INTEGRATED PTSA/MEMBRANE METHOD AND SYSTEM FOR H2S AND CO2 REMOVAL FROM BIOGAS

Abstract

Biogas containing H.sub.2S and CO.sub.2 is upgraded by removing H.sub.2S using PTSA and CO.sub.2 using two stages of gas separation membranes. The first stage permeate may optionally be used a regeneration gas stream. The second stage permeate may optionally be used a cool down gas stream. The PTSA unit includes two or more adsorbent beds each selective for water, VOCs, and H.sub.2S over CO.sub.2 and for H.sub.2S over methane.

Claims

1. A biogas upgrading system based upon PTSA and gas separation membranes, comprising: a source of raw biogas comprising methane, CO.sub.2, water, VOCs, and H.sub.2S; a main compressor including a suction inlet in fluid communication with the source and receiving a stream of raw biogas from the source; a PTSA unit comprising two or more adsorbent beds each of which is selective for water, VOCs, and H.sub.2S over CO.sub.2 and for H.sub.2S over methane, the PTSA unit being in downstream fluid communication with the main compressor and receiving a stream of a PTSA feed gas therefrom, the PTSA unit being adapted and configured to adsorb water, VOCs, and H.sub.2S from the PTSA feed gas and produce a PTSA product gas deficient in water, VOCs, and H.sub.2S in comparison to the PTSA feed gas; a first gas separation membrane stage comprising one or more gas separation membranes selective for CO.sub.2 and O.sub.2 over methane, a feed gas inlet of the first gas separation membrane stage being in downstream fluid communication with the PTSA unit, the first gas separation membrane stage being configured and adapted to separate the PTSA product gas into a first stage permeate gas stream and a first stage retentate gas stream; a second gas separation membrane stage comprising one or more gas separation membranes selective for CO.sub.2 and O.sub.2 over methane, a feed gas inlet of the second gas separation membrane stage being in downstream fluid communication with the retentate outlet of the first gas separation membrane stage and receiving the first stage permeate gas stream therefrom, the second gas separation membrane stage being adapted and configured to separate the first retentate gas stream into a second permeate gas stream and a second retentate gas stream, wherein: the PTSA unit is in fluid communication with the permeate gas outlet of the first gas separation membrane stages so as to receive a flow of the first stage permeate gas for use as a thermal regeneration gas to thermally regenerate and desorb water, VOCs, and H.sub.2S that was adsorbed upon the adsorbent beds from the PTSA feed gas stream; and the PTSA unit is in fluid communication with the permeate gas outlet of the second gas separation membrane stage so as to receive a flow of the second permeate gas stream for use as a cool down stream for cooling one or more adsorbent beds after thermal regeneration thereof; and a treatment unit in downstream fluid communication with the PTSA unit so as to receive a waste gas from the PTSA comprised of the thermal regeneration gas and water, VOCs, and H.sub.2S, the treatment unit being adapted and configured to either oxidize or burn the VOCs contained in the waste gas.

2. The system of claim 1, wherein the suction inlet of the main compressor is in fluid communication with the PTSA unit so as to receive the cool down gas stream from the PTSA unit and allow combination and compression with the raw biogas stream.

3. The system of claim 1, further comprising a secondary compressor including a suction inlet that is in fluid communication with the PTSA unit so as to receive the cool down gas stream from the PTSA, wherein the feed gas inlet of the first gas separation membrane stage is in downstream fluid communication with an outlet of the secondary compressor so as to receive the cool down gas stream after compression by the secondary compressor and separate a combined feed of the cool down gas stream and the PTSA product gas into the first stage permeate gas stream and a first stage retentate gas stream.

4. The system of claim 1, wherein the main compressor includes an oil cooling circuit including a heat exchanger adapted and configured to exchange heat between the first stage permeate and oil flowing in the cooling circuit so as to heat the first stage permeate to the temperature at which thermal regeneration of the adsorbent beds is to take place.

5. The system of claim 1, further comprising a H.sub.2S removal unit in flow communication between the main compressor and the PTSA unit, the H.sub.2S removal unit being adapted and configured to remove amounts of H.sub.2S present in the PTSA feed gas stream prior to feeding the PTSA feed gas stream to the PTSA unit, wherein the PTSA unit is adapted and configured to remove amounts of water and VOCs from the PTSA feed gas stream and also amounts of the H.sub.2S remaining in the PTSA feed gas stream after treatment by the H.sub.2S removal unit.

