The present invention applies to the field of liquefying natural gas.
Liquefaction of natural gas is a particularly important industrial process, with a global production capacity of about 300 million tons per annum (MTPA), mainly obtained from large-scale plants (baseload) with a capacity from 3 MTPA to 8 MTPA each.
The use of baseload plants has been justified so far by the economies of scale and by the increased energy efficiency, which can be obtained by increasing the production capacity; this was possible with significant initial investments.
Before sending the natural gas for liquefaction, it is necessarily subjected to a pre-treatment step for removing components and/or contaminants so as to allow an end-product to be obtained having determined features and also to allow the sending thereof to the cryogenic unit, in particular, to the liquefaction unit, in particular, avoiding the solidification of some components.
Typical contaminants to be removed include CO2, H2O, Hg, sulfur compounds and aromatic or heavy hydrocarbons.
The pre-treatment units are normally positioned upstream of the liquefaction unit and are independent thereof.
Typically, the following are used in plants of the baseload type:
The pre-treatment units significantly contribute to the energy consumption of the plant.
After the pre-treatment, the natural gas is sent to the liquefaction unit where it is gradually cooled.
Three main cooling steps can be identified:
For a baseload plant, the choice of the liquefaction technology, together with the choice of the cooling machines and plants, is fundamental, since it influences the total investment cost, production capacity and plant availability.
The world of processes for LNG baseload plants is dominated by technologies based on hydrocarbon refrigerants.
The most commonly used process is C3/MR, which was introduced by Air Products and Chemicals Inc. at the beginning of the Seventies and it is based on propane refrigeration cycles (C3) and a Mixed Refrigerant (MR) consisting of methane, ethane, propane, nitrogen and, sometimes, butane.
The following processes are also very common Single MR (with a single MR cycle), Dual MR (with two MR cycles in series) and Conoco-Phillips Optimized Cascade, with three refrigeration cycles in cascade, with propane, ethane and methane, respectively.
The efficiency of the liquefaction technologies increases as the number of refrigeration cycles in series increases, at the expense of the complexity of the plant and the operating and installation cost (CAPEX) thereof.
It is known that, in general and in the field of application of this industry, the liquefaction efficiency is greater as the pressure of the natural gas increases; for example, for pressures comprised between 45 barg and 70 barg, the gain in terms of production amounts to about 0.5% for each additional bar.
Recent developments in the LNG industry and the drive to use natural gas as a “clean” fuel, replacing diesel fuel and diesel, have favored the development of the market of small-scale LNG plants, with an annual capacity from 0.05 MTPA to 1 MTPA.
This new market, driven by various factors from economies of scale, has introduced the use of new solutions for the purpose of reaching a wider range of clients and offering simpler products, with a smaller CAPEX, less equipment, easier manageability, and reduced delivery times, also accepting a lower energy efficiency.
Small-scale plants also differ from the baseload ones in the liquefaction technology: to favor the simplicity of the process and use in offshore applications, the commonest technologies are based on the use of non-hydrocarbon refrigerants, such as nitrogen (including the design based on Moss' patent RS NO305525B1), hydrocarbon refrigerants, such as the Single MR and, more recently, cycles have also been proposed using natural gas.
Nitrogen Refrigeration Cycles
Nitrogen cycles are based on the Brayton thermodynamic cycle (inverted).
In an ideal process, the global efficiency is independent of the type of refrigerant and, in fact, the efficiency of the machines is equal to 100%, the release of energy occurs reversibly without load or working losses and the expansion/compression of the gas is reversible and isentropic.
Whereas, in a real cycle, different effects, represented by imperfect equipment, load losses, non-isentropic expansions and compressions, which are neither reversible nor isotherm, must be taken into account.
Small Scale Natural Gas Pre-Treatment
Small-scale plants differ from the baseload ones in their small dimensions and capacity; these features enable the applicability of alternative technologies for pre-treating the gas, which operate at a lower temperature than traditional ones.
In particular, the use of regenerative molecular sieves is known for removing CO2, aromatic and sulfur compounds, with the option of carrying out the regeneration of the pre-treatment units.
Further technologies allow the removal of undesired components from the gas (CO2 and sulfur compounds), by means of sublimation or deposition by freezing on cold surfaces of the same.
Some of these technologies are described, for example, in patent documents U.S. Pat. No. 4,265,088, WO 2009/047341, U.S. Pat. No. 7,073,348.
Prior art documents CN 105737515A (
In the process described by CN 105375151, the solidified carbon dioxide is separated in the solid-liquid separator 14.
In the process described by CN 105890281 the raw natural gas is cooled at −40° C. through the heat exchanger for pre-cooling the natural gas 1, then it enters the separator for heavy hydrocarbons 4 to remove the heavy hydrocarbons; after removing the heavy hydrocarbons, the natural gas enters the heat exchanger for a further cooling of the natural gas 8 and is cooled at −160° C., then it enters the separator at a low temperature of carbon dioxide 9, to remove the solid carbon dioxide. After removing the carbon dioxide, the natural gas passes through the valve 11 and continues through the exit 17 at the LNG storage pressure.
