[0001] The invention relates to a process for hydrocracking a hydrocarbon feedstock to obtain
more valuable lower boiling products such as liquefied petroleum gas (LPG), naphtha,
kerosene, and diesel. In particular, the invention concerns a process whereby heavy
polynuclear aromatic compounds are concentrated in a portion of the unconverted oil
so they can be removed, resulting in increased conversion and yield of products.
[0002] The complete conversion of petroleum or synthetic heavy gas oils to distillate products
such as gasoline, jet and diesel fuel in a hydrocracker is practically limited by
the formation of heavy polynuclear aromatic (HPNA) compounds. These compounds, formed
by undesired side reactions, are stable and virtually impossible to hydrocrack. HPNA
are fused polycyclic aromatic compounds having 7+ rings for example coronenes C
24H
12, benzocoronenes C
28H
14, dibenzocoronenes C
32H
16 and ovalenes C
32H
14.
[0003] HPNA with 7+ aromatic rings are by-products of hydrocracking reactions that can potentially
cause significant problems in hydrocracking units. When the solubility limit for the
HPNA is exceeded, solids form in transfer lines, valves and on heat exchanger surfaces.
Furthermore the HPNA can contribute to catalyst deactivation by reversible inhibition
and coke formation. HPNA problems particularly occur when processing heavy feedstocks
with high distillation endpoints and more aromatic cracked stocks in high conversion
recycle units.
[0004] Consequently, HPNA build up to high levels in the recycle streams normally employed
in high conversion processes, resulting in fouling of the catalysts and equipment.
[0005] The conventional solution to this problem is to remove a portion of the recycle oil
stream as an unconverted oil stream to purge the HPNA compounds from the system, effectively
balancing the HPNA purge rate with the rate of their formation by reactions. This
approach limits the total conversion level achievable in the hydrocracker.
[0006] In a conventional high conversion hydrocracking process, a hydrocarbonaceous heavy
gas oil feedstock is combined with a hydrogen-rich gas and reacted over catalyst to
obtain a hydrocracked effluent comprising less dense, lower molecular weight products.
The hydrocracked effluent from the reactor is condensed and separated in a separation
zone into a liquid portion comprising primarily hydrocarbons and a vapour portion
comprising primarily un-reacted hydrogen. The vapour from this separation may be combined
with hydrogen makeup to account for hydrogen consumed by reaction and may then be
compressed and re-circulated back to the reactor vessel. The first liquid portion
from the separation zone is then directed to a fractionation section where the lighter
products are distilled from the heavy unconverted products in a fractionation section
e.g. a fractionation tower or a series of fractionation towers. Heat is normally input
to this recovery operation in order to provide the necessary energy for separation.
[0007] The conventional approach to controlling the build-up of HPNA compounds in the recycle
oil is to withdraw a purge of recycle oil product from the unit as unconverted oil.
The purge rate may be adjusted so as to balance the rejection of HPNA with the net
production. Such a purge essentially reduces the achievable total conversion level
by hydrocracking to less than 100 percent. Depending on the feed quality and process
conditions the purge rate can be from one or two percent up to as high as 10 percent
of the fresh feed rate. The yield of valuable distillate products are correspondingly
reduced at substantial economic loss to the refiner.
[0008] U.S. patent No. 6,361,683 discloses a hydrocracking process whereby the hydrocracked effluent is hydrogen stripped
in a stripping zone to produce a gaseous hydrocarbonaceous stream which is passed
through a post-treatment hydrogenation zone to saturate aromatic compounds. The fractionation
zone is associated with a stripping zone which is fed with stripped hydrocarbonaceous
liquid obtained by stripping the hydrocracked effluent. Stripping to remove HPNA is
also considered.
[0009] U.S. patent No. 6,858,128 discloses a hydrocracking process which utilises a fractionation zone having a bottom
section with a dividing wall to include sections suitable for steam stripping to concentrate
HPNA.
[0010] U.S. patents No. 4,961,839 and
5,120,427 disclose a hydrocracking process in which all of the bottoms fraction is fed to a
stripping column, provided as a stub column at the bottom of the fractionation zone.
The fractionation zone is fed by a vapourised stream, for recovering a majority of
light hydrocarbons, while enabling a purge of a liquid net bottoms stream rich in
HPNA. The patent employs a high degree of vapourisation of the feed to the fractionation
in order to minimize the purged stream and to ensure that only a PNA free fraction
is recycled, but this high degree of vapourisation is associated with an undesired
consumption of energy.
