CATEGORY: REACTORS
PATENT
Reactor
With Reactor Head and Integrated Valve (Exxonmobil)
Publication number US20130317801 A1
Publication type Application
Application number US 13/957,488
Publication date Nov 28, 2013
Also published as CN102917784A, EP2576041A1, US8524159, US20110291051,
WO2011149635A1
Inventors
Frank Hershkowitz, 6 More »
Original Assignee
Exxonmobil Chemical Patents Inc.
Abstract
A
reactor with minimal dead volume especially suited to reverse-flow applications
comprises: a) a reactor body; b) a first head engaged with said reactor body;
c) a first conduit extending from outside said head to at least partially
through said head; and d) a first valve in flow communication with said first
conduit controlling fluid flow along a flow path extending from the first valve
and through the reactor body. The reactor is especially suited for use in a
process for rapid stream-switching of at least two streams in a reverse-flow
reactor.
FIELD
The present invention relates to a reactor, e.g., reverse-flow reactor, whose
configuration includes a valve associated with the reactor head which minimizes
dead volume between the valve and reactor bed and provides for a durable valve
arrangement. The present invention also relates broadly to a process for using
such a reactor.
BACKGROUND
Reverse-flow reactors (RFRs) are known in the art, for example, Wulff pyrolysis
and regenerative reactor and other regenerative reactors, including
regenerative thermal oxidizers (RTO). These reactors are typically used to
execute cyclic, batch-generation, high temperature chemistry. Regenerative
reactor cycles are either symmetric (same chemistry or reaction in both
directions) or asymmetric (chemistry or reaction changes with step in cycle).
Symmetric cycles are typically used for relatively mild exothermic chemistry,
examples being regenerative thermal oxidation (RTO) and autothermal reforming
(ATR). Asymmetric cycles are typically used to execute endothermic chemistry,
and the desired endothermic chemistry is paired with a different chemistry that
is exothermic (typically combustion) to provide heat of reaction for the
endothermic reaction. Examples of asymmetric cycles are Wulff pyrolysis
processes and pressure swing reforming processes (PSR).
To operate the RFRs, various operational features should be considered. For
instance, one feature of RFRs is a gas hourly space velocity, which is the
space velocity of a gas over a given reactor volume. Typically, a high gas
hourly space velocity (and hence reactor productivity) has a small reactor cycle
time, while low has hourly space velocity has a longer reactor cycle time. For
pyrolysis processes using a RFR, high velocities are needed to achieve short
residence times that facilitate conversion to preferred products. A second
feature is that the volume of gas remaining in the RFR at the end of one cycle
(void volume) should be managed, e.g., swept out, before the beginning of the
next cycle, which gas-volume management may result in inefficiency and
additional costs. A third feature is that bed structures (packing) needed to
provide rapid heat transfer (for sharp thermal gradients and resulting high
efficiency) also results in high pressure drop. Thus, the RFR design should
consider space velocity, void volume, and packing properties to properly manage
the system. Accordingly, certain drawbacks in conventional RFRs, such as
properties of conventional packing and long cycle times, have prevented these
reactors from being broadly used in the energy and petrochemical fields.
RFRs have historically utilized different packing material in the bed
structures. Typically, these reverse-flow reactors utilize checker brick,
pebble beds or other available packing. This type of bed structure typically
has low geometric surface area (aV), which minimizes pressure drop per unit of
reactor length, but also reduces volumetric heat transfer rate. One basic
principle of an asymmetric reverse flow reactor is that heat is stored in one
step and is used to accomplish a desired endothermic chemistry in a second
step. Thus, the amount of desired chemistry that can be achieved, per volume of
reactor, is directly related to the volumetric heat transfer rate. Lower heat
transfer rates thereby require larger reactor volumes to achieve the same
amount of desired chemical production. Lower heat transfer rates may
inadequately capture heat from RFR streams, leading to greater sensible heat
loss and consequently lower efficiency. Lower heat transfer rates may also lead
to longer cycle times, as the stored heat is used more slowly, and therefore
lasts longer for a given bed temperature specification. Historic RFR's, with
low-aV checker-brick or pebble bed packing, are larger (e.g., longer and more
capital intensive) and have cycle times of two minutes or greater. As such,
these reactors limit reactor efficiency and practical reactor size.
