U.S. patent application number 14/594452 was filed with the patent office on 2015-05-07 for fischer tropsch method for offshore production risers for oil and gas wells.
The applicant listed for this patent is Robert P. Herrmann. Invention is credited to Robert P. Herrmann.
Application Number | 20150122504 14/594452 |
Document ID | / |
Family ID | 49758774 |
Filed Date | 2015-05-07 |
United States Patent
Application |
20150122504 |
Kind Code |
A1 |
Herrmann; Robert P. |
May 7, 2015 |
Fischer Tropsch Method for Offshore Production Risers for Oil and
Gas Wells
Abstract
A method and an apparatus is disclosed that uses a gas lift
tubing arrangement to produce synthetic hydrocarbon related
products. Using the Fischer Tropsch process as an example, the
tubing is packed with a suitable catalyst and then hydrogen and
carbon monoxide are injected into the top of the tubing in a
fashion similar to a gas lift process. As the gases travel past the
catalyst, synthetic hydrocarbons are formed and heat is rejected.
The synthetic hydrocarbons and water flow out of the bottom of the
tubing and travel up the annulus to the surface. In some
embodiments, this process is carried out in a producing well or a
in producing riser. In a producing well or a producing riser, the
production from the well which flows up the annulus cools the
synthetic hydrocarbon derived products. In additional and alternate
embodiments, this process can be used in non-flowing wells.
Inventors: |
Herrmann; Robert P.;
(Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Herrmann; Robert P. |
Houston |
TX |
US |
|
|
Family ID: |
49758774 |
Appl. No.: |
14/594452 |
Filed: |
January 12, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13839825 |
Mar 15, 2013 |
|
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14594452 |
|
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61660709 |
Jun 16, 2012 |
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Current U.S.
Class: |
166/367 |
Current CPC
Class: |
E21B 17/20 20130101;
E21B 43/122 20130101; C10G 2/32 20130101; E21B 43/40 20130101; B01J
8/008 20130101; E21B 17/01 20130101; C10G 2/00 20130101; C10G 2/341
20130101; C07C 1/041 20130101 |
Class at
Publication: |
166/367 |
International
Class: |
E21B 17/01 20060101
E21B017/01; C07C 1/04 20060101 C07C001/04; E21B 17/20 20060101
E21B017/20; E21B 43/12 20060101 E21B043/12; E21B 43/40 20060101
E21B043/40 |
Claims
1-10. (canceled)
11. An apparatus for producing synthetic hydrocarbons comprising: a
marine riser, wherein the marine riser is suspended in a body of
water; a tube configured to insert into the top of the marine
riser, wherein a Fischer-Tropsch catalyst is comprised inside the
tube, and wherein the top of the tube is configured to receive
hydrogen and carbon monoxide such that contact of the hydrogen and
carbon monoxide with the Fischer-Tropsch catalyst produces
synthetic hydrocarbons; and an annulus configured to receive the
produced synthetic hydrocarbons., wherein heat generated by contact
of the hydrogen and carbon monoxide with the Fischer-Tropsch
catalyst is rejected into the body of water during production of
the synthetic hydrocarbons from the annulus.
12. The apparatus of claim 11, wherein the annulus is between an
outside wall of the tube and an inside wall of the riser, and
wherein the tubing tube is configured such that synthetic
hydrocarbons and water generated during contacting flow out of the
bottom of the tube and travel up the annulus to the surface.
13. The apparatus of claim 11, wherein any unreacted hydrogen or
carbon monoxide travels up the annulus to the surface where the
unreacted hydrogen Of carbon monoxide, or both is reprocessed and
re-injected into the top of the tubing.
14. The apparatus of claim 11, wherein the marine riser is a
producing well.
15. The apparatus of claim 11, wherein production from the
producing well flows up the annulus and cools the synthetic
hydrocarbons.
16. (canceled)
17. (canceled)
18. The apparatus of claim 11, wherein the apparatus is placed in a
non-flowing well.
19. The apparatus of claim 18, further comprising another tube
positioned around the tube, wherein the apparatus is capable of
circulating cooling fluid up an annulus between the another tube
and the inside wall of the riser, where the cooling fluid mixes
with the synthetic hydrocarbons, and at the surface, the cooling
fluid is separated and cooled for re-injection.
20-31. (canceled)
32. An apparatus for producing synthetic hydrocarbon derived
products comprising: a marine riser, wherein the marine riser is
suspended in a body of water; a tube configured to insert into the
top of the marine riser, wherein one or more catalysts are
comprised inside the tube, and wherein the top of the tube is
configured to receive feedstock such that contact of the feedstock
with at least one of catalysts produces synthetic products; and an
annulus configured to receive the produced synthetic products,
wherein heat generated by contact of the hydrogen and carbon
monoxide with the Fischer-Tropsch catalyst is rejected into the
body of water during production of the synthetic products from the
annulus.
33. The apparatus of claim 32, wherein the annulus is between an
outside wall of the tube and an inside wall of the riser, and
wherein the tube is configured such that the synthetic hydrocarbons
and water generated during production of the synthetic products
flow out of the bottom of the tube and travel up the annulus to the
surface.
34. The apparatus of claim 32, wherein any feedstock not converted
to the synthetic products travels up annulus to the surface where
the non-converted feedstock is reprocessed and re-injected.
35. The apparatus of claim 32, wherein the feedstock and the
catalyst are suitable for producing the synthetic products from a
process selected from the group consisting of the Haber process,
the Haber-Bosch process, processes used to industrially produce
ammonia or synthesis gas, the Claus process, the gas desulfurizing
process, processes used to recover elemental sulfur from gaseous
hydrogen sulfide, the Bergius Process, processes used to produce
liquid hydrocarbons for use as synthetic fuel by hydrogenation of
high-volatile bituminous coal at high temperature and pressure, the
Deacon process, the Deacon-Leblanc process, the Sabatier process,
the Sabatier-Senderens process, hydrogenation processes, oxidation
processes, ammonia oxidation processes, the Andrussov synthesis,
hydrocracking processes, alkylation processes, hydrotreating
processes, catalytic reforming processes, coke formation, naphtha
reforming processes, processes for the formation, reformation and
functionalization of aromatics, cyclar processes, M2-forming
process, catalytic dewaxing processes, isomerization processes,
isopropyl alcohol formation, acetone formation, bisphenol-A
formation, cumene formation, vinyl chloride formation,
oxychlorination processes, formation of synthetic rubber from
butadiene and styrene, formation of butadiene from butane or
butenes, styrene production, nylon production, production of nylon
intermediates, formation of adipic acid, formation of
hexamethylenediamine, formation of nylon polymer, the Snia-Viscosa
process, hydroformylation and carbonylation processes, metathesis
of olefins, the Shell Higher-Olefins process, polyethylene
formation, polypropylene formation, formation of ammonia synthesis
gas, feedstock purification processes, hydrodesulfurization
processes, processes for chlorine removal, sulfur adsorption, steam
reforming, carbon monoxide removal, carbon monoxide conversion, and
methanation, formation of methanol synthesis gas, formation of OXO
synthesis gas, hydrogen production, processes for steam reforming
of reducing gas, town gas production, autothermal reforming
processes, the Claude Process, processes for volatile organic
compound removal, the Fischer-Tropsch process, dry carbon dioxide
(CO.sub.2) reforming, hydrocarbon cracking of hydrocarbons, and
steam reforming.
36. The apparatus of claim 32, wherein the feedstock and the
catalyst are suitable for producing a synthetic products from a
process selected from a group consisting of the Fischer-Tropsch
process, dry carbon dioxide (CO.sub.2) reforming, hydrocarbon
cracking, and steam reforming.
37. The apparatus of claim 32, wherein the marine riser is a
producing well.
38. The apparatus of claim 37, wherein production from the
producing well flows up the annulus and cools the synthetic
hydrocarbons.