[0011] There is substantial economic incentive to maximize the conversion of the heavy feed
and a key feature of most such processes is the recycle of unconverted oil back to
the reaction system thereby controlling the cracking severity and improving the selectivity
of the hydrocracking reactions to more desirable end products such as gasoline, jet
fuel and diesel fuel. All known hydrocracking processes and catalysts are, however,
subject to undesirable side reactions leading to the formation of heavy poly-nuclear
aromatic (HPNA) compounds, which accumulate in the unconverted oil, recycle stream.
These compounds are virtually impossible to convert by hydrocracking reactions and
show a strong tendency to build up to high concentration levels in the recycle oil
stream. As the concentration builds up, the performance of the reactor system is continuously
degraded leading to uneconomic conditions.
[0012] It is an objective of the invention to provide a hydrocracking process whereby conversion
of the heaviest and highest molecular weight materials into products is increased,
resulting in reduced net yield of unconverted oil.
[0013] It is a further objective of the hydrocracking process to minimize the need for purge
by concentrating the HPNA compounds in a portion of the unconverted oil stream.
[0014] These objectives are achieved by a hydrocracking process comprising the steps of:
- (a) combining a hydrocarbonaceous feedstock and a heavy bottom fraction recycle stream
with a hydrogen-rich gas to obtain a mixture comprising hydrocarbonaceous feedstock
and hydrogen;
- (b) catalytically hydrocracking the mixture comprising hydrocarbonaceous feedstock
and hydrogen in a hydrocracking zone to obtain a hydrocracked effluent;
- (c) separating the hydrocracked effluent into a first vapour portion and a first liquid
portion in a separation zone;
- (d) heating the first liquid portion to form a substantially vapourised first liquid
portion;
- (e) feeding the vapourised first liquid portion to a fractionation section producing
individual product fractions including a heavy bottom fraction comprising unconverted
oil at the bottom zone of the fractionation section;
- (f) withdrawing from the fractionation section the heavy bottom fraction;
- (g) splitting the heavy bottom fraction into a stream for stripping and a heavy bottom
fraction recycle stream;
- (h) stripping the stream for stripping, with a stripping medium, in a counter current
stripping column to form an overhead vapour and a stripped liquid;
- (i) feeding the overhead vapour to the fractionation section, to a recycle stream
or to a position upstream the fractionation section; and
- (j) removing at least a part of the stripped liquid from the the counter current stripping
column as a net purge of unconverted oil.
[0015] In one embodiment the vapourised first liquid portion is at least 50%, preferably
at least 75%, even more preferably at least 85%, and most preferably at least 90%
vapourised, and at most 95%, preferably at most 90%, even more preferably at most
85%, and most preferably at most 75% vapourised with the associated effects of increasing
separation of HPNA and product in the fractionation zone with increasing degree of
vapourisation, and increasing energy efficiency with decreasing vapourisation, as
any recycled vapourised fractions will undergo an additional phase change prior to
recycle.
[0016] In one embodiment a part of the stripped liquid is recycled, combined with the stream
for stripping and directed to an inlet of the counter current stripping column, resulting
in an increased concentration of HPNA in the net purge.
[0017] In one embodiment the recycled portion of the stripped liquid and/or the stream for
stripping is heated by heat exchange with the heavy bottom fraction, with the benefit
of increased recuperation of waste heat, and a better flow and separation of the liquid
in the stripper.
[0018] In a further embodiment, the stream for stripping is heated prior to the stripping
process to raise its temperature above its bubble point such as above 300°, preferably
above 320°C and most preferably above 330°C which has the effect of concentrating
the HPNA even further, by facilitating the evaporation of other constituents.
[0019] In a further embodiment thermal energy is transferred from the heavy bottom fraction
to the stripping medium by heat exchange, which allows heat exchange on streams which
have not been concentrated further into heavy unconverted oil by stripping.
[0020] In a further embodiment, the stripping medium is steam preferably medium pressure
steam having a pressure between 1 and 20 barg, more preferably between 3.5 and 10
barg and most preferably between 3.5 and 6 barg.
[0021] In an embodiment the first vapour portion comprises lighter low molecular weight
products and unconverted hydrogen.
[0022] Another embodiment provides as the heavy bottom fraction the highest normal boiling
fraction from the fractionation section, comprising hydrocarbonaceous material
[0023] In one embodiment improved separation is obtained in the counter current stripping
column as it comprises multiple equilibrium stages in the form of trays or packing
material.
