Patent Application
20100154637
The present invention relates to a process for the purification of gaseous mixtures, in particular of natural gas, containing mercaptans and other acid gases, as well as an absorbent solution for the implementation of said process.
Within the framework of the production of natural gas (containing mainly methane) or liquefied natural gas, it is necessary to purify said natural gas, which originates from a deposit, by removing a certain number of contaminants, including primarily what are called “acid gases”, i.e. carbon dioxide (CO2), hydrogen sulphide (H2S), mercaptans (R—SH), carbonyl sulphide (COS) and carbon disulphide (CS2).
Carbon dioxide and hydrogen sulphide can represent a significant part of the gaseous mixture originating from a natural gas deposit, typically from 3 to 70% (in molar concentration). COS is present in smaller quantities, typically varying from 1 to 50 ppm by volume.
The contaminants which have to be removed include mercaptans, molecules of formula R—SH where R is an alkyl group. The total quantity of mercaptans in a gaseous mixture originating from a natural gas production site can represent a few hundred ppm by volume. The main two mercaptans concerned are methyl mercaptan and ethyl mercaptan, but other mercaptans (in particular molecules of type C3SH to C6SH) can also be present, generally at a lower concentration.
Numerous methods currently exist for deacidifying and removing mercaptans from natural gas (simultaneously or sequentially), using solvents capable of absorbing mercaptans and/or other acid gases chemically and/or physically (by dissolution).
Among the processes currently in use on an industrial scale, the so-called “Sulfinol” process involves eliminating the H2S, CO2, COS, CS2 gases and the natural gas mercaptans using a solvent constituted by a mixture of sulpholane, water and an amine (such as diisopropanolamine or methyl diethanolamine). Another example is the so-called “Selexol” process, which uses a solvent based on a dimethyl ether of polyethylene glycol.
Numerous other variants have been proposed, using alternative solvents. By way of example there can be mentioned solvents based on alkanolpyridine (U.S. Pat. No. 4,360,363).
However, there is still a real need to discover other solvents capable of effectively absorbing, preferably simultaneously, the mercaptans and other acid gases present in a gaseous mixture.
In particular there is a need to discover solvents making it possible to implement processes for the deacidification and demercaptanization of gaseous mixtures with a lower solvent flow rate compared with the state of the art (at a comparable gaseous mixture flow rate), and more generally at a lower cost compared with the state of the art.
The invention makes it possible to meet the needs expressed above, thanks to the development of a novel hybrid solution constituted by a mixture of alkanolamine, water and thioalkanol, making it possible to effectively co-absorb the mercaptans and the other acid gases contained in a gaseous mixture.
The invention therefore relates primarily to a process for the purification of a gaseous mixture containing acid gases and preferably containing mercaptans and other acid gases comprising a stage of bringing said gaseous mixture into contact with an absorbent solution comprising an alkanolamine, a C2-C4 thioalkanol and water.
Preferably, said gaseous mixture is natural gas.
Preferably, the mercaptan or mercaptans comprise methyl mercaptan and/or ethyl mercaptan.
Preferably, the other acid gas or gases comprise hydrogen sulphide and/or carbon dioxide and/or carbonyl sulphide.
According to an advantageous embodiment, the alkanolamine is diethanolamine.
According to a particular embodiment, the C2-C4 thioalkanol is ethylene dithioethanol.
Advantageously, the C2-C4 thioalkanol is thiodiethylene glycol.
According to a preferred embodiment of the process according to the invention, the absorbent solution comprises:
According to a particularly preferred embodiment of the process according to the invention, the absorbent solution comprises:
According to a most preferred embodiment of the process according to the invention, the absorbent solution comprises:
Preferably, the above-mentioned purification process is implemented in an absorber at a temperature comprised between approximately 40 and approximately 100° C., preferably approximately 50 and approximately 90° C.
Advantageously, in the purification process as defined above, the gaseous mixture is brought into contact with the absorbent solution at a gaseous mixture flow rate comprised between 0.23×106 Nm3/day and 56×106 Nm3/day and at an absorbent solution flow rate comprised between 800 m3/day and 50000 m3/day.
Advantageously, the purification process as defined above moreover comprises a stage of regeneration of the absorbent solution loaded with mercaptans and other acid gases at a regeneration pressure comprised between 0 and 20 bar and preferably between 1 and 2 bar, and at a temperature comprised between 100 and 140° C.
According to a preferred embodiment, the invention relates to the purification process as defined above, for reducing the concentration of mercaptans contained in the gaseous mixture to a value of less than approximately 5 ppm.
According to a preferred embodiment, the invention relates to the purification process as defined above, for reducing the concentration of hydrogen sulphide contained in the gaseous mixture to a value of less than approximately 4 ppm.
According to a preferred embodiment, the invention relates to the purification process as defined above, for reducing the concentration of carbon dioxide contained in the gaseous mixture to a value of less than approximately 50 ppm.
According to a preferred embodiment, the invention relates to the purification process as defined above, for reducing the concentration of carbonyl sulphide contained in the gaseous mixture to a value of less than approximately 1 ppm.