6. The system of claim 1, further comprising a heat exchanger adapted and configured to exchange heat between hot gas from the treatment unit and the regeneration gas stream so as to heat the regeneration gas stream to the temperature above the PTSA feed gas temperature.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements are given the same or analogous reference numbers and wherein:

[0034] FIG. 1 is a schematic of one general embodiment of the method and system of the invention.

[0035] FIG. 1 is a schematic of another general embodiment of the method and system of the invention.

[0036] FIG. 1 is a schematic of another general embodiment of the method and system of the invention.

[0037] FIG. 1 is a schematic of another general embodiment of the method and system of the invention.

[0038] FIG. 2A is a schematic of a first phase of a first two-bed embodiment of the method and system of the invention.

[0039] FIG. 2B is a schematic of a second phase of the first two-bed embodiment of the method and system of the invention.

[0040] FIG. 2C is a schematic of a third phase of the first two-bed embodiment of the method and system of the invention.

[0041] FIG. 2D is a schematic of a fourth phase of the first two-bed embodiment of the method and system of the invention.

[0042] FIG. 2A is a schematic of a first phase of a second two-bed embodiment of the method and system of the invention.

[0043] FIG. 2B is a schematic of a second phase of the second two-bed embodiment of the method and system of the invention.

[0044] FIG. 2C is a schematic of a third phase of the second two-bed embodiment of the method and system of the invention.

[0045] FIG. 2D is a schematic of a third phase of the second two-bed embodiment of the method and system of the invention.

[0046] FIG. 2A is a schematic of a first phase of a third two-bed embodiment of the method and system of the invention.

[0047] FIG. 2B is a schematic of a second phase of the third two-bed embodiment of the method and system of the invention.

[0048] FIG. 2C is a schematic of a third phase of the third two-bed embodiment of the method and system of the invention.

[0049] FIG. 2D is a schematic of a fourth phase of the third two-bed embodiment of the method and system of the invention.

[0050] FIG. 2A is a schematic of a first phase of a fourth two-bed embodiment of the method and system of the invention.

[0051] FIG. 2B is a schematic of a second phase of the fourth two-bed embodiment of the method and system of the invention.

[0052] FIG. 2C is a schematic of a third phase of the fourth two-bed embodiment of the method and system of the invention.

[0053] FIG. 2D is a schematic of a fourth phase of the fourth two-bed embodiment of the method and system of the invention.

[0054] FIG. 3A is a schematic of a first phase of a first three-bed embodiment of the method and system of the invention.

[0055] FIG. 3B is a schematic of a second phase of the first three-bed embodiment of the method and system of the invention.

[0056] FIG. 3C is a schematic of a third phase of the first three-bed embodiment of the method and system of the invention.

[0057] FIG. 3A is a schematic of a first phase of a second three-bed embodiment of the method and system of the invention.

[0058] FIG. 3B is a schematic of a second phase of the second three-bed embodiment of the method and system of the invention.

[0059] FIG. 3C is a schematic of a third phase of the second three-bed embodiment of the method and system of the invention.

[0060] FIG. 3A is a schematic of a first phase of a third three-bed embodiment of the method and system of the invention.

[0061] FIG. 3B is a schematic of a second phase of the third three-bed embodiment of the method and system of the invention.

[0062] FIG. 3C is a schematic of a third phase of the third three-bed embodiment of the method and system of the invention.

[0063] FIG. 3A is a schematic of a first phase of a fourth three-bed embodiment of the method and system of the invention.

[0064] FIG. 3B is a schematic of a second phase of the fourth three-bed embodiment of the method and system of the invention.

[0065] FIG. 3C is a schematic of a third phase of the fourth three-bed embodiment of the method and system of the invention.

[0066] FIG. 4A is a schematic of a first phase of a first four-bed embodiment of the method and system of the invention.

[0067] FIG. 4B is a schematic of a second phase of the first four-bed embodiment of the method and system of the invention.

[0068] FIG. 4C is a schematic of a third phase of the first four-bed embodiment of the method and system of the invention.