[0024] In a further embodiment a part of the heavy bottom fraction is directed into a stream
of heavy bottom fraction for recycling and combined with the hydrocarbonaceous feedstock
for being input to the hydrocracking zone, to provide hydrocracking of unconverted
oil.
[0025] In an embodiment the flow rate of the stream for stripping is controlled by a flow
control unit according to a desired flow rate of the net purge of unconverted oil,
such that the net purge flow may be optimised.
[0026] The hydrocarbonaceous feedstock may be hydrotreated prior to hydrocracking.
[0027] In an embodiment some or all of the energy for heating of the stream for stripping
is provided from heat exchange with one or more streams from the hydrocracking process
e.g. a reactor effluent, or from heat exchange with an external source of heating
medium such as high pressure steam, hot flue gas from a fired heater, or by electrical
heating.
[0028] An embodiment involves a process wherein the stripped liquid comprises heavy polynuclear
aromatic compounds in an amount larger than the amount comprised in the heavy bottom
fraction withdrawn from the fractionation column, thus reducing the share of unconverted
oil in the net purge stream.
[0029] In a further embodiment stripping medium output from the stripping unit may be added
to the fractionation section, resulting in a saving of stripping medium consumption.
[0030] In a further embodiment the process further comprises the step of recycling some
of the stripped liquid from the counter current stripping column and mixing it with
the the stream for stripping, for feeding it to the counter current stripping column,
with the associated effect of providing an even higher concentration of HPNA in the
unconverted oil. In this case it may be necessary to add further heat to the counter
current stripping process, to ensure the liquid is above its bubble point temperature
during stripping.
[0031] In a further embodiment HPNA is extracted from the net purge by adsorption on an
adsorbent, to allow the net purge to be recycled to the process, with the benefit
of increased yield.
[0032] Fig. 1 illustrates an embodiment of the process according to the invention in which
flow control is employed on the stream for stripping and a part of the heavy bottom
fraction is recycled.
[0033] The disclosed process utilizes specific process steps to reduce the net purge of
unconverted oil from a hydrocracker. This reduction may be accomplished by taking
the bottom fraction stream from the bottom of the product fractionation section such
as a fractionation column, heating it substantially above its bubble point and then
stripping with steam in a counter-current column with fractionating trays or packing
material. The stripping step at elevated temperature vapourises a substantial amount
of the bottom fraction stream compared to simply stripping the heavy bottom fraction
at its bubble point without heating. The overhead vapour of the heavy bottom fraction
may be returned to the fractionation section e.g. at the bottom. The stripped part
of the heavy bottom fraction remains a liquid and is collected in the bottom of the
stripping tower. This stream is having a substantially higher boiling point than the
original unconverted oil and therefore HPNA is concentrated in the heavier bottoms
liquid, which may then be removed as net purge from the hydrocracker.
[0034] The higher concentration of HPNA in the stripped liquid allows the removal of the
desired amount of HPNA at lower purge rate in a net purge stream. The reduced net
purge rate results in higher total conversion in the hydrocracker together with increased
yields of valuable distillate products.
[0035] The concentration of HPNA in the net purge may even be further increased by recycling
a part of the stripped liquid of the heavy bottom fraction to an inlet of the stripper.
The recycled stream may be heated by heat exchange with e.g. the heavy bottom fraction
to optimise the heat consumption of the process.
[0036] This disclosure provides a simple process for concentrating the HPNA compounds in
a portion of the unconverted oil stream and thereby minimizing the required purge
flow rate. The required purge flow rate is reduced substantially leading to higher
conversion and better yields of final products.
[0037] The disclosure utilizes specific process steps to reduce the required purge of unconverted
oil from the hydrocracker substantially, such as at least 25 percent and preferably
by 50 percent or more. This reduction is accomplished by withdrawing a bottom fraction
comprising unconverted oil in a first purge stream from the fractionation section,
heating it substantially above its bubble point and then stripping with steam in a
counter-current column with fractionating trays or packing material. The stripping
step vapourises a substantial amount, such as at least 25 percent and preferably 50
percent or more of the bottom fraction stream returning this overhead vapour to the
bottom of the fractionation section. The remainder of the bottom fraction stream remains
as a stripped liquid and is collected in the bottom of the stripping tower. This liquid
is substantially higher boiling than the original unconverted oil and because of the
very high normal boiling point of the HPNA compounds, the physical separation concentrates
the HPNA in the heavier bottoms liquid, which is then removed as net purge from the
hydrocracker. The higher concentration of HPNA in the stripped liquid allows the removal
of the required HPNA at lower purge flow rate. The reduced purge rate results in higher
total conversion in the hydrocracker together with increased yields of valuable distillate
products.
