Chemistry: fischer-tropsch processes; or purification or recover – Liquid phase fischer-tropsch reaction
Reexamination Certificate
2001-09-14
2003-12-23
Parsa, J. (Department: 1621)
Chemistry: fischer-tropsch processes; or purification or recover
Liquid phase fischer-tropsch reaction
C518S702000, C166S267000, C095S150000
Reexamination Certificate
active
06667347
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to removing CO
2
from CH
4
-containing gases. In particular, the present invention is directed to scrubbing CO
2
from a CH
4
-containing gas using an aqueous stream, forming a CO
2
-reduced CH
4
-containing gas and a CO
2
-enriched aqueous stream, processing the CO
2
-reduced CH
4
-containing gas to form salable liquid products, and disposing of the CO
2
-enriched aqueous stream.
2. Description of the Related Art
The conversion of remote natural gas assets into transportation fuels has become more desirable because of the need to exploit existing natural gas assets as a way to satisfy the increasing need for transportation fuels. Generally, the term “remote natural gas” refers to a natural gas asset that cannot be economically shipped to a commercial market by pipeline.
Conventionally, two approaches exist for converting remote natural gases into conventional transportation fuels and lubricants including, but not limited to, gasoline, diesel fuel, jet fuel, lube base stocks, and the like. The first approach comprises converting natural gas into synthesis gas by partial oxidation, followed by a Fischer-Tropsch process, and further refining of resulting Fischer-Tropsch products. The second approach comprises converting natural gas into synthesis gas by partial oxidation, followed by methanol synthesis wherein the synthesized methanol is subsequently converted into highly aromatic gasoline by a Methanol-To-Gasoline (MTG) process. Both of these approaches use synthesis gas as an intermediate. Also, while other approaches exist for using natural gas in remote locations, such approaches do not produce conventional transportation fuels and lubricants, but instead produce other petroleum products including, but not limited to, liquified natural gas (LNG) and converted methanol. The Fischer-Tropsch and MTG processes both have advantages and disadvantages. For instance, the Fischer-Tropsch process has the advantage of forming products that are highly paraffinic. Highly paraffinic products are desirable because they exhibit excellent combustion and lubricating properties. Unfortunately, a disadvantage of the Fischer-Tropsch process is that the Fischer-Tropsch process emits relatively large amounts of CO
2
during the conversion of natural gas assets into salable products. An advantage of the MTG process is that the MTG process produces highly aromatic gasoline and LPG fractions (e.g., propane and butane). However, while highly aromatic gasoline produced by the MTG process is generally suitable for use in conventional gasoline engines, highly aromatic MTG gasoline may be prone to form durene and other polymethyl aromatics having low crystallization temperatures that form solids upon standing. In addition, the MTG process is more expensive than the Fischer-Tropsch process and the products produced by the MTG process cannot be used for lubricants, diesel engine fuels or jet turbine fuels.
Catalysts and conditions for performing Fischer-Tropsch reactions are well known to those of skill in the art, and are described, for example, in EP 0 921 184A1, the contents of which are hereby incorporated by reference in their entirety. A schematic of a conventional Fischer-Tropsch process is shown in FIG.
1
.
The Fischer-Tropsch process can be understood by examining the stoichometry of the reaction that occurs during a Fischer-Tropsch process. For example, during Fischer-Tropsch processing, synthesis gas (i.e., a mixture including CO
2
and hydrogen), is generated, typically from at least one of three basic reactions. Typical Fischer-Tropsch reaction products include paraffins and olefins, generally represented by the formula nCH
2
. While this formula accurately defines mono-olefin products, it only approximately defines C
5
+
paraffin products. The value of n (i.e., the average carbon number of the product) is determined by reaction conditions including, but not limited to, temperature, pressure, space rate, catalyst type and synthesis gas composition. The desired net synthesis gas stoichiometry for a Fischer-Tropsch reaction is independent of the average carbon number (n) of the product and is about 2.0, as determined by the following reaction equation:
nCO+2nH
2
→nH
2
O+nCH
2
where nCH
2
represents typical Fischer-Tropsch reaction products such as, for example, olefins and paraffins.