[0069] FIG. 4D is a schematic of a fourth phase of the four-bed embodiment of the method and system of the invention.

[0070] FIG. 4A is a schematic of a first phase of a second four-bed embodiment of the method and system of the invention.

[0071] FIG. 4B is a schematic of a second phase of the second four-bed embodiment of the method and system of the invention.

[0072] FIG. 4C is a schematic of a third phase of the second four-bed embodiment of the method and system of the invention.

[0073] FIG. 4D is a schematic of a fourth phase of the second four-bed embodiment of the method and system of the invention.

[0074] FIG. 4A is a schematic of a first phase of a third four-bed embodiment of the method and system of the invention.

[0075] FIG. 4B is a schematic of a second phase of the third four-bed embodiment of the method and system of the invention.

[0076] FIG. 4C is a schematic of a third phase of the third four-bed embodiment of the method and system of the invention.

[0077] FIG. 4D is a schematic of a third phase of the third four-bed embodiment of the method and system of the invention.

[0078] FIG. 4A is a schematic of a first phase of a fourth four-bed embodiment of the method and system of the invention.

[0079] FIG. 4B is a schematic of a second phase of the fourth four-bed embodiment of the method and system of the invention.

[0080] FIG. 4C is a schematic of a third phase of the fourth four-bed embodiment of the method and system of the invention.

[0081] FIG. 4D is a schematic of a third phase of the fourth four-bed embodiment of the method and system of the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0082] The invention is a hybrid PTSA/membrane method system for upgrading of biogas. It removes amounts of H.sub.2S, water, VOCs, and CO.sub.2 to yield a product gas meeting natural gas specifications. The H.sub.2S content of the product gas is no more than 100 ppm (v/v) for on-site use in generators or no more than 4 ppm (v/v) for meeting typical pipeline specifications for sale. For pipeline quality natural gas, the H.sub.2S level in the product gas may alternatively expressed as no more than 1 grain per 100 stdft.sup.3, typically no more than 0.3 grain per 100 stdft.sup.3. The product gas also contains no more than 0.4%, typically no more than 0.2% (v/v) of O.sub.2, and no more than 2% (v/v) of CO.sub.2.

[0083] The biogas may be obtained from a landfill or an anaerobic digester.

[0084] The composition of the raw landfill gas may vary but typically includes 40-60% (v/v) methane, 40-60% (v/v) CO.sub.2, 2-15% (v/v) N.sub.2, 0.1-1% (v/v) O.sub.2, 0.001-0.3% NH.sub.3 (v/v), 0.01-0.5 VOCs (excluding methane), and sometimes up to 1% (v/v) total sulfur compounds, up to 0.2% (v/v) H.sub.2, up to 0.2% (v/v) CO, and varying levels of siloxanes. The H.sub.2S content can vary as widely as 50 ppm (v/v) to 15,000 ppm (v/v) but more typically is present at levels of 100 ppm (v/v) or less.

[0085] The composition of the digester gas may vary depending upon the type of waste processed, such as animal waste, food processing waste, or sewage. Digester gas typically contains 55-70% (v/v) methane and 25-45% (v/v) CO.sub.2. It also includes water at or near its dew point, 3-4 ppm (v/v) NH.sub.3, and up to 50 ppm (v/v) siloxanes. The H.sub.2S content of digester gas can reach as high as 10,000 ppm (v/v) H.sub.2S, but more typically it is in the range of 40-3,000 ppm (v/v) and even more typically in the range of 300-2,500 ppm (v/v).

[0086] Before feeding a stream of the biogas to a compressor, it may optionally be passed through an inlet filter. The compressor compresses the biogas to a typical pressure of 50 to 500 psig, more typically 100-300 psig and often 150-250 psig. The compressor is cooled with cooling oil which is cooled at a heat exchanger that is either integrated with the compressor or separate from the compressor.

