Patent Application
20190240616
The invention relates to the field of membrane gas separation and can be used for the removal of undesirable components of natural and process gas mixtures. The main purpose of the invention is the separation of acid gases (CO2 and H2S) from natural and associated petroleum gases for their conditioning for transport by pipeline. The invention relates to a method for removing components of a gas mixture, based on membrane pertraction and selective absorption of a gas-phase component into a liquid phase through a nanoporous membrane. Improved characteristics of the separation process and prevention of mutual permeation of gas into the liquid phase of an absorbent and the liquid absorbent into the gas phase are achieved by the use of nanoporous membranes having a pore diameter of 5 to 500 nm and a uniform pore size distribution, allowing the process to be performed at a transmembrane pressure maintained below the membrane bubble point pressure. The method provides a record CO2 extraction rate of more than 0.3 nm3/(m2·h) at a packing density of the hollow fiber membrane of up to 3200 m2/m3, which corresponds to a specific volumetric performance of acid gas removal of up to 1000 nm3/(m3·h). This allows an efficient processing of natural and associated petroleum gases based on acidic components, using small-sized absorption modules, and a significant reduction in capital investment and operating costs of gas processing facilities.
The membrane pertraction technology is a process of penetrant transfer from gas phase to liquid phase through a membrane. The process is implemented in a membrane contactor [Falk-Pedersen, O.; Dannstrom, H. Method for Removing Carbon Dioxide from Gases, 2001]. A high contact surface area in a “gas-absorbent” system, created by hollow fibers, significantly reduces the dimensions of the membrane contactor and, as a consequence, the operating and capital costs of their construction.
There is a method for removing CO2 from gases (U.S. Pat. No. 6,228,145B1 (WO98/04339)), using a hollow fiber membrane contactor. Acid gas is fed to hollow fibers, while the absorbent washes the outer surface. This design provides a reduction in the weight of the facility by 70-75%, a reduction in the size by 65%, and also a significant reduction in the loss of the absorbent compared to the traditional absorption column. The patent proposes the use of hollow fibers, both in an absorber and in a desorber for the absorbent regeneration. The hollow-fiber membrane packing density is 250-1000 m2/m3. The pore size of the membrane in the patent is proposed to be selected so as to exclude penetration of absorbent molecules (solvent) through the membrane, which limits the range of used materials to microporous membranes having extremely low CO2 permeability (typically up to <<1 m3/(m2·atm·h)). The patent does not provide for the use of transmembrane pressure, which inevitably leads to wetting a membrane with an amine solution, degradation of its internal structure and, during long-term operation, penetration of the liquid absorbent into gas phase. In addition, when the liquid absorbent penetrates the membrane pores, because in the liquid CO2 diffusion coefficients are significantly lower than in the gas phase, the rate of gas transfer through the membrane significantly decreases, which negatively affects its performance.
U.S. Pat. No. 8,702,844 provides a method for improving the “absorbent-acidic component” contact and a membrane contactor based on it. The essence of the method consists in the modification of membrane material with nanoparticles different in chemical composition from the composition of the membrane material. The introduction nanoparticles of different chemical nature allows the surface wetting contact angle of the membrane material to be varied. It is proposed to use modified hollow fibers in both the absorber and regenerator. A disadvantage of the method is the need for an additional step of modification, which increases the cost of the membrane material, as well as the possibility of microdefects at the “nanoparticle-membrane material” boundary, which significantly reduces the chemical resistance of the membrane material.
A method of membrane gas separation using a membrane contactor based on polyacetylenes substituted with trimethylsilyl groups is also known from international patent U.S. Pat. No. 7,591,878. The invention is useful for desorption of carbon dioxide from absorbents at a high pressure. The process is performed under transmembrane overpressure (more than 1 bar) on the liquid phase side. A disadvantage of the invention is the use of polytrimethylsilylpropyne as polymeric material, which plasticizes under high pressure in the presence of carbon dioxide and loses its high permeability due to physical aging.
A similar method is implemented in a utility model of a high-pressure membrane contactor and an absorption-desorption device on its basis for separation and recovery of carbon dioxide from associated and flue gases (RU Patent No. 128515). The main disadvantage of this utility model is the use of a membrane based on polytrimethylsilpropine that undergoes rapid physical aging under exposure to CO2, which is accompanied by physical degradation and a sharp decrease in the membrane permeability.
A similar method is also used in a device for mass transfer between liquid and gas phases (patent RU 2392038), the device comprising a mass transfer chamber formed by two porous polymer membranes non-wettable by liquid phase, between which a porous polymer material is placed, wherein the porous polymer material is non-wettable by liquid phase and comprises a system of open-ended channels through which the liquid phase is pumped. The outer surface of the membranes is washed by gas phase. The process is performed under overpressure on the liquid phase side, maintaining the transmembrane pressure lower than the capillary pressure of the porous materials. The device provides an increased efficiency of mass transfer processes in a liquid-gas system, but its industrial-scale implementation is too difficult. In addition, the overpressure on the liquid side leads to gradual wetting of porous materials and their degradation.