[0038] By providing the stripping of the unconverted oil in a separate process step, multiple
advantageous effects are obtained. An independent temperature and flow control is
made possible, which allows an optimisation of the stripping conditions, and counter
current flow is enabled, which has a better stripping efficiency compared to co-current
flow.
[0039] Reference is made to Fig. 1, which illustrates schematically the process flows and
equipment configuration as embodied in this invention.
[0040] Fresh feedstock consisting of a hydrocarbonaceous feed, such as petroleum or synthetic
heavy gas oils of mineral or biological origin
1 is combined with hydrogen rich gas
2 and an optional recycle stream of unconverted product
16 and fed to a hydrocracking zone
3 consisting of one or more catalysts contained in one or more reaction vessels. The
catalysts promote the hydroconversion of the hydrocarbonaceous feedstock, which may
include hydrogenation to a lighter hydrocracked effluent. The hydrocracking effluent,
comprising hydrocarbon products together with excess hydrogen not consumed by the
reaction exits the hydrocracking zone
4 and enters a separation zone
5 consisting of one or more vessels that perform separation into a first vapour portion
and a first liquid portion. The first vapour portion
6 from the separation zone may be combined with makeup hydrogen
7 to replenish the hydrogen consumed by reaction. The hydrogen rich stream may then
be compressed in compressor
8 for recycle back to the hydrocracking zone.
[0041] The first liquid portion
9 from the separation step passes to a process heater
10 supplying energy for substantially vapourising the fluid
11 before feeding the product fractionation section
12. The fractionation section consists of one or more towers or columns with multiple
equilibrium stages in the form of trays or packing material which may be operated
in counter-current flow. The towers are normally stripped with steam or reboiled to
facilitate vapourisation of the products. The fractionation section performs the separation
of individual product and intermediate fractions
13, 14 such as gasoline, jet fuel and diesel fuel according to differences in their normal
boiling points. At the bottom zone of the fractionation section the heaviest bottom
fraction, i.e. unconverted oil
15, may be collected and withdrawn as an unconverted oil product or returned to the reactor
in line
16 as a recycle oil stream for further conversion.
[0042] The aim of a hydrocracking process is to convert all or as much of the heaviest and
highest molecular weight materials into products resulting in no or a minimal net
yield of unconverted oil
15. However, a first purge of unconverted oil or heavy bottom fraction
17 must be withdrawn from the hydrocracker possibly on flow control
18 in order to avoid a build-up of HPNA within the reaction system. In a heavy bottom
fraction stripping system, the heavy bottom fraction stream for stripping is routed
to a process heater
19 such that the temperature of this stream for stripping
20 is raised substantially above the bubble point of the stream for stripping and of
the temperature of the fractionation section bottom. This heated stream for stripping
is then fed to the top of a counter-current stripping tower
21 consisting of multiple equilibrium stages in the form of trays or packing material.
Steam is added to the bottom of the stripping tower
22 to facilitate vapourisation of the unconverted oil. The overhead vapour from the
top of the stripping tower
23 is routed to the bottom of the fractionating column
12. The stripped liquid portion of the stream for stripping which is not vapourised in
the stripper flows to the bottom of the tower and is then removed from the hydrocracker
as a net purge of unconverted oil
24.
[0043] The operating conditions in the heavy bottom fraction stripping system are established
such that the net purge of unconverted oil
24 from the bottom of the stripper is substantially less than the heavy bottom fraction,
i.e. unconverted oil
17 removed from the heavy bottom fraction stream for stripping, while sufficiently removing
the undesired HPNA.
[0044] Reference is made to Fig. 2, which illustrates schematically the process flows and
equipment configuration in a detail of a preferred embodiment, employing the same
reference numbers as Fig. 1 for similar elements in similar function.
[0045] Fig. 2 shows the flow scheme at the outlet of the fractionation section. The earlier
elements of the process correspond to those of Fig. 1 as described above.