The removal of carbon dioxide directly from LNG, i.e. downstream of the natural gas liquefaction, raises serious problems regarding the operability of the main exchanger by the accumulation of solid CO2 therein, with the probable stratification on the exchange surface with the refrigerant.
In general, the affordability of a small-scale liquefaction plant, which exploits nitrogen cycles (or nitrogen-natural gas), is largely affected by the inefficiency of the cycle itself with respect to the hydrocarbon cycles of the baseload plants.
Furthermore, the energy efficiency is further compromised by the failed integration between the pre-treatment units and the cooling and liquefaction units.
The inventors of the present patent application have developed a small-scale process for treating and liquefying the natural gas (NG) with high energy efficiency in the removal of acidic compounds.
In a first object, the present invention describes a process for purifying and liquefying the natural gas (NG).
According to a particular aspect, such process is a small-scale process.
Particular embodiments of the described process represent further objects of the invention.
In a second object, a plant is described for purifying and liquefying the natural gas (NG).
In a first object, the present invention describes a process for purifying and liquefying the natural gas (NG).
More specifically, the process comprises the steps of:
According to a particular aspect of the present invention, in the pre-treatment step 2), a first high-pressure flow 22 can be used, which is separated from the first compressed recirculation flow 7 obtained from step 4).
Such first high-pressure flow 22 is used to carry out the pre-treatment of the pre-cooled flow 1, e.g. by means of a heat exchange.
Furthermore, for the purposes of the present invention, one or more of the cooling steps according to steps 1), 6a), 7a) reported above, can be carried out by means of a flow of nitrogen 46, which circulates inside a closed nitrogen refrigeration cycle 100.
Such closed nitrogen refrigeration cycle 100 is supplied by a flow of nitrogen 60 and is described below in greater detail.
In an embodiment of the invention, after step 1), said pre-cooled flow 1 can be expanded by means of a second valve V2 obtaining a further pre-cooled and expanded flow 2.
The expansion results in a further cooling of the flow 1.
Therefore, the successive pre-treatment step 2) can be carried out on the pre-cooled flow 1 or on the further pre-cooled and expanded flow 2.
In particular, said pre-treatment step 2) comprises one or more purification processes, which are known in the art.
Such purification processes aim at separating the carbon dioxide, hydrogen sulfide, water, other sulfur compounds and aromatic or heavy hydrocarbons (>C5).
For example, molecular sieves can be used or removal systems by means of freezing.
According to a preferred aspect of the present invention, the purified flow 3 obtained after the pre-treatment step 2) has a CO2 content of less than 250 ppmv and preferably less than 50 ppmv.
According to another preferred aspect of the present invention, the purified flow 3 obtained after the pre-treatment step 2) has an H2S content of less than 10 mg/Nm3 and preferably less than 5 mg/Nm3.
According to a further preferred aspect of the present invention, the purified flow 3 obtained after the pre-treatment step 2) has an H2O content of less than 5 ppmv and preferably less than 1 ppmv.
In an embodiment of the invention, the purified flow 3 obtained after the pre-treatment step 2) can be further expanded by means of a third valve V3 obtaining a purified and further expanded flow 4.
Therefore, the heat recover step 3) can be carried out on the purified flow 3 or on the purified and further expanded flow 4.
As described above, as for step 4) this is carried out on the higher temperature flow 5, with which the third natural gas recirculation flow 16 at a higher temperature is reunited, forming the overall recirculation flow 6, which is then compressed in the first compressor GK1, obtaining a first compressed recirculation flow 7.
As reported above, after the compression, the first compressed recirculation flow 7 is cooled in a first cooler for the natural gas (GC1) obtaining a cooled flow 8.
According to an embodiment of the present invention, the obtainment of a flow of natural gas cooled at the liquefaction pressure of steps 4) and 5) can be obtained with a plurality of successive partial steps.
To this end, for example, as shown in the diagram in
Since a respective cooling step is carried out in further respective natural gas coolers (GC2, GC3), after each compression step, further compressed and cooled recirculation flows are obtained (10,12), respectively.
As for step 5), the cooling can be obtained according to techniques known in the field, e.g. air or water heat exchange, or by means of other fluids.
Therefore, for the purposes of the present invention, the successive steps 6) and 7) are carried out on portions of the compressed and cooled flow 8 or on a further compressed and cooled recirculation flow 10,12 or, in any case, on the last compressed and cooled flow obtained.
For the purposes of the present invention, the capacity of said flow 17 subjected to step 6a) is comprised between 10-40% and preferably between 15-30% of the capacity of the flow 8, 10, 12 or, in any case, on the last compressed and cooled flow obtained.
According to an embodiment of the present invention, a first compressed flow portion 23, a second compressed flow portion 24, or further compressed flow portions can be separated from one or more of the further compressed flows 9,11 or, in any case, from each compressed flow obtained, respectively, which are not subjected to cooling, but which are reunited with the first compressed flow 22 forming a treatment flow 22′, which, as described above, can be used in the pre-treatment step 2).