39. (canceled)
40. (canceled)
41. The apparatus of claim 32, wherein the marine riser is placed
in a non-flowing well.
42. The apparatus of claim 41, further comprising another tube
positioned around the tube wherein the apparatus is capable of
circulating cooling fluid up an annulus between the another tube
and the inside wall of the riser, where the cooling fluid mixes
with the synthetic products, and at the surface, the cooling fluid
is separated and cooled for re-injection.
43. A system for producing synthetic hydrocarbons comprising: a
marine riser positioned in a body of water; a tube configured to be
inserted into the marine riser; one or more catalysts capable of
being distributed along the inside of the length of the tube; a
pressurizing unit coupled to the tube, the pressurizing unit
capable of pressurizing a feedstock in a downwardly direction
through the tube when the tube is inserted in the marine riser,
wherein contact of the feedstock with at least one of the catalysts
produces a mixture comprising synthetic hydrocarbons; and wherein
contacting generates heat, and the generated heat is transferred to
the produced mixture in an annulus of the marine riser, and then to
the outside wall of the marine riser.
44. The system of claim 43, wherein a length of the tube is
sufficient to control the conversion rate or product yield along
the length of the tube.
45. The system of claim 43, wherein tube is coiled, and wherein the
tube is capable of being uncoiled during insertion of the tube into
the marine riser.
47. The apparatus of claim 1, wherein the tube further comprises
another catalyst coated on an outside wall of the tube, and wherein
contact of the produced synthetic hydrocarbons with the other
catalyst to produces additional synthetic hydrocarbons.
48. The apparatus of claim 20, wherein the tube further comprises
another catalyst coated on an outside wall of the tube, and wherein
contact of the produced synthetic hydrocarbons with the other
catalyst to produces additional synthetic hydrocarbons.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The pressent application is a divisional application of U.S.
application Ser. No. 13/839,825, filed Mar. 15, 2013, which claims
the benefit of U.S. Provisional Application 61/660,709 filed on
Jun. 16, 2012, which is incorporated by reference in its
entirety.
TECHNICAL FIELD
[0002] The present disclosure relates generally to the production
of synthetic hydrocarbon derived products. More specifically, the
present disclosure provides a method and an apparatus capable of
producing synthetic hydrocarbon derived products using a gas lift
apparatus equipped with a tubing comprising a catalyst.
BACKGROUND OF THE INVENTION
[0003] A process used for converting gas to liquid petroleum can be
accomplished using a Fischer-Tropsch catalyst. Since the invention
of the original process by Franz Fischer and Hans Tropsch, working
at the Kaiser Wilhelm Institute in the 1920s, many refinements and
adjustments have been made to this process. The term
"Fischer-Tropsch" now applies to a wide variety of similar
processes (Fischer-Tropsch synthesis or Fischer-Tropsch chemistry).
Fischer and Tropsch filed a number of patents, e.g., U.S. Pat. No.
1,746,464, related to this process.
[0004] The Fischer-Tropsch process involves a series of chemical
reactions that lead to a variety of hydrocarbons (C--H.sub.(2n+2)).
Useful reactions give alkanes:
(2n+1) H.sub.2+n CO.fwdarw.C.sub.nH.sub.(2n+2)n H.sub.2O (1)
[0005] where the term "n" represents a positive integer. The
formation of methane (n=1) is generally unwanted. Most of the
alkanes produced tend to be straight-chain hydrocarbons, suitable
for use as a diesel fuel. In addition to alkane formation,
competing reactions give small amounts of alkenes, as well as
alcohols and other oxygenated hydrocarbons.
[0006] Several reactions are employed to adjust the H.sub.2/CO
ratio. Most important is the water gas shift reaction, which
provides a source of hydrogen at the expense of carbon
monoxide:
H.sub.2O+CO.fwdarw.H.sub.2+CO.sub.2 (2)
[0007] For Fischer-Tropsch plants that use methane as the
feedstock, another important reaction is steam reforming, which
converts the methane into CO and H.sub.2:
H.sub.2O+CH.sub.4.fwdarw.CO+3 H.sub.2 (3)
[0008] The conversion of CO to alkanes involves hydrogenation of
CO, the hydrogenolysis (cleavage with H.sub.2) of C-0 bonds, and
the formation of C--C bonds. Such reactions are assumed to proceed
via initial formation of surface-bound metal carbonyls. The CO
ligand is speculated to undergo dissociation, possibly into oxide
and carbide ligands. Other potential intermediates are various C-1
fragments including formyl (CHO), hydroxycarbene (HCOH),
hydroxymethyl (CH.sub.2OH), methyl (CH.sub.3), methylene
(CH.sub.2), methylidyne (CH), and hydroxymethylidyne (COH).
Furthermore, and critical to the production of liquid fuels, are
reactions that form C--C bonds, such as migratory insertion. Many
related stoichiometric reactions have been simulated on discrete
metal clusters, but homogeneous Fischer-Tropsch catalysts are
poorly developed and of little commercial importance.
[0009] Generally, the Fischer-Tropsch process is operated in the
temperature range of 150-300.degree. C. (302-572.degree. F.).
Higher temperatures usually lead to faster reactions and higher
conversion rates, but also tend to favor methane production. For
this reason, the temperature is usually maintained at the low to
middle part of the range. Increasing the pressure leads to higher
conversion rates and also favors formation of long-chained alkanes,
both of which are desirable. Typical pressures range from one to
twenty atmospheres. High pressure may reduce the reaction
temperature which would make the Fischer-Tropsch process compatible
with most oilfield operations.
[0010] A variety of synthesis-gas compositions can be used. For
cobalt-based catalysts the optimal H.sub.2:CO ratio is around
1.8-2.1. Iron-based catalysts promote the water-gas-shift reaction.
Accordingly, iron-based catalysts can tolerate lower ratios of
H.sub.2:CO. This reactivity can be important for synthesis gas
derived from coal or biomass, which tend to have relatively low
H.sub.2:CO ratios (<1).
[0011] In general the product distribution of hydrocarbons formed
during the Fischer-Tropsch process follows an Anderson-Schulz-Flory
distribution, which can be expressed as:
Wn/n=(1-.alpha.)2.alpha.n-1 (4)
[0012] Where Wn is the weight fraction of hydrocarbon molecules
containing n carbon atoms. The term "a" represents the chain growth
probability or the probability that a molecule will continue
reacting to form a longer chain. In general, a is largely
determined by the catalyst and the specific process conditions.
[0013] Examination of equation (4) reveals that methane will always
be the largest single product so long as a is less than 0.5.
However, by increasing value of a to about one, the total amount of
methane formed can be minimized compared to the sum of all of the
various long-chained products. Increasing a increases the formation
of long-chained hydrocarbons. The very long-chained hydrocarbons
are waxes, which are solid at room temperature. Therefore, for
production of liquid transportation fuels it may be necessary to
crack some of the Fischer-Tropsch products. In order to avoid this,
some researchers have proposed using zeolites or other catalyst
substrates with fixed sized pores that can restrict the formation
of hydrocarbons longer than some characteristic size (usually
n<10). This way they can drive the reaction so as to minimize
methane formation without producing lots of long-chained
hydrocarbons. Such efforts have met with only limited success.
[0014] A variety of catalysts can be used for the Fischer-Tropsch
process, but the most common are the transition metals cobalt,
iron, and ruthenium. Cobalt, nickel, iron, molybdenum, tungsten,
thorium, ruthenium, rhenium and platinum are known to be
catalytically active, either alone or in combination, in the
conversion of synthesis gas into hydrocarbons and oxygenated
derivatives thereof. Of the aforesaid metals, cobalt, nickel and
iron have been studied most extensively. Nickel tends to favor
methane formation ("methanation"). Generally, the metals are used
in combination with a support material, of which the most common
are alumina, silica and carbon.