As an enhancement, some RFRs may utilize engineered packing within the bed
structure. The engineering packing may include a material provided in a
specific configuration, such as a honeycomb, ceramic foams or the like. These
engineered packings have a higher geometric surface area (aV), as compared to
other bed structures. The use of this type of packing allows for higher gas
hourly space velocity, higher volumetric reactor productivity, higher thermal efficiency,
and smaller, more economical reactors. However, these more-economical reactors
use heat more rapidly and thus may require reduced cycle times. Pressure swing
reforming processes (PSR) are an example of such a preferred RFR.
Further, as a result of using this type of packing material, the size of the
reactor may be reduced, which provides significant capital cost savings.
However, adjusting the packing material of the reactors impacts other
operational features. For instance, the increase in volumetric surface area
(aV) is typically accomplished using smaller flow channels that result in
higher pressure drop per unit of reactor length. To compensate for this, these
enhanced RFR's are configured to have short lengths. When applied to large
petrochemical applications, diameter is increased to enable high productivity,
but length is limited by pressure drop, thus leading to a high ratio for
diameter per length (D/L). Conventional reactor designs typically collect
fluids emerging from a bed and duct those fluids to some external valve. The
volume of such ducting is in some proportion to the reactor diameter, because
the ducting needs to collect gas from the entire diameter. Thus, for a
conventional reactor having a high D/L ratio, the volume of ducting can be very
large compared to the volume inside the bed. Use of a conventional reactor
design for an enhanced RFR thus results in large void volumes (primarily in the
ducting), which creates problems for gas volume management.
Unfortunately, conventional reactor valve systems have certain limitations that
do not operate properly for enhanced, high-productivity reactors (e.g., compact
reactors employing short cycle times). For instance, conventional reactor valve
systems typically fail to meet the durability requirements of RFRs and may not
handle the short cycle times. Petrochemical valves can have maximum cycle
lifetimes on the order of 500,000 cycles, is which correspond to less than one
year of operation—inadequate for petrochemical use involving rapid cycle times.
In addition, conventional valves are placed outside the reactor and use
manifolding to carry gases between the bed and the valve, while providing
uniform flow distribution across the bed. Given the wide and short beds of
RFRs, this manifolding holds a large gas volume that has to be managed on every
cycle change.
As an example, Japanese Patent Application No. 280,921/1999 to Taga discloses a
high-temperature heat exchanger with a plurality of high-temperature gas
switching poppet valve pairs which control the flow of high-temperature
preheated air and high-temperature waste gas over a regenerative heat exchange
element.
U.S. Patent Application Publication No. 2009/0008292 to Keusenkothen et al.
discloses pyrolyzing hydrocarbons in a reverse-flow type regenerative pyrolysis
reactor system.
U.S. Pat. No. 7,491,250 to Hershkowitz et al. discloses production of synthesis
gas through a cyclic, packed-bed operation which includes reforming by
preheating a first zone, introducing a hydrocarbon-containing feed with steam
through the first zone inlet, and reforming over a catalyst in the first zone
to form synthesis gas which is passed to a second zone where it is cooled.
U.S. Patent Application Publication No. 2007/0144940 to Hershkowitz et al. and
U.S. Patent Application Publication No. 2008/0142409 to Sankaranarayanan et al.
teach a regenerative bed reverse flow reactor wherein the location of the
exothermic reaction is controlled. The regenerative reactor bed is regenerated
by supplying a first reactant through a first channel to a first regenerative
bed and a second reactant through a second channel in the first regenerative
bed, combining first and second reactants in a gas mixer, and reacting to
produce a heated reaction product which is passed through a second regenerative
bed to transfer heat thereto.