The invention moreover relates to an absorbent solution comprising:
The absorbent solution according to the invention preferably comprises:
According to a preferred embodiment of the above-mentioned absorbent solution, the alkanolamine is diethanolamine.
According to a preferred embodiment of the above-mentioned absorbent solution, the C2-C4 thioalkanol is thiodiethylene glycol or ethylene dithioethanol.
The invention is now described in greater detail and non-limitatively in the following description.
The invention allows the treatment of a gaseous mixture, and in particular according to a preferred embodiment, of natural gas. The latter contains mercaptans, in particular methyl mercaptan and/or ethyl mercaptan, in quantities by volume varying from 0 to 400 ppm.
The gaseous mixture also comprises other acid gases, in particular hydrogen sulphide and/or carbon dioxide and/or carbonyl sulphide, all in quantities by volume of: less than 50% H2S, less than 50% CO2 and between 0 and 100 ppm COS.
Although the invention is particularly useful for treating a gaseous mixture containing mercaptans, it must be noted that the invention is used more generally for the purification of any gaseous mixture containing acid gases, with or without mercaptans. Apart from the field of natural gas treatment, the invention can also be used for example in the treatment of flue gases.
The invention uses a novel absorption solution, in a standard absorption/regeneration process. The novel solution provides a chemical and physical absorption according to the components to be absorbed.
The absorbent solution according to the invention generally comprises:
A preferred solution comprises the above components in a ratio of 40/40/20.
Diethanolamine (DEA) is the compound of formula HN(CH2—CH2OH)2, which is the preferred alkanolamine. Apart from DEA, other examples of alkanolamines which can be used in the process according to the invention include by way of example monoethanolamine (MEA), triethanolamine (TEA), diisopropanolamine (DIPA) and methyl diethanolamine (MDEA), or even activated methyl diethanolamine (for example methyl diethanolamine enriched with hydroxyethyl piperazine or piperazine) or also sterically hindered amines.
Generally, the C2-C4 thioalkanol has the formula R—S—C2-4—OH, where R is any group, for example, an alkyl group or an alcohol group or a thiol group or an alkylthioalkanol group, the group containing in particular up to 6 carbon atoms.
According to a particular embodiment, the C2-C4 thioalkanol is a dimeric molecule.
An example of C2-C4 thioalkanol which can be used according to the invention is ethylene dithioethanol, of formula (HO—CH2—CH2)—S—(CH2—CH2)—S—(CH2—CH2—OH).
Thiodiethylene glycol or thiodiglycol (TDG) is the compound of formula S(CH2—CH2—OH)2, which is the preferred thioalkanol. Apart from TDG, other C2-C4 thioalkanols can also be used according to the invention, in particular methyl thioethanol. It is also possible to use a mixture of the above compounds.
The preferred composition of the absorbent solution according to the invention (40% DEA, 40% water and 20% TDG) results from a compromise: in fact the more TDG the absorbent solution contains, the greater the solubility of the CO2 and the mercaptans, which is favourable to the purification of the gaseous mixture; in return, the more TDG the absorbent solution contains, the lower the surface tension of the solution, and the greater the viscosity of the solution, which is unfavourable to the transfer of the mercaptans and other acid gases into the solution. It is to be noted however that the effect on viscosity of an increase in the TDG concentration can be counterbalanced by an increase in temperature, which makes it possible to be free of the viscosifying effect of the thioalkanol.
When another compound, for example ethylene dithioethanol, is used instead of TDG, its preferred concentration is generally the same as that of TDG.
The invention uses a standard absorption regeneration process but with a novel absorption solution.
The absorption stage is implemented in an absorber at a temperature comprised between approximately 40 and approximately 100° C., preferably approximately 50 and approximately 90° C.
The pressure in the column is comprised between 1 and 150 bar, preferably between 40 and 100 bar.
As a column, it is possible to use any type of useful column, and in particular a perforated plate tray column, a valve column or a cap column.
The implementation of the absorption is carried out by bringing the gaseous mixture into contact with the absorbent solution at a gaseous mixture flow rate of between 0.23×106 Nm3/day and 56×106 Nm3/day and at an absorbent solution flow rate of between 800 and 50000 m3/day.
As regards the absorbent solution regeneration stage, it is implemented in a standard fashion by heating and separation of the mercaptans and other acid gases absorbed by the solution in a regeneration column. In fact, the amine solution loaded with H2S, CO2 and RSH (so-called rich amine) originating from the bottom of the absorber is sent into an intermediate-pressure flash drum. The gases originating from the flash of the rich amine are used as fuel gases.
The rich amine is then reheated and optionally partially vaporized in an amine/amine exchanger by the hot amine at the bottom of the regenerator, then fed to the regeneration column.
The reboiler generates vapour which rises in counter-current in the column, entraining the acid constituents H2S, CO2 and RSH. This desorption is encouraged by the low pressure and the high temperature prevailing in the regenerator.