[0015] Cobalt-based catalysts are highly active, although iron may
be more suitable for low-hydrogen-content synthesis gases such as
those derived from coal due to its promotion of the water-gas-shift
reaction. In addition to the active metal, the catalysts typically
contain a number of "promoters," including potassium and copper.
Group 1 alkali metals, including potassium, are a poison for cobalt
catalysts but are promoters for iron catalysts. Catalysts are
supported on high-surface-area binders/supports such as silica,
alumina, or zeolites. Cobalt catalysts are more active for
Fischer-Tropsch synthesis when the feedstock is natural gas.
Natural gas has a high hydrogen to carbon ratio, so the
water-gas-shift is not needed for cobalt catalysts. Iron catalysts
are preferred for lower quality feedstocks such as coal or
biomass.
[0016] Unlike the other metals used for this process (Co, Ni, Ru),
which remain in the metallic state during synthesis, iron catalysts
tend to form a number of phases, including various oxides and
carbides during the reaction. Control of these phase
transformations can be important in maintaining catalytic activity
and preventing breakdown of the catalyst particles.
[0017] Fischer-Tropsch catalysts are sensitive to poisoning by
sulfur-containing compounds. The sensitivity of the catalyst to
sulfur is greater for cobalt-based catalysts than for their iron
counterparts.
[0018] Promoters also have an important influence on activity.
Alkali metal oxides and copper are common promoters, but the
formulation depends on the primary metal. Alkali oxides on cobalt
catalysts generally cause activity to drop severely even with very
low alkali loadings. C.sub.5 and CO.sub.2 selectivity increase
while methane and C.sub.2--C.sub.4 selectivity decrease. In
addition, the olefin to paraffin ratio increases.
[0019] The use of cobalt as a catalytically active metal in
combination with a support has been described in, for example,
EP-A-127220, EP-A-142887, GB-A-2146350, GB-A-2130113 and
GB-A-2125062. EP-A-127220, for example discloses the use of a
catalyst comprising (i) 3-60 pbw cobalt, (ii) 0.1-100 pbw
zirconium, titanium, ruthenium or chromium, per 100 pbw silica,
alumina or silica-alumina, (iii) the catalyst having been prepared
by kneading and/or impregnation.
[0020] EP 261870 describes a composition for use after reductive
activation as a catalyst for the conversion of synthesis gas to
hydrocarbons comprising as essential components (i) cobalt either
as the elemental metal, oxide or a compound thermally decomposable
to the elemental metal or oxide and (ii) zinc in the form of the
oxide or a compound thermally decomposable to the oxide. The
resultant catalysts, in contrast to many prior art
cobalt-containing catalysts, are more selective to hydrocarbons in
the C5-C120 range and can be very selective to a waxy hydrocarbon
product. These catalysts may also contain in elemental form or
oxide form one or more of the following metals as promoters:
chromium, nickel, iron, molybdenum, tungsten, zirconium, gallium,
thorium, lanthanum, cerium, ruthenium, rhenium, palladium or
platinum suitably in amount up to 15% w/w. Exemplified compositions
included chromium, zirconium, gallium and ruthenium as
promoters.
[0021] U.S. Pat. No. 4,039,302 describes a catalyst containing
cobalt oxide and zinc oxide for use in the synthesis of C1-C3
aliphatic hydrocarbons
[0022] U.S. Pat. No. 4,826,800 describes a process for preparing a
catalyst comprising cobalt and zinc oxide for use after reductive
activation as a catalyst in the conversion of synthesis gas to
hydrocarbons. The catalyst is prepared by mixing a solution, of a
soluble zinc salt and a soluble cobalt salt with a precipitant such
as ammonium hydroxide or ammonium carbonate and recovering the
precipitate. The ratio of carbonate to metal is high in the
described method, which has been found detrimental to the strength
of the catalyst.
[0023] U.S. Pat. No. 5,345,005 relates to a Cu--Zn catalyst on
alumina for the preparation of alcohols by hydrogenation of e.g. a
ketone. In a comparative example, the preparation of a Cu--Zn--Co
catalyst on alumina is described, wherein use is made of soda ash.
However, the use of soda ash is found to be potentially detrimental
to the strength of the catalyst. The particle size distribution
range within which 90% of the volume of the Cu--Zn--Co catalyst
described in U.S. Pat. No. 5,345,005 lies, is not specified. It is
however expected that the use of soda ash in the preparation of the
catalyst leads to a broadening in the particle size
distribution.
[0024] U.S. Pat. No. 5,945,458 and U.S. Pat. No. 5,811,365 describe
a Fischer-Tropsch process in the presence of a catalyst composition
of a group VIII metal, e.g. cobalt, on a zinc oxide support. Such a
catalyst is made by first preparing the support by adding a
solution of zinc salt and other constituents to an alkaline
bicarbonate solution. Next, the precipitate is separated from the
bicarbonate solution by filtration to form a filter cake, which can
thereafter be dried, calcined and loaded with the group VIII metal.
The catalyst material is then formed into tablets, which tablets
are crushed to form particles with a size of 250-500 .mu.m, that
can be used in a Fischer-Tropsch process. Additional
post-treatments such as crushing, are required in order to obtain a
catalyst powder with good strength properties. However, the
obtained average particle size; as indicated above, is still
relatively large. Moreover, crushing results in a broad particle
size distribution and catalysts with such a large particle size and
a broad particle size distribution tend to be less suitable for
processes involving a bubble column, a slurry phase reactor or a
loop reactor.
[0025] WO-A-01/38269 describes a three-phase system for carrying
out a Fischer-Tropsch process wherein a catalyst suspension in a
liquid medium is mixed with, gaseous reactants in a high shear
mixing zone, after which the mixture is discharged in a post mixing
zone. Thus mass transfer is said to be enhanced. As suitable
catalysts inter alia cobalt catalysts on an inorganic support, such
as zinc oxide are mentioned. The surface area of the support used
for the preparation of these known catalysts is less than 100
g/m.sup.2. These prior art cobalt based catalysts can be prepared
by depositing cobalt on a suitable support, such as a zinc oxide
support, by impregnation methodology. Other conventional
preparation methods include precipitation routes, which typically
involve crushing of a hard filter cake of catalyst material,
resulting from the catalyst preparation process, into small
particles.
[0026] WO 03/090925 describes a Fischer-Tropsch catalyst comprising
particles of a cobalt and zinc co-precipitate having specific
volume average particle size and particle size distributions. The
catalysts essentially consist of cobalt and zinc oxide but may also
contain other components commonly employed in Fischer-Tropsch
catalysts such as ruthenium, hafnium, platinum, zirconium,
palladium, rhenium, cerium, lanthanum, or a combination thereof.
When present such promoters are typically used in a cobalt to
promoter atomic ratio of up to 10:1.
[0027] EP 221598 describes supported catalysts comprising a metal
component of iron, nickel or cobalt promoted by zirconium and in
addition a noble metal from Group VIII of the Periodic Table. The
catalysts are suitable for the preparation of hydrocarbons from
carbon monoxide and hydrogen. Preferred noble metals include
platinum or palladium and the catalysts are most suitably supported
on silica or alumina.
[0028] Fischer-Tropsch plants associated with coal or related solid
feedstocks (sources of carbon) must first convert the solid fuel
into gaseous reactants, i.e. CO, H.sub.2, and alkanes. This
conversion is called gasification. Synthesis gas obtained from coal
gasification tends to have a H.sub.2/CO ratio of about 0.7 compared
to the ideal ratio of about 2. This ratio is adjusted via the
water-gas shift reaction. Coal-based Fischer-Tropsch plants can
produce varying amounts of CO.sub.2, depending upon the energy
source of the gasification process. However, most coal-based plants
rely on the feed coal to supply all the energy requirements of the
Fischer-Tropsch process.