U.S. Pat. No. 7,544,340 provides a method for creating a more efficient contact of an acidic component with an absorbent in a hollow fiber membrane contactor. The method is implemented by supplying the absorbent under a pressure, which is higher so as to overcome a resistance to wetting of the microporous hollow fiber. As a result, the absorbent partially penetrates the pores of the hollow fiber. A disadvantage of this method is a possible degradation of the hollow fiber surface over time under an overpressure on the liquid phase side, which leads to a decrease in the rate of gas transfer through the membrane when the pores are filled with the liquid phase and to the ingress of the liquid absorbent into gas phase during long-term operation. This technical solution was chosen as a prototype for the claimed method of extracting components of gas mixtures.
Thus, the main problem of the extraction of components of gas mixtures by pertraction using “gas-liquid” membrane contactors is the gradual wetting of the membrane with an absorbent solution under overpressure on the liquid phase side, which leads to the degradation of the membrane material, a reduction in the transfer rate of components when the pores are filled with the liquid phase and, during long-term operation, penetration of the liquid absorbent into the gas phase.
To prevent pores from filling with liquid phase, the most promising solution is the maintenance of overpressure in gas phase, but, in the absence of the affinity of a liquid absorbent for membrane material, this inevitably leads to the formation of gas bubbles and diffusion of the gas into the liquid phase. To prevent this phenomenon, the outer surface of membrane material must have chemical affinity for the absorbent, and the pressure between the gas and liquid phases should not exceed the bubble point of the membrane, which determines the minimum gas pressure under which the liquid is pressed out of membrane pores with a maximum diameter. Thus, the bubble point determines the maximum pressure drop between gas and liquid, at which the membrane gas separation is possible, while avoiding penetration of gas into liquid and vice versa.
Since the bubble point of a membrane is determined, according to the Laplace equation, by the largest pores, the maximum allowable pressure for the pertraction process will be limited by the membrane pore diameter. For significant transmembrane pressures (0.1-10 bar), the membrane pore diameter should be in the nanometer range (5-500 nm). In addition, a sufficiently low dispersion in the pore size distribution (less than 50%) is an essential parameter that ensures the homogeneity of membrane properties and the displacement of liquid from all pores. In a wide distribution of pore sizes, small pores can be filled with a liquid absorbent phase due to capillary pressure, which will reduce the performance of the membrane and lead to its degradation.
The present method is aimed at solving the problem of extracting undesirable components from natural and process gas mixtures, including natural and associated petroleum gas, by pertraction in a membrane contactor with an increased efficiency.
The proposed method is based on the passage of components of a gas mixture through a nanoporous membrane and selective absorption of the components with an absorbent contacting the nanoporous membrane, wherein a pressure difference between the gas phase and the liquid absorbent is maintained below the membrane bubble point pressure. The proposed method prevents penetration of the liquid phase into the membrane pore volume, which significantly increases its performance and prevents the material from degradation. This allows for an efficient processing and purification of natural and process gases to meet the technical requirements, including on acidic components, using a small-size absorption modules, and a significant reduce in capital investment and operating costs of gas processing facilities, and an increase in the resistance of the membrane contactor to operational failures.
This technical result for the method of extracting components from natural and process gas mixtures is achieved by using a nanoporous membrane with a pore diameter in the range of 5-500 nm and a low dispersion of the pore size distribution (less than 50%), and by maintaining a transmembrane pressure between a gas phase and a liquid absorbent in the membrane contactor below the membrane bubble point pressure.
A nanoporous membrane can be made in a flat-frame and tubular geometry, as well as in the form of hollow fibers. Structurally, the membrane can be made in the form of an asymmetric membrane with a nanoporous selective layer on a large pore substrate. The membrane can be made on the basis of both inorganic and organic materials resistant to the action of an absorbent, and its outer surface can be chemically modified to provide a higher affinity for a solvent [N. Hilal, M. Khayet, C. J. Wright Membrane modification: technology and application, 2012]. The membrane material can be anodic alumina, tracking polymers (polycarbonate, polyethylene terephthalate), as well as polyvinylidene difluoride (PVDF), polysulfone, polyethersulfone, polypropylene. The listed materials are characterized by a size pore distribution that does not exceed 50%, a pore size in the range of 5-250 nm, and a bubble point value of up to 2 bars.
Aqueous solutions of primary, secondary and tertiary amines, as well as mixtures of amines of different basicity, glycol solutions, physical absorbents used for processing natural and process gases by absorption can be used as the absorbent [A. L. Kohl and R. Nielsen, Gas Purification, 1997].
