent liquid. This residual solids product was slurried in
fresh hydrogen-donor solvent to a solids concentration of about 25
weight percent before being charged to the coking zone. The char
yield was only 18.1 weight percent, showing a further reduction in
char yield due to the further increase in additional donor solvent
in the coker feed.
Example 7
Depleted donor solvent was charged to the coker at 1,000.degree. F.
and 10 p.s.i.g. Only 1.2 weight percent was degraded to gas and 0.2
weight percent to char, with 98.4 weight percent being recovered
undegraded. This establishes the fact that solvent losses due to
passage through the coking zone are quite low and are almost
negligible. It has been found by mass spectographic analysis that
five-sixths of the hydrogen transferred in the coker from donor
solvents was donated to the liquid products and only one-sixth to
molecular hydrogen. This indicates that only slight degradation of
the donor solvent is suffered in the coking zone, and only minor
amounts of the hydrogen transferred was lost as molecular
hydrogen.
a preferred specific application of the present invention is shown
in the drawing, which represents a schematic diagram of a coal
liquefaction scheme utilizing a fluidized coker for processing the
effluent from the coal liquefaction zone.
Referring now to the drawing, it is seen that particulate coal is
introduced by way of line 100 into a mixer 102, wherein it is
combined with a recycle oil stream introduced by way of line 104 to
form a paste. The solvent/coal ratio in the mixer may suitably be
about 1.2 parts of solvent per part of coal (by weight). The slurry
from the mixer 102 is conducted by way of line 106 into a
liquefaction zone 108 which is maintained under liquefaction
conditions including a temperature of about 800.degree. F. and a
pressure of about 1,000 p.s.i.g. Hydrogen also may be introduced (2
weight percent, based on m.a.f. coal feed) in the gaseous form by
way of line 110 if desired, although it is not necessary for the
basic H.sub.2 donor process. Within the liquefaction zone 108,
hydrogen is transferred from the hydrogen-donor solvent to the
coal, causing a depolymerization of the coal along with the
solvation effect of the solvent. Thus, within the liquefaction zone
108 is produced a mixture of undepleted hydrogen-donor solvent,
depleted hydrogen-donor solvent, dissolved coal, undissolved coal,
and mineral matter. This mixture remains in the liquid phase, and a
vapor phase of lighter hydrocarbons and gases is maintained above
the liquid phase.
The liquid mixture is removed by way of line 111 and is transported
into a fluid coker 114. The flash vessel 112 may be employed, if
desired, as will be hereinafter discussed. The fluid coker is
operated to maintain a dense phase bed 115 of coke particles within
the lower portion thereof. The bed is maintained in the fluidized
state by steam introduced through line 116 and by the evolution of
vapors from volatilization and cracking of the feed stream being
introduced by way of line 117.
Within the coker 114, the liquid hydrocarbons undergo thermal
cracking and, because of the presence of undepleted hydrogen-donor
solvent, hydrogen donation does occur so as to enhance the
depolymerization and cracking of the coal molecules thereby
maximizing the production of vaporous products and minimizing the
amount of char which is produced and laid down on the bed of
coke.
A portion of the coke in the coker 114 is withdrawn by way of line
118 and is carried through the line 120 by an entraining gas stream
such as steam introduced by way of line 122 and is introduced into
a fluidized bed 124 in the burner 126. The fluidized bed of coke
124 is maintained in the fluidized state by air which is introduced
by way of line 128 as well as fluidizing steam which may also be
introduced. It is also partially maintained by the evolution of
combustion products from the reaction of air with the carbon and
hydrogen which make up the coke particles. A flue gas is removed by
way of line 130, while hot coke particles are removed by way of
line 132 and are entrained in a carrying steam stream introduced by
way of line 134 for passage through line 136 and reintroduction
into the coker 114.