[0029] In summary, the Fischer-Tropsch process is performed by
forcing hydrogen and carbon monoxide over a catalyst. The gases
recombine into water and a petroleum product which can range
between diesel and paraffin. Heat and water are also generated in
this process. Currently, there is a need to improve the efficiency
of this process. The present disclosure presents a method and an
apparatus that improves the efficiency of catalytic processes.
BRIEF SUMMARY OF THE INVENTION
[0030] In general, the present disclosure provides a method and an
apparatus that uses a gas lift tubing arrangement to produce
synthetic hydrocarbons. In some embodiments, this method and
apparatus uses a Fischer-Tropsch process to produce synthetic
hydrocarbons. In the gas lift tubing arrangement, the tubing is
packed and/or coated with a suitable catalyst and then hydrogen and
carbon monoxide are injected into the top of the tubing in a
fashion similar to a gas lift process. As the gases travel past the
catalyst, synthetic hydrocarbons are formed and heat is rejected.
The synthetic hydrocarbons and fluid flow out of the bottom of the
tubing and travel up the annulus to the surface. Also, any gas not
converted to synthetic hydrocarbons travels up annulus to the
surface where it is reprocessed and re-injected. In some
embodiments, this process is carried out in a producing well or a
in producing riser. In a producing well or a producing riser, the
production from the well which flows up the annulus cools the
synthetic hydrocarbons. In additional and alternate embodiments,
this process can be used in non-flowing wells. In this case cooling
fluid is circulated up the annulus where it mixes with the newly
formed petroleum product, and at the surface, the fluid is
separated and cooled for re-injection.
[0031] In additional embodiments, the outside of the tubing is
coated with a reverse water shift catalyst which converts CO.sub.2
in the production stream to CO and H.sub.2O. In some embodiments,
the catalyst or the concentration of the catalyst is distributed
along length the tubing to control the conversion rate or product
yield along the tubing. In specific examples, the catalyst is
distributed or segregated along the tubing such that different
heavy components of the gas stream (C2-C6) are converted into
liquids which may be mixed with crude oil.
[0032] In alternate embodiments, more than one type of catalyst may
be distributed along the length of the tubing. In some embodiments,
the catalyst is distributed along the tubing in a plurality of
segregated zones. This apparatus and method can be used to convert
a first feedstock into a final product using a plurality of
catalyst distributed along the tubing in a plurality of zones. For
example, a first feedstock is converted into a first product using
a first catalyst in the first zone. The first product from the
first zone then becomes the second feedstock for the second zone,
and in the second zone, the second feedstock is converted into a
second product by a second catalyst. This process can be carried
out over a plurality of zones to produce a final product.
[0033] In additional embodiments, the interaction between the
catalyst and the feedstock produces an exothermic reaction. In this
situation, the gas lift arrangement is configured such that the
energy produced from this exothermic reaction is used to inhibit
hydrate formation in the annulus where production is flowing (oil,
gas, or both).
[0034] The foregoing has outlined rather broadly the features and
technical advantages of the present invention in order that the
detailed description of the invention that follows may be better
understood. Additional features and advantages of the invention
will be described hereinafter which form the subject of the claims
of the invention. It should be appreciated by those skilled in the
art that the conception and specific embodiment disclosed may be
readily utilized as a basis for modifying or designing other
structures for carrying out the same purposes of the present
invention. It should also be realized by those skilled in the art
that such equivalent constructions do not depart from the spirit
and scope of the invention as set forth in the appended claims. The
novel features which are believed to be characteristic of the
invention, both as to its organization and method of operation,
together with further objects and advantages will be better
understood from the following description when considered in
connection with the accompanying figures. It is to be expressly
understood, however, that each of the figures is provided for the
purpose of illustration and description only and is not intended as
a definition of the limits of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] For a more complete understanding of the present invention,
reference is now made to the following descriptions taken in
conjunction with the accompanying drawing, in which:
[0036] FIG. 1 shows a Fischer-Tropsch Process in a marine
riser;
[0037] FIG. 2 shows a Fischer Tropsch Process in a dummy well;
[0038] FIG. 3 provides an example of a coil tubing rig installing
the gas lift tubing in a marine riser;
[0039] FIG. 4 shows an example of a gas lifting process through a
gas lift string diverter valve;
[0040] FIG. 5A shows side view of the nozzle on the gas lift
string;
[0041] FIG. 5B shows a plane view the nozzle on the gas lift
string;
[0042] FIG. 6 shows an example of a gas lift string placed in a
riser/flowline;
[0043] FIG. 7 shows the arrangement of the gas lift installation
apparatus between the injector and the diverter.
DETAILED DESCRIPTION OF THE INVENTION
[0044] In oil wells and deepwater production risers , gas is
sometimes injected through a tube running to or near the bottom of
the well or riser to lift production fluid to the surface. This
process is called gas lift and the equipment for doing this is in
common use. In general, a gas lift apparatus is made of at least a
gas lift tube and an annulus. The length of the tube (the gas lift
string) varies but is typically 3,000 feet to 5,000 feet in length
and made from 1'' to 3.5'' pipe.
[0045] Gas lift is one of a number of processes used to
artificially lift oil or water from wells where there is
insufficient reservoir pressure to produce the well. The normal gas
lift process involves injecting gas through a tubing and returning
up an annulus. The annulus of an oil well refers to any void
between any piping, tubing or casing and the piping, tubing, or
casing immediately surrounding it.
[0046] Injected gas aerates the fluid to reduce its density; the
formation pressure is then sufficient to lift the oil column and
force the fluid out of the wellbore. Gas may be injected
continuously or intermittently, depending on the producing
characteristics of the well and the arrangement of the gas-lift
equipment.
[0047] The amount of injected gas needed to maximize oil production
varies based on well conditions and geometries. Too much or too
little injected gas will result in less than maximum production.
Generally, the optimal amount of injected gas is determined by well
tests, where the rate of injection is varied and liquid production
(oil and perhaps water) is measured.
[0048] Although the gas is recovered from the oil at a later
separation stage, the process requires energy to drive a compressor
in order to raise the pressure of the gas to a level where it can
be re-injected.
[0049] A coil-tubing rig 12 may be located on a production facility
in a field in 7000 feet of water where production arrives via five
separate steel catenary risers (SCR), with 8.5'' inner diameter.
The coil-tubing rig may be used for deploying a gas lift string 13
inside the marine production risers 14. FIG. 3 provides an example
of a coil tubing rig 12.
[0050] A common use of a coil-tubing rig 12 is to deploy a gas lift
string inside the marine riser 14, about 8,000 feet measured depth
(MD). The coil tubing size ranges from 23/8'' to 31/2'' and handles
up to 30 million or more standard cubic feet per day (mmscfd) of
lift gas. A typical injection pressure is 2,500 pounds per square
inch (psi). The coil tubing 13 is deployed by an injector 15
through a BOP which is nippled up to a diverter valve similar to
that shown in FIG. 4.
[0051] A simple coil tubing gas lift string is often employed with
no gas lift valves. FIGS. 5A and 5B show the nozzle on the inner
string. In some embodiments, the jetting sub may be used to reduce
vibration and provide effective mixing of the fluid. The shape of
the sub and direction of the jet pin the bottom of the string
against the riser. In some embodiments a jointed gas lift string
utilized instead one conveyed by a coil-tubing rig.
[0052] The lift gas is often injected using export compressors
which can deliver gas at 2,500 psi. In some embodiments a dedicated
compressor is used to deliver lift gas.
[0053] Once rigged up a coil-tubing rig can deploy or pull a gas
lift string within one day.
[0054] A typical steel catenary riser in 7,000 ft will have a 12
degree top angle and the length of the suspended riser is 8,800 ft.
For example, FIG. 6 shows an example of a gas lift string 13 placed
in a riser/flowline 19 having catenary curvature. Some embodiments
use a flexible hose riser or a steel or flexible riser outfitted
with buoyancy to create a second catenary curve (sometimes called a
lazy-wave riser.