[0046] As mentioned the aim of a hydrocracking process is to convert all or as much of the
heaviest and highest molecular weight materials into products resulting in no or a
minimal net yield of unconverted oil
15. However, a first purge of unconverted oil or heavy bottom fraction
17 must be withdrawn from the hydrocracker possibly on flow control
18 in order to avoid a build-up of HPNA within the reaction system. In a heavy bottom
fraction stripping system according to the present disclosure, the withdrawn heavy
bottom fraction stream is directed as a stream for stripping, and may be routed to
a process heater
19 such that the temperature of the stream for stripping
20 is raised substantially above the bubble point of the heavy bottom fraction stream
for stripping and of the temperature of the fractionation section bottom. This heated
stream for stripping is then fed to the top of a counter-current stripping tower
21 consisting of multiple equilibrium stages in the form of trays or packing material.
Steam is added to the bottom of the stripping tower
22 to facilitate vapourisation of the unconverted oil. The overhead vapour from the
top of the stripping tower
23 is routed to the bottom of the fractionation section
12. The stripped liquid from the stream for stripping which is not vapourised in the
stripper will flow to the bottom of the tower. A part of this stripped liquid is removed
from the hydrocracker as a net purge (a necessary purge) of unconverted oil
24, and another part
25 is recycled to an inlet of the stripping tower
22, which may either be the same or one different from the inlet through which the stream
for stripping from the fractionation section is fed. In Fig. Two, the recycled liquid
27 is heated by heat exchange
26 with the heavy bottom fraction
15 of the fractionation section.
[0047] The operating conditions in the heavy bottom fraction stripping system are established
such that the net purge of unconverted oil
24 from the bottom of the stripper is substantially less than the heavy bottom fraction,
i.e. unconverted oil
17 removed from the heavy bottom fraction stream for stripping, while sufficiently removing
the undesired HPNA.
[0048] In an alternate embodiment of the invention illustrated in Fig. 3, a portion
25 of the stripped liquid
24 is recycled and fed to the top of the stripper
21 after being heated by heat exchange with the heavy bottom fraction stream
24. Heating of this recycled stripped liquid is required because of the temperature drop
caused by contacting with the large volume of stripping steam. Substantial thermal
energy can be supplied to the stripped liquid and unconverted oil in this manner without
raising the temperature excessively above the feed temperature to the stripper. This
has the benefit of reducing the thermal degradation of the unconverted oil compared
to feeding the heavy bottom fraction to the stripper at a higher temperature. Further
in the embodiment of Fig. 3 the overhead vapour 23 is directed to a position upstream
the fractionation section 12 and not directly to the fractionation section, which
may require less reconfiguration in the case of retrofitting an existing unit, compared
to the embodiments where the overhead vapour is directed directly to the fractionation
section 12.
[0049] Under certain process conditions, it may be beneficial to avoid directing the high
boiling recycled stripped liquid to a heat exchanger. Therefore, under such process
conditions, it may be preferred to use the embodiment of Fig.4, in which the heat
of the heavy bottom fraction
15 is recovered by heat exchange in heat exchanger
30 with a steam line
22, providing superheated steam
31 which is fed to the stripper
21. A sufficient amount of low pressure steam of 170 °C may be heated to superheated
steam at 330°C in such a situation, while reducing the temperature of the heavy bottom
fraction by only about 5°C.
[0050] Dependent on the configuration of the hydrotreater and fractionation section, alternative
configurations of the stripping tower exist.
[0051] In alternative cases where the fractionation section
12 is a vacuum distillation column, or is a main fractionator with a fired reboiler,
such that it is not operated with steam, the HPNA concentrator will not be configured
to return a steam output to the fractionator. In these cases the HPNA concentrator
may be configured with a condenser for condensing the steam and the overhead hydrocarbons.
The overhead water from the steam may be reused as wash water, and the overhead hydrocarbons
may be fed to the fractionator, to the recycle stream or a position upstream the fractionator,
such as a feed surge drum.
[0052] In such alternative embodiments the heavy bottom fraction from the fractionation
column may still be used to preheat the recycled stripped liquid stream.
[0053] The pressure conditions of the stripper would be configured accordingly, e.g. to
operate under vacuum or low pressure if required, by being attached to the vacuum
system and using only a small amount of low pressure steam to strip the unconverted
oil.
[0054] In alternative embodiments alternatives to steam as stripping medium such as methane
or other gases, may also be used.
[0055] Further alternative destinations of the overhead vapour from the stripper may include
any position upstream the fractionation section including the inlet to the process
heater
10.
[0056] To optimise the yield further it is also possible to withdraw HPNA by adsorption
on a bed of activated carbon, or another absorbent, as it is disclosed in
US 4,447,315. Such a bed will work especially well in the case of a high concentration HPNA purge
stream, since the size of the bed may be smaller. Operation may involve operating
two parallel beds alternating, such that one bed may be regenerated or replaced without
interrupting plant operation.