The three general reactions that produce synthesis gas from methane are as follows:
1. steam reforming of methane: CH
4
+H
2
O→CO+3H
2
;
2. dry reforming, or reaction between CO
2
and methane: CH
4
+CO
2
→2CO+2H
2
; and
3. partial oxidation using oxygen: CH
4
+1/2O
2
→CO+2H
2
.
Although the above general reactions are the basic reactions used to produce synthesis gas, the ratio of hydrogen to carbon monoxide produced by the above reactions is not always adequate for the desired Fischer-Tropsch conversion ratio of 2.0. For example, in the steam reforming reaction, the resulting ratio of hydrogen to carbon monoxide is 3.0, which is higher than the desired hydrogen to carbon ratio of 2.0 for a Fischer-Tropsch conversion. Similarly, in the dry reforming reaction, the resulting hydrogen to carbon monoxide ratio is 1.0, which is lower than the desired hydrogen to carbon monoxide ratio of 2.0 for a Fischer-Tropsch conversion. In addition to exhibiting a hydrogen to carbon monoxide ratio that is lower than the desired ratio for a Fischer-Tropsch conversion, the above dry reforming reaction also suffers from problems associated with rapid carbon deposition. Finally, because the above partial oxidation reaction provides a hydrogen to carbon monoxide ratio of 2.0, the partial oxidation reaction is the preferred reaction for Fischer-Tropsch conversions.
In commercial practice, an amount of steam added to a partial oxidation reformer can control carbon formation. Likewise, certain amounts of CO
2
can be tolerated in the feed. Thus, even though partial oxidation is the preferred reaction for Fischer-Tropsch conversions, all of the above reactions can occur, to some extent, in an oxidation reformer.
During partial oxidation, CO
2
forms because the reaction is not perfectly selective. That is, some amount of methane in the reaction will react with oxygen to form CO
2
by complete combustion. The reaction of methane with oxygen to form CO
2
is generally represented by the following reactions:
CH
4
+O
2
→CO
2
+2H
2
and
CH
4
+2O
2
→CO
2
+2H
2
O.
Furthermore, steam added to the reformer to control coking, or steam produced during the Fischer-Tropsch reaction can react with CO to form CO
2
in a water gas shift reaction represented by the following general reaction:
CO+H
2
O→CO
2
+H
2
.
Thus, invariably a significant amount of CO
2
is formed during the conversion of methane into transportation fuels and lubricants by the Fischer-Tropsch process. The CO
2
produced during the Fischer-Tropsch process exits the Fischer-Tropsch/Gas-To-Liquid (GTL) process in a tail gas exiting a Fischer-Tropsch facility. Tail gases exiting a Fischer-Tropsch/GTL process comprise any gases that remain unconsumed by the Fischer-Tropsch process.
The above equations represent general stoichiometric equations, they do not reflect an optimum synthesis gas composition for the kinetics or selectivity of a Fischer-Tropsch reaction. Moreover, depending on the nature of the Fischer-Tropsch catalyst, synthesis gas ratios other than about 2.0, typically less than about 2.0, are used to prepare the feed to a Fischer-Tropsch facility. However, because Fischer-Tropsch facilities typically produce products exhibiting a hydrogen to carbon ratio of about 2.0, the limiting reagent, typically H
2
, is consumed first. The extra reagent, typically CO, is then recycled back to the Fischer-Tropsch facility for further conversion. Synthesis gas compositions having hydrogen to carbon ratios other than about 2.0 are typically generated by recycling unused reagents.
As a result, ther
Munson Curtis
O'Rear Dennis J.
Burns Doane Swecker & Mathis L.L.P.
Chevron U.S.A. Inc.
Parsa J.
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