[0055] A tubing hanger is often run at the top of the gas lift
string. The hanger is hung off in a valve block which seals the
lower section of the valve block from the upper section. Lift gas
is injected with pressure in the upper section where it enters the
gas lift string. The lift gas exits at the bottom of the gas lift
string where it mixes with the production in the annulus. The
mixture returns up the annulus to the lower section of the valve
block where it exits to the production facility. This valve block
is often called a diverter valve.
[0056] FIG. 7 shows the arrangement of the gas lift apparatus
between the coil-tubing rig injector and the diverter valve block
16 & 21. As shown in FIG. 7, the injector is connected to the
diverter valve via a BOP stack. This arrangement is for installing
a coil tubing gas lift string. Another embodiment uses a jointed
gas lift string and is installed with a different type rig.
[0057] The present invention modifies this process. The modified
process takes advantage of a gas lift tubing that is packed with a
catalyst and/or coated with a catalyst. In specific embodiments,
the gas lift tubing is packed with a Fischer-Tropsch catalyst. In
other embodiments, the tubing is coated with a Fischer-Tropsch
catalyst. Any Fischer-Tropsch catalyst suitable for the conversion
of synthesis gas or H.sub.2 and CO into hydrocarbons by the
Fischer-Tropsch process may be used in the gas lift tubing
arrangement described herein.
[0058] This modified process provides several advantages and
provides solutions for several industry-wide problems. For example,
this apparatus and process takes advantage of the fact that the
catalyst deposited inside the tubing makes it easier to change and
remove the catalyst by simply removing the tubing. Also, the
process may be modified to transform a second feedstock into a
particular product by simply removing the tubing containing a first
catalyst and inserting a second tubing that has a second catalyst
which is a different catalyst from the first catalyst. This
demonstrates the ease in which the coil tubing can be replaced as
well as the ease in which the catalyst and/or process can be
changed. The arrangement also allows for the chemical reaction to
take place at a much higher pressure. In normal reactors the
maximum pressure is around 150 psi. However by using a modified gas
lift string the reaction pressure can be raised to 10,000 psi or
more with standard oilfield equipment. The higher pressure
increases the efficiency of the chemical reaction whenever the
reaction results in fewer molecules (as in the Fischer Tropsch
process). This is called the Le Chatelier Principle. The higher
pressure should also lower the reaction temperature.
[0059] In particular, the BOP is used in running the gas lift
string (or tubing). Once the gas lift string is in place, the BOP
is removed. The diverter valve consists of a multivalve block with
an internal receptacle that allows a tubing hanger to be set. The
hanger seals the annulus of the block and supports the tubing.
Below this seal is an outlet valve through which the mixed
production (the products) and the injection gas (the feedstock)
exits the valve block. Gas is injected in the top of the hanger and
the seal forces the gas to exit at the bottom of the gas lift
string (the tubing).
[0060] In this process, hydrogen and carbon monoxide are injected
into the top of the tubing packed with a suitable Fischer-Tropsch
catalyst. Also, gas is injected through the tubing and the
synthetic hydrocarbons flow out of the bottom of the tubing and
travel up the annulus to the surface. As the gases (H.sub.2 and CO)
travel past the catalyst, synthetic hydrocarbons are formed and
heat is produced. In some embodiments, the process is controlled by
using cooling water or cooling oil. As the synthetic hydrocarbons
and water flow out of the bottom of the tubing and travel up the
annulus to the surface, any gas (H.sub.2 and CO) not converted to
synthetic hydrocarbons travels up annulus to the surface where it
is reprocessed and re-injected through the tubing.
[0061] In some embodiments, this process is carried out in a
producing well or in a producing riser. In a producing well or a
producing marine riser, the production from the well which flows up
the annulus cools the synthetic hydrocarbons. In additional and
alternate embodiments, this process can be used in non-flowing
wells. In this case cooling water or cooling oil is circulated up
the annulus where it mixes with the newly formed petroleum product,
and at the surface, the water is separated and cooled for
re-injection.
[0062] The tubing can be adapted to carry out other processes in
addition to the Fischer-Tropsch process. For example, these
processes include, but are not limited to, the Haber process, the
Haber-Bosch process, processes used to industrially produce ammonia
or synthesis gas, the Claus process, the gas desulfurizing process,
processes used to recover elemental sulfur from gaseous hydrogen
sulfide, the Bergius Process, processes used to produce liquid
hydrocarbons for use as synthetic fuel by hydrogenation of
high-volatile bituminous coal at high temperature and pressure, the
Deacon process, the Deacon-Leblanc process, the Sabatier process,
the Sabatier-Senderens process, hydrogenation processes, oxidation
processes, ammonia oxidation processes, the Andrussov synthesis,
hydrocracking processes, alkylation processes, hydrotreating
processes, catalytic reforming processes, coke formation, naphtha
reforming processes, processes for the formation, reformation and
functionalization of aromatics, cyclar processes, M2-forming
process, catalytic dewaxing processes, isomerization processes,
isopropyl alcohol formation, acetone formation, bisphenol-A
formation, cumene formation, vinyl chloride formation,
oxychlorination processes, formation of synthetic rubber from
butadiene and styrene, formation of butadiene from butane or
butenes, styrene production, nylon production, production of nylon
intermediates, formation of adipic acid, formation of
hexamethylenediamine, formation of nylon polymer, the Snia-Viscosa
process, hydroformylation and carbonylation processes, metathesis
of olefins, the Shell Higher-Olefins process, polyethylene
formation, polypropylene formation, formation of ammonia synthesis
gas, feedstock purification processes, hydrodesulfurization
processes, processes for chlorine removal, sulfur adsorption, steam
reforming, carbon monoxide removal, carbon monoxide conversion, and
methanation, formation of methanol synthesis gas, formation of OXO
synthesis gas, hydrogen production, processes for steam reforming
of reducing gas, town gas production, autothermal reforming
processes, the Claude Process, and processes for volatile organic
compound removal. These exemplary processes are well known and it
is within the skill of the ordinary artisan to be able to select
the appropriate feedstock and catalyst needed to carry out any of
these processes. The apparatus and method as described herein can
be modified to carry out each of the aforementioned processes.
These processes are well known by the skilled artisan. The
appropriate feedstock, catalyst and resulting products are
described for each of these processes in Lawrie Lloyd's Handbook of
Industrial Catalyst (Springer 2011), which is incorporated herein
by reference in its entirety.
[0063] In particular, the apparatus and methods disclosed herein
are capable of carrying out the Fischer-Tropsch process, dry carbon
dioxide (CO.sub.2) reforming, hydrocarbon cracking of hydrocarbons,
and/or steam reforming.
[0064] Carbon Dioxide Reforming
[0065] Carbon dioxide (CO.sub.2) reforming (also known as dry
reforming) is a method of producing synthesis gas (mixtures of
hydrogen and carbon monoxide) from the reaction of carbon dioxide
with hydrocarbons such as methane. Synthesis gas is conventionally
produced via the steam reforming reaction. The methane carbon
dioxide reforming reaction may be represented by:
CO.sub.2+CH.sub.4.fwdarw.2H.sub.2+2CO (5)
[0066] In some embodiments, the gas lift tubing contains a catalyst
suitable for carbon dioxide reforming. In this embodiment, carbon
dioxide and methane (or other hydrocarbons) is the feedstock and
the hydrogen and carbon monoxide are the products of this
process.
[0067] Hydrocarbon Cracking
[0068] Cracking is the process whereby complex organic molecules
such as kerogens or heavy hydrocarbons are broken down into simpler
molecules such as light hydrocarbons, by the breaking of
carbon-carbon bonds in the precursors. The rate of cracking and the
end products are strongly dependent on the temperature and presence
of catalysts. Cracking is the breakdown of a large alkane into
smaller, more useful alkanes and alkenes. Simply put, hydrocarbon
cracking is the process of breaking long-chain hydrocarbons into
short ones.