EXAMPLES
Example 1
[0057] In order to test the potential split of HPNA in the proposed invention, a sample
of hydrocracked unconverted oil obtained from a commercially operating hydrocracking
plant with the properties shown in Table 1 was distilled in an ASTM D-1160 apparatus.
Since this apparatus does not utilize reflux it generates a physical separation with
substantial overlap between the overhead and bottoms product and corresponds well
to the vapour/liquid separation in a simple steam stripper.
Table 1
| Properties of Unconverted Oil Sample |
| Specific Gravity |
|
0.844 |
| Heavy Poly-Nuclear Aromatics |
|
|
| Coronene |
wtppm |
394 |
| 1-MethylCoronene |
wtppm |
132 |
| NaphCoronene |
wtppm |
127 |
| Ovalene |
wtppm |
91 |
| Total HPNA |
wtppm |
744 |
| Distillation |
|
|
| Initial Boiling Point |
°C |
342 |
| 10% |
°C |
397 |
| 50% |
°C |
451 |
| 90% |
°C |
513 |
| Final Boiling Point |
°C |
572 |
[0058] Two laboratory distillations were performed using the ASTM D-1160 method and apparatus,
the first yielding a bottoms fraction of 50 volume percent of the initial charge and
a second yielding a bottoms fraction of only 20 volume percent of the charge, to document
how the HPNA would partition in the overhead and bottoms fractions. The results of
HPNA analysis and distillation analysis on both the bottom fraction and the overhead
vapour fractions are summarized in Table 2.
Table 2
| Properties of Distilled Fractions |
| Case |
|
I |
II |
| Fraction |
|
Bottoms |
Distiltillate |
Bottoms |
Distiltillate |
| Yield |
%vol. |
50 |
50 |
20 |
80 |
| Specific Gravity |
|
0.849 |
0.838 |
0.855 |
0.840 |
| Heavy Poly-Nuclear |
|
|
|
|
|
| Aromatics |
|
|
|
|
|
| Coronene |
wtppm |
650 |
105 |
775 |
245 |
| 1-MethylCoronene |
wtppm |
240 |
20 |
385 |
55 |
| NaphCoronene |
wtppm |
235 |
<5 |
565 |
<5 |
| Ovalene |
wtppm |
175 |
<5 |
475 |
<5 |
| Total HPNA |
wtppm |
1300 |
130 |
2200 |
305 |
| Initial Boiling Point |
°C |
406 |
288 |
440 |
338 |
| 10% |
°C |
439 |
380 |
473 |
391 |
| 50% |
°C |
479 |
426 |
510 |
441 |
| 90% |
°C |
531 |
463 |
550 |
483 |
| Final Boiling |
°C |
583 |
511 |
596 |
529 |
| Point |
|
|
|
|
|
[0059] These results clearly show that the ASTM distillation has achieved a substantial
separation of HPNA between the overhead distillate and bottoms fraction. This is a
consequence of the very low volatility of the HPNA compounds. In a hydrocracker, it
is necessary to purge sufficient HPNA from the system to balance the net production
of HPNA by reaction. In this example, Case I results in an increase of the total HPNA
concentration by a factor of from 744 ppmwt to 1300 ppmwt or 175 percent. Case II
results in an increase of total HPNA by a factor of from 744 ppmwt to 2200 ppmwt or
295 percent.
Example 2
[0060] Performance of the invention was evaluated based on a steam stripper under the conditions
shown in Table 3 below.
Table 3
| Process Conditions for Steam Stripping Column |
| Theoretical Trays |
|
4 |
| Stripping Steam Rate (22) |
kg/hr |
3243 |
| Column Top Pressure |
barg |
1.30 |
| Column Bottom Pressure |
barg |
1.36 |
[0061] Process experiments were performed at two different stripper feed temperatures, 350°C
and 380°C to illustrate the split of overhead vapour and bottoms liquid products.
Coronene HPNA molecule was also included in the experiment to show how the vapour-liquid
equilibria would predict the distribution of the lightest HPNA species. The results
based on 350°C stripper feed temperature are presented in Table 4 below. At this feed
temperature, 50 weight percent is distilled overhead and 50 percent is recovered in
the bottoms liquid product. The coronene component has been concentrated in the stripper
bottoms from 461 ppmwt in the feed to by 691 ppmwt in the bottoms corresponding to
150 percent.