[0087] The compressed biogas feed stream (i.e., the PTSA feed gas stream) is fed to a PTSA unit that includes two or more (typically 2-4) adsorbent beds containing adsorbent. Each bed is selective for water, VOCs, and H.sub.2S over CO.sub.2 and for H.sub.2S over methane. Each bed is optionally also selective for siloxanes over methane. The selectivity for H.sub.2S over CO.sub.2 is not an arbitrary feature. While H.sub.2S and CO.sub.2 adsorb strongly on most adsorbents used in the field of adsorbent-based gas separations, for gases containing relatively high levels of CO.sub.2 in comparison to H.sub.2S (such as biogas), the H.sub.2S winds up being adsorbed in relatively lower amounts in comparison to CO.sub.2. For this reason, it is important that the adsorbent beds be selective for H.sub.2S over CO.sub.2. Otherwise, much of the adsorption sites needed for adsorption of H.sub.2S would tend to be blocked by adsorbed CO.sub.2. The aforementioned selectivity properties may be accomplished by using a single adsorbent meeting each of these selectivities or by using multiple adsorbents in a layered bed. While it is desired to remove H.sub.2O and VOCs at the same time as removing H.sub.2S, the adsorbent used for H.sub.2S removal may not be the most advantageous for removal of H.sub.2O or VOCs. Thus, multiple adsorbents can be used in the PTSA beds that are targeted to the composition of the PTSA feed gas stream being treated. Such adsorbents are normally installed in layers and such composite beds are commonly used and well know to one skilled in the art. The bed may be layered with an adsorbent particularly suitable for sorbing water and VOCs at the inlet of the bed and a different adsorbent (downstream of the inlet) particularly suitable for sorbing H.sub.2S. Further, as with other PTSA systems, the adsorber vessels are insulated and either internal or external insulation can be applied with no change to the invention.

[0088] Suitable adsorbents include but are not limited to silica gel such as available from Grace or BASF (under the trade name Sorbead), SulfaTrap available from SulfaTrap, Inc., various molecular sieves including 4A, 5A and 13X versions, natural zeolites, or alumina.

[0089] Each of the beds of the PTSA unit is operated in PTSA cycle phases of adsorption, depressurization, thermal regeneration using a regeneration gas stream heated to a temperature above that of the PTSA feed gas stream, cool down using a cool down gas stream, and repressurization with the PTSA feed gas, PTSA product gas and/or retentate gas stream from a first or second gas separation membrane stage (discussed below). During the adsorption phase, the PTSA feed gas stream (typically at a temperature of about 0 to 40 C. and at a pressure of 50 to 500 psig, more typically 150-250 psig) is fed to a regenerated, cooled, and pressurized adsorbent bed that selectively adsorbs water, VOCs, and H.sub.2S from the PTSA feed gas stream to produce a PTSA product gas which is further upgraded by the gas separation membranes.

[0090] Following the adsorption phase, the adsorption bed is depressurized down to the pressure at which regeneration takes place, for example, at 14-20 psia.

[0091] Once a suitable pressure has been reached, the adsorption bed is thermally regenerated by passing a relatively hot regeneration gas stream through the bed and desorbing the water, VOCs, and H.sub.2S that was adsorbed from the PTSA feed gas stream. A waste gas comprised of the gas of the thermal regeneration gas stream plus the desorbed water, VOCs, and H.sub.2S is withdrawn from the PTSA unit.

[0092] While the regeneration temperature may be selected dependent upon the impurities adsorbed upon the adsorbent from the PTSA feed gas stream and also upon the selected adsorbent applied, typically the regeneration temperature ranges from 250-600 F.

[0093] Following regeneration, the adsorbent bed is cooled down to a suitable temperature to prepare it for the adsorption phase of the next PTSA cycle. Once the suitable temperate is reached, the adsorbent bed is repressurized with PTSA feed gas in order to reach the pressure maintained during the adsorption phase. Following the cool down and repressurization, the PTSA cycle may be repeated.

[0094] A water, VOCs, and H.sub.2S-depleted PTSA product gas stream is withdrawn from the PTSA unit and fed to a first of two gas separation membrane stages each of which includes one or more gas separation membranes. Each of the gas separation membranes of the two stages is selective for permeating CO.sub.2 and O.sub.2 over methane. Thus, the first gas separation membrane separates the PTSA product gas stream into a permeate gas stream that is enriched in CO.sub.2 and O.sub.2 over methane (in comparison to the PTSA product gas) and a retentate gas stream that is enriched in methane over CO.sub.2 and O.sub.2 (in comparison to the PTSA product gas). While the selective layer of the membranes of the first gas separation membrane stage may include any membrane known in the field of gas separation membranes to be selective for CO.sub.2 over methane, typically, the selective layer is made of a polyimide.