[0069] Here is an example of cracking of butane
CH.sub.3-CH.sub.2-CH.sub.2-CH.sub.3
[0070] The first possible mechanism is responsible for an estimated
48% of butane cracking products where breaking is done on the
CH.sub.3--CH.sub.2 bond which results in the following radical
products: CH.sub.3. and .CH.sub.2--CH.sub.2--CH.sub.3. After a
certain number of steps, an alkane and an alkene are obtained:
CH.sub.4+CH.sub.2.dbd.CH--CH.sub.3.
[0071] The second possible mechanism is responsible for an
estimated 38% of butane cracking products where breaking is done on
the CH.sub.2--CH.sub.2 bond which results in the following radical
products: CH.sub.3--CH.sub.2. and .CH.sub.2--CH.sub.3. After a
certain number of steps, an alkane and an alkene are obtained:
CH.sub.3--CH.sub.3+CH.sub.2.dbd.CH.sub.2
[0072] The third possible mechanism is responsible for an estimated
14% of butane cracking products where the C--H bond is broken.
After a certain number of steps, an alkene and hydrogen gas is
obtained: CH.sub.2.dbd.CH--CH.sub.2--CH.sub.3+H.sub.2 this is very
useful since the catalyst is not exhausted and can be used for
further cracking of hydrocarbons.
[0073] The catalytic cracking process involves the presence of acid
catalysts (usually solid acids such as silica-alumina and zeolites)
which promote a heterolytic (asymmetric) breakage of bonds yielding
pairs of ions of opposite charges, usually a carbocation and the
very unstable hydride anion. Carbon-localized free radicals and
cations are both highly unstable and undergo processes of chain
rearrangement, C--C scission in position beta as in cracking, and
intra- and intermolecular hydrogen transfer or hydride transfer. In
both types of processes, the corresponding reactive intermediates
(radicals, ions) are permanently regenerated, and thus they proceed
by a self-propagating chain mechanism. The chain of reactions is
eventually terminated by radical or ion recombination.
[0074] In some embodiments, the gas lift tubing contains a catalyst
suitable for hydrocarbon cracking. In this embodiment, a
hydrocarbon (i.e. a hydrocarbon containing a range of carbons
between 2 and 45 carbons, and/or any other range or specific number
found between 2 and 45) is the feedstock and an alkane, alkene
and/or hydrogen are the products of this process.
[0075] Steam Reforming
[0076] Steam reforming of natural gas or synthetic gas sometimes
referred to as steam methane reforming (SMR) is the most common
method of producing commercial bulk hydrogen as well as the
hydrogen used in the industrial synthesis of ammonia. At high
temperatures (700-1100.degree. C.) and in the presence of a
metal-based catalyst (nickel), steam reacts with methane to yield
carbon monoxide and hydrogen. These two reactions are reversible in
nature.
CH.sub.4+H.sub.2OCO+3 H.sub.2 (6)
[0077] Additional hydrogen can be recovered by a lower-temperature
gas-shift reaction with the carbon monoxide produced. The reaction
is summarized by:
CO+H.sub.2O.fwdarw.CO.sub.2+H.sub.2 (7)
[0078] The first reaction is strongly endothermic (consumes heat),
the second reaction is mildly exothermic (produces heat).
[0079] In some embodiments, the gas lift tubing contains a catalyst
suitable for steam reforming. In this embodiment, methane and water
are the feedstock and an carbon monoxide and hydrogen are the
products of first stage of this process. For the second stage of
this process, carbon monoxide and water are the feedstock and
carbon dioxide and hydrogen are the products.
[0080] In additional embodiments, the dry reforming process takes
place in the annulus where there is CO.sub.2 and CH.sub.4 in the
oil stream. In this embodiment, the catalyst coats the tubing on
the outside and the particular catalyst used is a dry reforming
catalyst. This approach solves the basic problem of carbon
formation with dry reforming. In conventional settings, the carbon
plugs the reactor in a few hours and makes the process impractical.
In the apparatus disclosed herein, the crude oil washes the carbon
from the catalyst and allows the process to continue.
[0081] Once the reformed hydrogen and carbon monoxide are recovered
they are pumped down the interior of tubing where they are
hydrogenated. In an alternate embodiment, the method and the
apparatus may incorporate a catalyst in part of the tubing that
makes solvents, and these newly formed solvents may aid in cleaning
the outside of the tubing.
[0082] In some embodiments, it is most practical to coat both the
inside and outside of the tubing in the gas lift apparatus. For
example, the gas lift apparatus could be adapted to breakdown the
heavier oils in the annulus by thermal cracking In this example, a
catalyst coated on the outside on the tubing may facilitate this
process especially when the tubing is heated using the heat from
the internal exothermic catalytic process occurring on the interior
of the tubing.
[0083] There are a number of advantages to using the apparatus and
methods described herein. For example, the apparatus and method is
carried out using a small footprint because the process is carried
out in a linear arrangement. Due to the linear arrangement of the
apparatus, it is possible to carry out the process in multiple
stages where the catalyst is segregated along the tubing in
multiple stages. Another advantage is that this apparatus and
method removes the need for a heat exchanger. One of the most
important advantages is that the process does not have to deliver a
precise product, almost any liquid hydrocarbon will suffice because
all of the products are combined and mixed with the crude unrefined
product. As mentioned above, another advantage is that the catalyst
can be easily changed. Furthermore, the method and apparatus can be
conducted under high pressure. Also, the method and apparatus can
be used as a hydrate mitigation system and eliminate costly
insulation for marine risers.
[0084] The processes of the present disclosure may be carried out
using the method(s) and apparatus described herein. These methods
can be further modified and optimized using the principles and
techniques of chemical engineering, mechanical engineering,
petroleum chemistry, organic chemistry and/or polymer chemistry as
applied by a person skilled in the art. Such principles and
techniques are taught, for example, in Lawrie Lloyd's Handbook of
Industrial Catalyst (Springer 2011), which is incorporated herein
by reference in its entirety.
[0085] As an example of the gas lift apparatus being modified to
carry out an alternative process, ethene may be converted to
ethanol. In general, when there are other gases (other than
synthetic gas) being injected into the tubing, these other gasses
may be converted to other valuable products. For example, an ethene
component in the gas stream may be converted to ethanol by passing
ethene over a catalyst either packed in the tubing or through a
tubing having a catalyst coated wall.
[0086] As an alternate example, the tubing may be coated, either on
the outside or on the inside, with a water shift catalyst which
would be used to convert CO.sub.2 in the production stream to CO
and H.sub.2O.
[0087] In some examples, it may be necessary to control the rate at
which the feedstock is converted to the desired product. The
conversion rate may be controlled by varying the concentration of
the catalyst distributed along the tubing. For example, the
catalyst composition along the tubing may be segregated so that
different heavy components of the gas stream (C2-C6) are converted
into liquids at different points along the tubing. This segregation
may allow for better control of the conversion rate as well as
better control of the products obtained. These more defined
products can then be mixed with crude oil. The same is true for
converting any feedstock or gas stream constituents into the
desired materials.
[0088] An additional advantage of segregating the catalyst in the
tubing is that the same tubing can be used for multi-stage
conversions. For example, the tubing can be segregated into two or
more sections. In the first section, a first catalyst type may be
used for a particular conversion. In the second section, a second
catalyst type may use the product of the conversion taking place in
the first section as a feedstock for a second type of conversion.
The use of this type of tandem conversion within the same tubing is
extremely beneficial and useful in reducing the industrial
footprint needed to carry out this type of operation.