Table 4
| Stripper Feed and Product Rates and Properties |
| Stream Description |
|
Stream for stripping |
Stripped liquid |
Overhead vapour |
| Stream No. |
|
20 |
24 |
23 |
| Stream Temperature |
°C |
350 |
209 |
312 |
| Yield (% of Feed) |
%wt. |
100 |
50 |
50 |
| Heavy Poly-Nuclear |
|
|
|
|
| Aromatics |
|
|
|
|
| Coronene |
Wt ppm |
461 |
691 |
231 |
| Distillation |
|
|
|
|
| IBP |
°C |
300 |
340 |
282 |
| 10% |
°C |
360 |
393 |
344 |
| 50% |
°C |
427 |
447 |
407 |
| 90% |
°C |
483 |
505 |
455 |
| FBP |
°C |
560 |
563 |
511 |
[0062] The stripper results based on 380°C stripper feed temperature are presented in Table
5 below. At this feed temperature, 64 weight percent is distilled overhead and 36
percent is recovered in the bottoms liquid product. The coronene component has been
concentrated in the stripper bottoms from 466 ppmwt in the feed to 727 ppmwt in the
bottoms corresponding to 156 percent. Most of the HPNA molecules of concern in hydrocracker
are in fact heavier and less volatile than coronene and can be expected to further
concentrate in the stripper bottoms stream.
Table 5
| Stripper Feed and Product Rates and Properties |
| Stream Description |
|
Stream for stripping |
Stripped liquid |
Overhead vapour |
| Stream No. |
|
20 |
24 |
23 |
| Stream Temperature |
|
380 |
195 |
325 |
| Yield (% of Feed) |
%wt. |
100 |
36 |
64 |
| Heavy Poly-Nuclear Aromatics |
|
|
|
|
| Coronene |
Wt ppm |
466 |
727 |
319 |
| Distillation |
|
|
|
|
| IBP |
°C |
300 |
346 |
288 |
| 10% |
°C |
360 |
398 |
350 |
| 50% |
°C |
427 |
454 |
414 |
| 90% |
°C |
483 |
515 |
462 |
| FBP |
°C |
560 |
554 |
524 |
Example 3
[0063] The performance of an embodiment based on recycling the stripper bottoms in the same
quantity as the feed stream and heating to the same temperature of 350°C is shown
in Table 6. A comparison of the distillation curve of the net purge stream
24 in Table 4 and Table 6 shows that with recycle of a part of the stripper output,
the amount of high boiling products in the net purge is increased, i.e. the temperature
of the highest boiling 10% is increased from 505°C to 527°C. At this higher degree
of concentration, it can be seen in Table 6 that the concentration of coronene in
the overhead vapour 23 is only slightly below that of the heavy bottoms fraction 15,
which indicates a large portion of this HPNA tracer has volatilized into the overhead
vapour fraction. However, other HPNA compounds that are heavier and higher boiling
than coronene would predominantly be concentrated in the heavy bottoms fraction and
be purged from the system.
Table 6
| Stripper Feed and Product Rates and Properties Alternate Bottoms Recycle Configuration |
| Stream Description |
|
Stream for stripping |
Stripper recycle |
Stripped liquid |
Overhead vapour |
| Stream No. |
|
20 |
27 |
24 |
23 |
| Stream Temperature |
°C |
350 |
350 |
254 |
326 |
| Yield (% of Feed) |
%wt . |
100 |
100 |
20 |
80 |
| Heavy Poly-Nuclear Aromatics |
|
|
|
|
|
| Coronene |
Wt ppm |
470 |
720 |
720 |
408 |
| Distillation |
|
|
|
|
|
| IBP |
°C |
301 |
376 |
376 |
295 |
| 10% |
°C |
361 |
415 |
415 |
355 |
| 50% |
°C |
428 |
472 |
472 |
419 |
| 90% |
°C |
484 |
527 |
527 |
465 |
| FBP |
°C |
527 |
554 |
554 |
488 |
[0064] These results demonstrate that under reasonable and practical conditions of temperature,
pressure and flow rate, the unconverted oil stream can be split by steam stripping
and result in the concentration of HPNA compounds in a bottoms liquid stream. This
concentration will lead to decreased net purge rates from the hydrocracker and corresponding
increased conversion and yields of distillate products.
[0065] An example of the conversion improvement comparing a case with net purge equal to
three volume percent of the hydrocarbonaceous feed to a case with net purge equal
to 0.6 volume percent of hydrocarbonaceous feed is shown in Table 7. The production
of naphtha, kerosene, and diesel increased from 107.45 to 109.84 volume percent of
hydrocarbonaceous feed.