At the head of the column, the acid gases are cooled in a condenser. The condensed water is separated from the acid gas in a reflux drum and sent either to the head of the regeneration column, or directly to the lean amine solution tank.
The regenerated amine (also called lean amine) is then recycled to the absorption stage.
It should be noted that a semi-regenerated operating mode can also be envisaged.
The process according to the invention makes it possible to achieve appreciable separation performances, and in particular to reduce the mercaptan concentration to a value of less than approximately 5 ppm, the hydrogen sulphide concentration to a value of less than approximately 4 ppm, the carbon dioxide concentration to a value of less than approximately 50 ppm and the carbonyl sulphide concentration to a value of less than approximately 1 ppm.
The natural gas treated then undergoes a dehydration stage and can then be available for the gas distribution network. It can also undergo cryogenic treatment in order to produce liquefied natural gas.
The following examples illustrate the invention without limiting it.
Several pilot tests were carried out on a Koch-Glitsch perforated tray column comprising 11 plate trays. The gas treated in the column contains approximately 12% CO2. The quantity of methyl mercaptan is variable according to the tests.
The parameters are the following:
Two absorbent solutions are tested:
The methyl mercaptan concentration is measured by assay at the level of different trays down the column, and the results are presented in
The results indicate that the absorbent solution according to the invention is more effective than the standard sulpholane-based absorbent solution for eliminating methyl mercaptan.
Pilot tests were carried out according to the same protocol as for Example 1, except that this time the absorbent solution flow rate is 610 kg/h, and that this time it is the CO2 concentration which is measured at the level of different trays, in the case of a standard absorbent solution (DEA 40%+water 40%+sulpholane 20%) and in the case of an absorbent solution according to the invention (DEA 40%+water 40%+TDG 20%). In both cases, the initial gaseous mixture is composed of approximately 88% N2 and 12% CO2, 0 to 50 ppm H2S and approximately 670 ppm of methyl mercaptan.
The results, which are represented in
The typical carbon dioxide absorption yields in pilot tests with the absorbent solution according to the invention are from 95 to 97%.
Pilot tests were carried out according to the same protocol as for Example 1, except that this time it is the H2S concentration which is measured after balancing the 11 plate trays. The gas flow rate is 200 kg/h, the liquid flow rate 1200 kg/h. The initial gaseous mixture, with a total pressure of 40 bar, contains CO2 at a partial pressure of approximately 3 bar and H2S at a partial pressure of approximately 1 bar. The composition of the gaseous mixture is as follows: 90% N2, 7.5% CO2, 2.5% H2S.
Pilot tests were carried out according to the same protocol as for Example 1, except that this time it is the COS concentration which is measured after balancing the 11 plate trays. The gas flow rate is 215 kg/h, the liquid flow rate 1200 kg/h. The gas pressure is 40 bar. The solution used is composed of 40% DEA, 40% water and 20% TDG. The solvent moreover contains a residual concentration of dissolved H2S (of the order of 0.1% by mass).
Two tests were carried out. In the first one (□ curve), the partial pressure of CO2 in the initial mixture (comprising mostly N2) is 4.4 bar and that of COS is 330 ppm; in the second one (∘ curve), the partial pressure of CO2 in the initial mixture is 4.1 bar.
The results are shown in
The absorption isotherm of methyl mercaptan by two absorbent solutions according to the invention was determined at 50° C., in the presence of CO2 at 500 mbar.
Experimental device: the absorbent solution was circulated in a 1.2 L double jacket reactor using a displacement pump. At the outlet of this pump, an exchanger is immersed in a thermostatic bath making it possible to maintain the reactor at a constant temperature, in order to compensate for the heat losses due to the passage of fluid in the pump. A Coriolis-effect mass flow meter continuously measures the density of the absorbent solution at the same temperature as that of the reactor. The introduction of the gaseous mixture is controlled by regulating mass flow meters, the pressure being kept constant by pressure adjustment. Circulation of the gases in the reactor is ensured by collecting them in the upper part and bubbling them into the absorbent solution using a disperser placed at the bottom of the latter. The whole gas circulation circuit, including the part leading to sampling by chromatography, is thermostatically controlled in order to avoid any condensation. The sampling output is recycled to the reactor in order to avoid modifying the pressure of the system.
Protocol: the absorbent solution is first introduced into the reactor. A certain quantity of gas is then introduced, followed by waiting for the pressure to stabilize, and if necessary a new quantity of gas is added until a stable final pressure is obtained. Nitrogen is optionally added in order to modify the partial pressure of the desired gas. Once equilibrium is reached, measurements are carried out, then the temperature of the system is modified by the thermostatically-controlled circuit in order to establish a new equilibrium.
Solution No. 1: 40% DEA; 40% water; and 20% TDG.
Solution No. 2: 40% DEA; 40% water; and 20% methyl thioethanol (CH3—S—CH2—CH3).
The two solubility curves obtained are shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 0600448 | Jan 2006 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FR2007/000073 | 1/16/2007 | WO | 00 | 1/5/2009 |