[0089] Furthermore, the apparatus disclosed herein is very
efficient in that it is configured such that the heat/energy
produced due to exothermic nature of the catalytic conversion may
be used to inhibit or facilitate other processes. For example, the
use of a tubing coated with a catalyst or a tubing packed catalyst
where the catalyst undergoes an exothermic reaction allows for the
energy produced from this exothermic reaction to be used to inhibit
hydrate formation in the annulus where production is flowing (oil
gas or both).
EXAMPLES
[0090] The following examples are included to demonstrate preferred
embodiments of the invention. It should be appreciated by those of
skill in the art that the techniques disclosed in the examples
which follow represent techniques discovered by the inventors to
function well in the practice of the invention, and thus can be
considered to constitute preferred modes for its practice. However,
those of skill in the art should, in light of the present
disclosure, appreciate that many changes can be made in the
specific embodiments which are disclosed and still obtain a like or
similar result without departing from the spirit and scope of the
invention.
Example 1
[0091] This example, provides an exemplary method for producing
synthetic hydrocarbons. Any and all of the selected method
embodiments disclosed herein may be adapted such that any disclosed
apparatus may be used to carry out any and all of the disclosed the
method embodiments.
[0092] In some embodiments, the method for producing synthetic
hydrocarbons comprises the steps of: (1) injecting hydrogen and
carbon monoxide into a gas lift apparatus; and, (2) forcing
synthetic hydrocarbons out of the gas lift apparatus. Also, this
method is adapted such that the gas lift apparatus comprises a
tubing and an annulus, the tubing is packed with a Fischer-Tropsch
catalyst, and the tubing is configured such that hydrogen and
carbon monoxide travel past the Fischer-Tropsch catalyst to form
synthetic hydrocarbons.
[0093] In additional embodiments, the apparatus is configured such
that the synthetic hydrocarbons and water flow out of the bottom of
the tubing and travel up the annulus to the surface.
[0094] In further embodiments, the method may include the following
additional steps: (1) separating any hydrogen or carbon dioxide
from the synthetic hydrocarbons forced out of the gas lift
apparatus; and, (2) reprocessing and re-injecting any hydrogen or
carbon dioxide not converted to synthetic hydrocarbons.
[0095] In specific embodiments, the method for producing synthetic
hydrocarbons is carried out in a producing well. In this
embodiment, the method may be modified such that production from
the producing well flows up the annulus and cools the synthetic
hydrocarbons.
[0096] In alternate embodiments, the method for producing synthetic
hydrocarbons is carried out in a producing riser. In this
embodiment, the method may be modified such that production from
the producing riser flows up the annulus and cools the synthetic
hydrocarbons.
[0097] In additional and/or alternate embodiments, the method for
producing synthetic hydrocarbons is carried out in a non-flowing
well.
[0098] In each of the aforementioned embodiments, the method may be
modified by including the following additional steps: (1)
circulating cooling fluid up the annulus wherein the cooling fluid
mixes with the newly formed synthetic hydrocarbons; (2) separating
the cooling fluid from the newly formed synthetic hydrocarbons
wherein the separating step takes place at the surface; (3)
re-cooling the cooling fluid; and, (4) re-injecting the re-cooled
cooling fluid.
[0099] FIG. 1 shows a low temperature high pressure Fischer-Tropsch
Process in a producing well. As shown in FIG. 1, the feedstock 1,
CO and H.sub.2, is injected at 2500 psi. As the CO and H.sub.2
travel down a cobalt packed two inch tubing 2, oil, gas and water
(250.degree. F.) are pushed out-up through the annulus 4. FIG. 1
provides an example of how synthesis gas is produced and mixed with
production 5. The well is producing 12,000 BBLD of oil 3 at 12
mmscfd, 200.degree. F., 1,800 psi and is a mixture of oil, methane
and water. As shown in FIG. 1, the tubing containing the catalyst
is approximately 5000 feet long.
[0100] FIG. 2 shows a Fischer-Tropsch Process in a dummy well. As
shown in FIG. 2, the feedstock 6, CO and H.sub.2, is injected at
2500 to 3000 psi at a rate of 1.2 mmscfd. As the CO and H.sub.2
flow down a cobalt packed two inch tubing 7, synthetic oil, hot oil
and water (205.degree. F.) are pushed out of the annulus 11. Also
in FIG. 2, cooling oil 9 is circulated through the cooling casing
10 and mixed with the synthetic hydrocarbon products in the annulus
8 and flow up the annulus and out of the annulus 11 at a rate of 90
gallons per minute (gpm) and at a temperature of 60.degree. F.
Example 2
[0101] This example, provides an exemplary apparatus for producing
synthetic hydrocarbons. Any and all of the selected apparatus
embodiments disclosed herein may be adapted such that the disclosed
method(s) may be carried out using any and all of the disclosed the
apparatus embodiments.
[0102] An apparatus for producing synthetic hydrocarbons comprises
at least a tubing and an annulus. For example, the apparatus for
producing synthetic hydrocarbons comprises a tubing packed with a
Fischer-Tropsch catalyst. The tubing is configured such that as
hydrogen and carbon monoxide are injected into the top of the
tubing, hydrogen and carbon monoxide travel past the
Fischer-Tropsch catalyst to produce synthetic hydrocarbons; and as
synthetic hydrocarbons are produced heat is rejected.
[0103] In some embodiments, the apparatus may be modified such that
the tubing is configured to direct synthetic hydrocarbons and water
out of the bottom of the tubing and up the annulus to the
surface.
[0104] In additional embodiments, the apparatus is modified such
that any hydrogen or carbon monoxide not converted to synthetic
hydrocarbons travels up the annulus to the surface where the
non-converted hydrogen or carbon monoxide is reprocessed and
re-injected.
[0105] In some embodiments, the apparatus is placed in a producing
well. In these embodiments, production from the producing well
flows up the annulus and cools the synthetic hydrocarbons.
[0106] In additional and/or alternate embodiments, the apparatus is
placed in a producing riser. In these embodiments, production from
the producing riser flows up the annulus and cools the synthetic
hydrocarbons.
[0107] In additional and/or alternate embodiments, the apparatus is
placed in a non-flowing well. In these embodiments and any of the
aforementioned embodiments in Example 3, the apparatus is capable
of circulating cooling water up the annulus where it mixes with the
newly formed petroleum product, and at the surface, the water is
separated and cooled for re-injection.
Example 3
[0108] In some embodiments, a method for producing synthetic
hydrocarbon derived products comprises the steps of: (1) injecting
a feedstock into a gas lift apparatus; and (2) forcing synthetic
hydrocarbon derived product out of the gas lift apparatus. The gas
lift apparatus comprises a tubing and an annulus, and the tubing
further comprises a catalyst. Also, the tubing is configured such
that the feedstock travels past the catalyst to form synthetic
hydrocarbon derived products.
[0109] In specific embodiments, the tubing is coated and/or packed
with a catalyst and/or the apparatus is configured such that the
synthetic hydrocarbon derived products flow out of the bottom of
the tubing and travel up the annulus to the surface.
[0110] In some embodiments the method further comprises the steps
of: (1) separating any remaining feedstock from the synthetic
hydrocarbon products forced out of the gas lift apparatus; and, (2)
reprocessing and re-injecting any feedstock not converted to
synthetic hydrocarbon products.