The vaporous products from the coker 114 pass upwardly through a
cyclone separator 140 and are therein separated from entrained coke
particles which are returned through the dip leg 142 beneath the
level of the fluidized bed. The vaporous products are fractionated
in a distillation tower (suitably mounted directly above the coker
vessel, as indicated) and a bottoms product such as hydrocarbons
boiling above 1,000.degree. F. are removed from the tower and
recycled by way of line 144 into the coke bed for further
conversion.
The fractionator also may be operated to produce a heavy gas-oil
stream boiling within the range from 700.degree. to 1,000.degree.
F. as indicated by line 146, a naphtha stream boiling up to about
400.degree. F. which is removed by way of line 148 and a gas stream
which is removed by way of line 150. A recycle solvent stream
boiling within the range from about 400.degree. to about
700.degree. F. is removed by way of line 152 and at least a portion
thereof is recycled for use as hydrogen-donor solvent by way of
branch line 154. If desired, a portion of this stream may be
removed for further treatment and disposition by way of product
line 156.
The recycle solvent is contacted in the hydrogenation zone 160 with
hydrogen which is introduced by way of line 162, in the presence of
a hydrogenation catalyst such as cobalt molybdate and under
hydrogenation conditions such as a temperature of about 700.degree.
F., a pressure of about 1,350 p.s.i.g., and a space velocity of
about 2 weights of liquid per hour per weight of catalyst. The
hydrogenated oil is removed by way of line 164 and may be passed
through a flash separation zone 166, for the removal of hydrogen
and light ends through line 168, if desired. The liquid from this
flash zone passes through line 167 into a stripping zone 190 where
the naphtha is removed through line 191. The solvent leaves the
stripping zone through line 193 and is optionally split into two
separate streams. Stream 194 can be used to enrich the coker feed
with fresh H.sub.2 donor oil and the other portion of the
hydrogenated liquid passed by way of line 104 into the mixer 102 as
discussed above. The stream 194 is best used in conjunction with
flash zone 112, wherein the liquid volume of the slurry may be
reduced by 50 percent and the volume reconstituted by addition of
fresh solvent.
If desired, the gaseous products from the liquefaction zone 108 may
be removed by way of line 170, passed through a separator 172, and
a gas stream removed by way of line 174. Light hydrocarbons in the
gaseous stream may be removed by way of line 176 and introduced
into the fractionating tower 145, for distillation along with the
products of the coker.
In order to provide a balanced unit, wherein hydrogen may be
manufactured from a portion of the coke from the coker 114, a
portion of the hot coke may be removed from the burner 126 by way
of line 180, entrained in steam introduced by way of line 182 and
passed by way of line 184 into a hydrogen production zone 186. In
the hydrogen production zone 186, the hot char is maintained in the
fluidized state with superheated steam introduced by way of line
188 and the transfer steam introduced by way of line 184.
In the hydrogen generator 186 the carbon in the char is converted
to carbon monoxide by reaction with the steam, with a net
production of hydrogen. The gaseous product, comprising a mixture
of carbon monoxide, hydrogen and water is removed by way of line
190 for further treatment such as reaction in a shift reactor to
convert the carbon monoxide into carbon dioxide by reaction with
steam, with a net production of more hydrogen. The product char is
removed from the hydrogen generator through a line (not shown).
Ultimately, the hydrogen may be purified by well-known processes
and returned for use as the hydrogen in the hydrogen-donor solvent
hydrogenation zone and for introduction into the liquefaction zone
if desired.
Thus, it is seen that the present invention does provide an
improved way of carrying out the liquefaction of coal and the
production of vaporous hydrocarbon products therefrom, wherein the
mechanical separation of solid particles from the extract from the
liquefaction zone is avoided and the formation of char in the
coking zone is minimized by the presence of the undepleted
hydrogen-donor solvent.
While the present invention has been discussed in connection with
the coking of coal extracts, it is equally applicable to the coking
of any heavy (e.g., 1,000.degree. F.+) hydrocarbon stream, such as
petroleum residua, where the production of liquid products should
be maximized and coke yield minimized.
Having disclosed our invention, what is to be protected by Letters
Patent should be limited only by the appended claims, and not by
the specific examples herein given.
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