In particular, such treatment flow 22′ is used in the pre-treatment flow of the pre-cooled flow 1 or 2, e.g. by means of heat exchange.
According to a preferred aspect of the present invention, the flow of liquefied natural gas 18 obtained from step 6a) has a temperature from −161° C. to −141° C. and on average of −147° C. and a pressure of barg and on average of 5 barg.
For the purposes of the present invention, the closed nitrogen refrigeration cycle 100 mentioned above is a cycle, in which one or more low-pressure nitrogen flows and one or more high-pressure nitrogen flows circulate, independently of each other.
According to an embodiment of the present invention (shown in
According to an embodiment of the present invention, the compression step A) of the low-pressure nitrogen flow 40 can be carried out in a plurality of successive partial steps.
To this end, as shown, for example, in the diagram in
Since, after each compression step, a respective cooling step is carried out, the further high-pressure nitrogen recirculation flow 43 is sent to a further cooler of the nitrogen cycle NC2 obtaining a further cooled high-pressure nitrogen recirculation flow 44.
Therefore, for the purposes of the present invention, step B) is carried out on a first cooled high-pressure nitrogen recirculation flow 42 or on a further cooled high-pressure nitrogen recirculation flow 44 or, in any case, on the last compressed and cooled nitrogen flow obtained.
According to an aspect of the present invention, in the closed nitrogen refrigeration cycle 100 the nitrogen flows vary the temperature and pressure conditions according to the indicative values reported in the following table:
According to an embodiment of the present invention, one portion 47 and a further portion 48 are separated, respectively, from the first high-pressure nitrogen recirculation flow 41 and/or from the further high-pressure nitrogen recirculation flow 43 or, in any case, from each high-pressure nitrogen recirculation flow obtained, which can be reunited, forming a treatment nitrogen flow 49, which can be used in the pre-treatment step 2), e.g. for regenerating the pre-treatment units.
Therefore, the pre-treatment step can be carried out by using one or more of the flows selected from: the first high-pressure flow 22, the treatment flow 22′, the first portion 47 of the high-pressure nitrogen recirculation flow or the portion 48 of the further portion of the first high-pressure nitrogen recirculation flow or the nitrogen treatment flow 49 or, according to an alternative not shown in the figures, an external current.
According to an embodiment, for example, shown in the diagram in
According to an embodiment of the present invention, for example, shown in the diagram in
According to another embodiment of the present invention, a portion 26 of said liquefied natural gas flow 19 obtained from step 6b) is used in the pre-treatment step 2), from which a flow 28 is recovered, which is subjected to an expansion step by means of a fourth valve V4 obtaining a natural expanded gas flow 29, which is reunited with the natural gas flow 5 at a higher temperature obtained from step 3 and sent to step 4).
Advantageously, in this way, the liquefied natural gas 19 refrigeration units are exploited.
For the purposes of the present invention, a flow of removed compounds 25, 50 is obtained from the pre-treatment step 2), comprising acidic or other compounds removed by means of the pre-treatment step, which can be sent to other plant units, e.g. for treating the fuel gas, or it can be recovered as a by-product or freed into the atmosphere.
According to a second object of the invention, a plant is described for purifying and liquefying the natural gas (NG) comprising (the numbers and references coincide for the steps of the process and the plant elements):
For the purposes of the present invention, inside said natural gas circuit, flows of natural gas circulate, which can be: low-pressure, high-pressure, compressed or expanded, cooled or heated.
For the purposes of the present invention, inside said nitrogen circuit, several flows of nitrogen circulate, which can be: low-pressure, high-pressure, compressed or expanded, cooled or heated.
According to a preferred aspect of the present invention, said cryogenic exchanger (CE) is built so as to allow thermal exchanges between one or more of said flows of natural gas with one or more of said flows of nitrogen and/or natural gas.
According to a preferred aspect of the present invention, the plant for purifying and liquefying the natural gas (NG) of the present invention is the plant in which the steps of the process described above are carried out.
From the above description of the present invention, the advantages offered by the present invention will be immediately apparent to those skilled in the art.
In particular, the process provided allows optimizing the liquefaction of the natural gas and the purification thereof with an optimum compromise between plant efficiency and complexity; by virtue of these features, the process lends itself well to offshore-type applications.
Furthermore, the combination with a nitrogen cycle allows operating more safely and more compactly, inter alia, avoiding importing, storing and managing hydrocarbon refrigerants.
These further characteristics make the process of the invention also ideal for applications of the floating type (on boats).
Again, the process of the present invention allows optimizing the pre-treatment and liquefaction steps, which are favored by mutually opposite operating conditions.
Furthermore, by virtue of the increased efficiency, the process of the invention can be carried out with a lower energy consumption, thereby reducing the operating costs of the plant (OPEX) and, ultimately, the environmental impact; this is even more apparent when part of the natural gas entering the plant is consumed to produce the energy to be used for pre-treatment and liquefaction.
Number | Date | Country | Kind |
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102020000026978 | Nov 2020 | IT | national |
Filing Document | Filing Date | Country | Kind |
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PCT/IB2021/060152 | 11/3/2021 | WO |