[0111] In specific embodiments of the method, the feedstock and
catalyst are suitable for performing a process selected from the
group consisting of the Haber process, the Haber-Bosch process,
processes used to industrially produce ammonia or synthesis gas,
the Claus process, the gas desulfurizing process, processes used to
recover elemental sulfur from gaseous hydrogen sulfide, the Bergius
Process, processes used to produce liquid hydrocarbons for use as
synthetic fuel by hydrogenation of high-volatile bituminous coal at
high temperature and pressure, the Deacon process, the
Deacon-Leblanc process, the Sabatier process, the
Sabatier-Senderens process, hydrogenation processes, oxidation
processes, ammonia oxidation processes, the Andrussov synthesis,
hydrocracking processes, alkylation processes, hydrotreating
processes, catalytic reforming processes, coke formation, naphtha
reforming processes, processes for the formation, reformation and
functionaliztion of aromatics, cyclar processes, M2-forming
process, catalytic dewaxing processes, isomerization processes,
isopropyl alcohol formation, acetone formation, bisphenol-A
formation, cumene formation, vinyl chloride formation,
oxychlorination processes, formation of synthetic rubber from
butadiene and styrene, formation of butadiene from butane or
butenes, styrene production, nylon production, production of nylon
intermediates, formation of adipic acid, formation of
hexamethylenediamine, formation of nylon polymer, the Snia-Viscosa
process, hydroformylation and carbonylation processes, metathesis
of olefins, the Shell Higher-Olefins process, polyethylene
formation, polypropylene formation, formation of ammonia synthesis
gas, feedstock purification processes, hydrodesulfurization
processes, processes for chlorine removal, sulfur adsorption, steam
reforming, carbon monoxide removal, carbon monoxide conversion, and
methanation, formation of methanol synthesis gas, formation of OXO
synthesis gas, hydrogen production, processes for steam reforming
of reducing gas, town gas production, autothermal reforming
processes, the Claude Process, processes for volatile organic
compound removal, the Fischer-Tropsch process, dry carbon dioxide
(CO.sub.2) reforming, hydrocarbon cracking of hydrocarbons, and
steam reforming.
[0112] In more specific embodiments of the method, the feedstock
and the catalyst are suitable for performing a process selected
from the group consisting of the Fischer-Tropsch process, dry
carbon dioxide (CO.sub.2) reforming, hydrocarbon cracking of
hydrocarbons, and steam reforming.
[0113] In some embodiments, the method is carried out in a
producing well. Also, the production from the producing well flows
up the annulus and cools the synthetic hydrocarbon derived
products.
[0114] In additional embodiments, the method is carried out in a
producing riser. Also, the production from the producing riser
flows up the annulus and cools the synthetic hydrocarbon derived
products.
[0115] In alternate embodiments, the method is carried out in a
non-flowing well.
[0116] In further embodiments, the method the further comprises the
steps of: (1) circulating cooling fluid up the annulus wherein the
cooling fluid mixes with the newly formed synthetic hydrocarbon
derived products; (2) separating the cooling fluid from the newly
formed synthetic hydrocarbon derived products wherein the
separating step takes place at the surface; (3) re-cooling the
cooling fluid; and, (4) re-injecting the re-cooled cooling
fluid.
Example 4
[0117] In some embodiments, the apparatus for producing synthetic
hydrocarbon derived products comprises (1) a tubing, and (2) an
annulus. The tubing is packed or coated with a catalyst. Also, the
tubing is configured such that (1) a feedstock is injected into the
top of the tubing, (2) the feedstock travels past the catalyst to
produce a synthetic hydrocarbon derived product; and, (3) heat is
rejected as the synthetic hydrocarbon derived product is
produced.
[0118] In particular embodiments, the tubing is configured such
that the synthetic hydrocarbon derived product and water flow out
of the bottom of the tubing and travel up the annulus to the
surface.
[0119] In some examples, any feedstock not converted to a synthetic
hydrocarbon derived product travels up the annulus to the surface
where the non-converted feedstock is reprocessed and
re-injected.
[0120] In particular examples, the feedstock and the catalyst are
suitable for producing a hydrocarbon derived product resulting from
a process selected from the group consisting of the Haber process,
the Haber-Bosch process, processes used to industrially produce
ammonia or synthesis gas, the Claus process, the gas desulfurizing
process, processes used to recover elemental sulfur from gaseous
hydrogen sulfide, the Bergius Process, processes used to produce
liquid hydrocarbons for use as synthetic fuel by hydrogenation of
high-volatile bituminous coal at high temperature and pressure, the
Deacon process, the Deacon-Leblanc process, the Sabatier process,
the Sabatier-Senderens process, hydrogenation processes, oxidation
processes, ammonia oxidation processes, the Andrussov synthesis,
hydrocracking processes, alkylation processes, hydrotreating
processes, catalytic reforming processes, coke formation, naphtha
reforming processes, processes for the formation, reformation and
functionaliztion of aromatics, cyclar processes, M2-forming
process, catalytic dewaxing processes, isomerization processes,
isopropyl alcohol formation, acetone formation, bisphenol-A
formation, cumene formation, vinyl chloride formation,
oxychlorination processes, formation of synthetic rubber from
butadiene and styrene, formation of butadiene from butane or
butenes, styrene production, nylon production, production of nylon
intermediates, formation of adipic acid, formation of
hexamethylenediamine, formation of nylon polymer, the Snia-Viscosa
process, hydroformylation and carbonylation processes, metathesis
of olefins, the Shell Higher-Olefins process, polyethylene
formation, polypropylene formation, formation of ammonia synthesis
gas, feedstock purification processes, hydrodesulfurization
processes, processes for chlorine removal, sulfur adsorption, steam
reforming, carbon monoxide removal, carbon monoxide conversion, and
methanation, formation of methanol synthesis gas, formation of OXO
synthesis gas, hydrogen production, processes for steam reforming
of reducing gas, town gas production, autothermal reforming
processes, the Claude Process, processes for volatile organic
compound removal, the Fischer-Tropsch process, dry carbon dioxide
(CO2) reforming, hydrocarbon cracking of hydrocarbons, and steam
reforming.
[0121] In specific embodiments, the feedstock and the catalyst are
suitable for producing a hydrocarbon derived product resulting from
a process selected from the group consisting of the Fischer-Tropsch
process, dry carbon dioxide (CO2) reforming, hydrocarbon cracking,
and steam reforming.
[0122] In some examples, the apparatus is placed in a producing
well. Also, production from the producing well flows up the annulus
and cools the synthetic hydrocarbons.
[0123] In other examples, the apparatus is placed in a producing
riser. The production from the producing riser flows up the annulus
and cools the synthetic hydrocarbons.
[0124] In alternate examples, the apparatus is placed in a
non-flowing well. Also, the apparatus is capable of circulating
cooling water up the annulus where it mixes with the newly formed
petroleum product, and at the surface, the water is separated and
cooled for re-injection.
REFERENCES
[0125] All patents and publications mentioned in the specification
are indicative of the level of those skilled in the art to which
the invention pertains. All patents and publications are herein
incorporated by reference in their entirety to the same extent as
if each individual publication was specifically and individually
indicated to be incorporated by reference.
Patents
[0126] U.S. Pat. No. 4,039,302
[0127] U.S. Pat. No. 4,826,800
[0128] U.S. Pat. No. 5,345,005
[0129] U.S. Pat. No. 5,811,365
[0130] U.S. Pat. No. 5,945,458
Publications
[0131] EP 127220
[0132] EP 142887
[0133] EP 221598
[0134] EP 261870
[0135] GB 2125062
[0136] GB 2130113
[0137] GB 2146350
[0138] WO 01/38269
[0139] WO 03/090925
[0140] Although the present invention and its advantages have been
described in detail, it should be understood that various changes,
substitutions and alterations can be made herein without departing
from the spirit and scope of the invention as defined by the
appended claims. Moreover, the scope of the present application is
not intended to be limited to the particular embodiments of the
process, machine, manufacture, composition of matter, means,
methods and steps described in the specification. As one of
ordinary skill in the art will readily appreciate from the
disclosure of the present invention, processes, machines,
manufacture, compositions of matter, means, methods, or steps,
presently existing or later to be developed that perform
substantially the same function or achieve substantially the same
result as the corresponding embodiments described herein may be
utilized according to the present invention. Accordingly, the
appended claims are intended to include within their scope such
processes, machines, manufacture, compositions of matter, means,
methods, or steps.
* * * * *