This method provides extraction of components, such as CO2, H2S, mercaptans, and water from natural and process gas mixtures, including natural and associated petroleum gas. The extraction extent of components reaches the level of 90-99%.
The absorbent regeneration is also possible through a nanoporous membrane by maintaining a pressure difference between the gas phase and the liquid absorbent below the membrane bubble point pressure and by using stripping gas that does not contain adsorbed components. The use of the claimed method also reduces the action of the liquid absorbent on the membrane material, significantly improves the resistance of the membrane contactor to operational impacts, increases the gas transfer efficiency, and in general reduces the capital investment and operating costs for gas processing facilities.
These features are essential and are associated with the formation of a stable combination sufficient to obtain a desired technical result.
The method significantly increases the extraction rate of acid gases (more than 0.3 nm3/(m2·h) for CO2) at a hollow fiber membrane packing density of up to 3,200 m2/m3, which corresponds to a specific volumetric performance of acid gas removal of up to 1000 nm3/(m3·h). This method provides an effective processing of natural and associated petroleum gases in regard to acidic components, on absorption modules and regeneration modules of a small size. The present invention is industrially applicable and can be carried out in an industrial scale.
The principle of extraction of components of natural and process gas mixtures by petraction on nanoporous membranes is shown in
The invention is illustrated by the following figures, wherein:
The present invention is illustrated in relationship to specific embodiments, which are not intended to limit the scope of the invention.
The process of extracting acidic components is carried out as follows. A feed gas is fed to the acid gas absorber of a pertraction module. The contact between an absorbent and the gas occurs at a temperature of ˜30° C., and the regeneration of an absorbent solution occurs at 80-130° C. For regeneration, the absorbent solution is cyclically fed to a regenerator where desorption of absorbed CO2 and H2S occurs.
The pertraction process is intensified by using a module designed for countercurrent mass exchange. The membrane pertraction module includes an absorber body with a cartridge of hollow polymer fibers and a regenerator. The module provides for the installation and preservation of hollow fiber membrane elements that provide a possible contact between liquid and gaseous media under a process pressure of up to 10 atm, a gas flow rate of up to 10 nm3/h, and a liquid flow rate of up to 0.1 nm3/h. The hollow fiber membrane module with a diameter of up to 150 mm is configured to be installed and replaced. The absorber body has a tubular shape with a length of 900 mm, an inner diameter of 160 mm, and a wall thickness of 3 mm. The housing of the regenerator completely repeats a similar element of the absorber. The system for supplying gas and liquid phases is configured to maintain a constant transmembrane pressure between the gas phase and a liquid absorbent by using an automatic pressure maintaining system and by means of a liquid absorbent column pressure.
An aqueous solution of monoethanolamine (25%) is used as the absorbent for carrying out the method. Hollow fibers based on polyvinylidene difluoride (PVDF), polyethersulfone, polysulfone and polypropylene are used as the nanoporous membrane. The main characteristics of the membranes are given in Table 1, and typical micrographs of the used membranes are shown in
The method was tested using a gas mixture consisting of 94.5% CH4, 5% CO2, and 0.5% H2S, and the flow rate of the feed mixture was ranged from 0.5 to 10 nm3/hour. The content of acid gases in the mixture was determined by chromatography.
It can be seen that the implementation of the method leads to almost complete removal of both CO2 and H2S (the detection limit of hydrogen sulfide by this method is 0.005 vol. % of H2S).
At the same time, a 90% extraction extent for CO2 provides processing a gas mixture with a content of carbon dioxide of up to 20% to the extent, which meets the requirements of the STO Gazprom 089-2010. Thus, the membrane pertraction module can be used for pre-conditioning of associated petroleum gas in regard to acidic components, with a specific acid gas extraction rate for CO2 over 0.3 nm3/(m2·h). At a hollow fiber membrane packing density of up to 3200 m2/m3, this corresponds to a specific volumetric performance of acid gas removal of up to 1000 nm3/(m3·hour).
The method for removing mercaptans was tested using a gas mixture consisting of 1.3% N2, 67.2% CH4, 4.5% CO2, 7.8% C2H6, 5.1% C3H8, 4.6% i-C4H10, 7.8% n-C4H10, 1.0% i-C5H12, 0.6% n-C5H12, and 0.1% C6H14, with a content of C2H6S of 54 mg/m3. The flow rate of the feed mixture ranged from 0.05 to 0.25 nm3/h. The content of mercaptans was determined by chromatography-mass spectrometry. Dependence of the extraction extent of mercaptans on the flow rate of the feed mixture is shown in
Thus, according to the obtained data, the claimed method allows effective extraction of undesirable components of natural and process gas mixtures and a significant reduction in the size of the absorption modules, which significantly reduces the capital investment and operating costs of gas processing facilities.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016140487 | Oct 2016 | RU | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/RU2017/050100 | 10/3/2017 | WO | 00 |