Table 7
| Yield Improvement due to stripping of purge |
| Yields in volume % of feed |
Without stripping of purge |
With stripped net purge |
| Naphtha |
23.42 |
23.94 |
| Kerosene |
54.42 |
55.63 |
| Diesel |
29.61 |
30.27 |
| Net Unconverted oil purge |
3.0 |
0.60 |
| Naphtha + kerosene + diesel |
107.45 |
109.84 |
1. A hydrocracking process comprising the steps of:
(a) combining a hydrocarbonaceous feedstock (1) and a heavy bottom fraction recycle
stream (16) with a hydrogen-rich gas (2) to obtain a mixture comprising hydrocarbonaceous
feedstock and hydrogen;
(b) catalytically hydrocracking the mixture comprising hydrocarbonaceous feedstock
and hydrogen in a hydrocracking zone (3) to obtain a hydrocracked effluent (4);
(c) separating the hydrocracked effluent into a first vapour portion (6) and a first
liquid portion (9) in a separation zone (5);
(d) heating the first liquid portion (9) to form a vapourised first liquid portion
(11);
(e) feeding the vapourised first liquid portion (11) to a fractionation section (12)
producing individual product fractions (13,14,15) including a heavy bottom fraction
(15) comprising unconverted oil at the bottom zone of the fractionation section (12);
(f) withdrawing from the fractionation section (12) the heavy bottom fraction (15);
(g) splitting the heavy bottom fraction (15) into a stream for stripping (17) and
the heavy bottom fraction recycle stream (16);
(h) directing, as a first stream the stream for stripping (17), as a second stream
a stripping medium (22) and as an optional third stream, a recycled portion of stripped
liquid (25), to a counter current stripping column (21) and withdrawing from said
stripping column (21) an overhead vapour (23) and a stripped liquid (24);
(i) feeding the overhead vapour (23) to the fractionation section (12), to a recycle
stream or to a position upstream the fractionation section; and
(j) removing at least a part of the stripped liquid (24) from the counter current
stripping column as a net purge of unconverted oil
characterized in said process further comprising the step of
(k) transferring thermal energy to at least one of said first stream (17), second
stream (22) and optional third stream (25) prior to directing said stream to the counter
current stripping column (21).
2. Process according to claim 1, wherein the vapourised first liquid portion (11) is
at least 50% vaporised.
3. Process according to claim 1 or 2, wherein the vapourised first liquid portion (11)
is at most 95% vaporised.
4. Process according to claim 1 to 3, wherein a part of the stripped liquid (25) is recycled
combined with the stream for stripping (20) and directed to an inlet of the counter
current stripping column (21).
5. Process according to claim 4, wherein the recycled portion of the stripped liquid
(25) and/or the stream for stripping (22) is heated by heat exchange with the heavy
bottom fraction (15).
6. Process according to any of the claims 1 to 5, wherein the stream for stripping (17)
is heated prior to the stripping process (21) to raise its temperature above its bubble
point, such as above 300°, preferably above 320°C and most preferably above 330°C.
7. Process according to any of the claims 1 to 4, wherein thermal energy is transferred
from the heavy bottom fraction (15) to the stripping medium (22) by heat exchange.
8. Process according to any of the claims 1 to 5, wherein the stripping medium (22) is
steam preferably medium pressure steam having a pressure between 1 and 20 barg.
9. Process according to any one of the claims 1 to 8, wherein the counter current stripping
column (21) comprises multiple equilibrium stages in the form of trays or packing
material.
10. Process according to anyone of claims 1 to 9, wherein the hydrocarbonaceous feedstock
is hydrotreated prior to hydrocracking.
11. Process according to anyone of claims 2 to 10, wherein some or all of the energy for
the heating is provided by heat exchange with one or more streams from the hydrocracking
process.
12. Process according to anyone of claims 2 to 11, wherein the heating of at least one
of said first stream (17), second stream (22) and optional third stream (25) directed
to the stripping column (21) is provided by heat exchange with a reactor effluent,
an external source of heating medium, high pressure steam, hot flue gas from a fired
heater or by electrical heating.
13. Process according to anyone of claims 1 to 12, wherein stripping medium output (23)
from the stripping unit is added to the fractionation column (12).
14. Process according to any one of the previous claims wherein HPNA is extracted from
the net purge by adsorption on an adsorbent.