U.S. Patent Application Publication No. 2009/008292 to Keusenkothen et al.
teaches pyrolyzing hydrocarbons containing non-volatiles in a regenerative
pyrolysis reactor system. Feedstock is heated to provide a vapor phase which is
fed to the pyrolysis reactor system and converted to form a pyrolysis product.
U.S. Patent Application Publication No. 2008/0314550 to Greco teaches a
regenerative heat exchanger that uses inlet and outlet poppet valves which are
operated in tandem and located outside the head space of the heat exchanger.
Accordingly, it is desirable to provide a reverse-flow reactor system that is
minimizes dead volumes between its valves and reactor beds, while providing
extended valve lifetimes to millions of cycles, in rugged, high-temperature
conditions at the reactor inlet and outlet. Further, there is a need for an
enhanced method and apparatus to implement an industrial-scale, high-GHSV
RFR's, which has valves that enhance the cycle time of RFRs and manage the
purging of fluid between cycles. The present techniques provide a method and
apparatus that overcome one or more of the deficiencies discussed above.
SUMMARY
In a first aspect, the present invention relates to a reactor comprising: a) a reactor
body; b) a first head engaged with said reactor body; c) a first conduit
extending from outside said head to at least partially through said head; and
d) a first valve in flow communication with said first conduit controlling
fluid flow along a flow path extending from the first valve and through the
reactor body. For present purposes, “flow path” may be characterized as the
total volume through which fluid passes, including an open flow path. For
present purposes, a “head” may be a dished head, meaning it is of substantially
concave shape internally, e.g., it can be substantially round, substantially
elliptical, substantially torispherical, or substantially hemispherical.
In a second aspect, the present invention relates to a reactor comprising: a) a
reactor body partially enclosing a reaction and/or heat exchange region
comprising two substantially opposing open ends; b) a first head capping one
end of the reactor body; c) a second head capping the opposing end of the
reactor body; d) a fixed bed comprising a region proximal to the first head, a
region proximal to the second head and a central region disposed therebetween,
which fixed bed is disposed within the reactor body and comprises solid
material capable of promoting heat exchange and/or reaction of a gas stream; e)
at least one gas stream inlet associated with the first head opening a pathway
through the first head and into the reactor body and at least one gas stream
outlet associated with the second head opening a pathway from the reactor body
and through the second head; f) at least one inlet poppet valve controlling the
gas stream inlet and integrated with the head associated with the inlet, the
inlet poppet valve comprising a linearly actuatable valve stem; g) at least one
outlet poppet valve controlling the gas stream outlet and integrated with the
head associated with the outlet, the outlet poppet valve comprising a linearly
actuatable valve stem; and h) at least one actuator engageable with the
linearly actuatable valve stem of f) and/or g) providing valve opening and
closing by imparting linear motion to the poppet valve to allow gases to pass
from outside the reactor to inside the reactor body, and from inside the
reactor body to is outside the reactor so as to provide changeable flow operation.
In a third aspect, the present invention relates to a process for rapid
stream-switching of at least two streams in a reverse-flow reactor comprising a
reactor body partially enclosing a reaction and/or heat exchange region
comprising two substantially opposing open ends with a first head capping one
end of the reactor body, a second head capping the opposing end of the reactor
body, a fixed bed disposed within the reactor body comprising solid material
capable of promoting heat exchange and/or reaction of a gas stream. The process
comprises: i) introducing from one or more inlet gas sources at least one first
gas stream to at least one gas stream inlet associated with the first head
through the first head and into the reactor body and withdrawing a treated
first gas stream from the reactor body and through the second head to at least
one gas stream outlet associated with the second head; wherein said introducing
and withdrawing are controlled respectively by at least one intake poppet valve
located in the first head and at least one exhaust poppet valve located in the
second head; and ii) introducing from one or more inlet gas sources at least
one second gas stream to at least one gas stream inlet associated with the
second head through the second head and into the reactor body and withdrawing a
treated second gas stream from the reactor body and through the first head to
at least one gas stream outlet associated with the first head, wherein said
introducing and withdrawing are controlled respectively by at least one intake
poppet valve or other intake flow control means located in the second head and
at least one exhaust poppet valve located in the first head.
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