[0095] The first stage retentate gas stream is fed to the second gas separation membrane stage. The second gas separation membrane stage separates the first stage retentate gas stream into a permeate gas stream that is enriched in CO.sub.2 and O.sub.2 over methane (in comparison to the first stage retentate gas stream) and a retentate gas stream that is enriched in methane over CO.sub.2 and O.sub.2 (in comparison to the first stage retentate gas stream). The second stage retentate gas stream is withdrawn as the product gas meeting natural gas specifications as described above. The selective layer of the membranes may be the same or different as that of the first gas separation membrane stage and may include any membrane known in the field of gas separation membranes to be selective for CO.sub.2 over methane. Typically, the selective layer is made of a polyimide.

[0096] A stream of the waste gas withdrawn from the PTSA unit may be vented or sent to a treatment unit for destruction of the VOCs and H.sub.2S. Suitable treatment units include burners (which may be supplemented with natural gas for flame stability) especially porous burners. Typically, however, the impurity-laden regeneration gas is treated in a thermal oxidizing (TOX) unit. The heat necessary for desorption of the impurities may be added to the regeneration gas stream by an external heater, and may also use some or all of recovered heat from hot gas or hot oil from the compressor or heat recovery from a thermal oxidizer or other source of waste heat.

[0097] While any gas may be used for thermal regeneration of the adsorbent beds, in one aspect of the invention, all or some of the first stage permeate gas stream is used as the thermal regeneration gas. Because some amounts of the methane contained in the PTSA product gas stream will necessarily permeate across the membranes of the first gas separation membrane stage, the first stage permeate gas stream will not only include CO.sub.2 but also methane. Typically, the first stage permeate gas stream contains 5-13% (v/v) methane. Because the waste gas will include the methane from the first stage permeate gas stream, thermal oxidization or burning of the VOCs is enhanced by the presence of the methane. Additionally, in the event that the effluent from the hybrid system of the invention is subject to regulatory control over the amount of methane emissions, those amounts of methane not recovered in the product natural gas stream will be burned or oxidized in the treatment unit. Finally, through use of the first stage permeate gas stream as the regeneration gas stream, there is no need to provide another source of gas that is suitably dry and impurity-free enough to allow satisfactory amounts of water, VOCs, and H.sub.2S to be desorbed from the adsorbent beds during thermal regeneration.

[0098] While any gas may be used to cool down regenerated adsorbent beds during the cool down phase of the PTSA cycle, in another aspect of the invention, all or some of the second stage permeate gas stream is used as the cool down gas stream. The second stage permeate gas stream withdrawn from the adsorbent bed undergoing cool down (as a recycle stream) is fed to the suction inlet of the main compressor where it is compressed and combined with the raw biogas feed stream to form the PTSA feed gas stream. After the second stage permeate gas is used as the cool down gas stream, it may be fed directly to the suction inlet of the main compressor, or alternatively, it instead may be compressed in a secondary compressor. While this alternative routing of the second stage permeate gas stream/recycle stream requires a second compressor, these gases are largely free of impurities so they may be routed directly to the first gas separation membrane stage after compression. This avoids an increase in the flow rate of the PTSA feed gas stream that must be treated by the PTSA unit. As a result, the size and cost of the PTSA unit may be decreased in comparison to the general scheme where the recycle stream is compressed and combined with the raw biogas feed stream at the main compressor.

[0099] When the first stage permeate is used as the regeneration gas stream and the second stage permeate is used as the cool down gas stream, various PTSA cycles may be created depending upon the number of beds in the PTSA unit.

[0100] A three-bed PTSA unit maximizes the uses of the first and second stage permeate gas streams as the regeneration and cool down gas streams. For a three-bed PTSA unit, a typical cycle is described in Table I below.

TABLE-US-00001 TABLE I typical PTSA cycle for three beds Phase # 1 2 3 Bed # 1 adsorption depressurization cool down then then repressurization regeneration 2 cool down then adsorption depressurization repressurization then regeneration 3 depressurization cool down then adsorption then regeneration repressurization

[0101] For feeds of biogas where excess regeneration gas is available, a more simple two bed cycle can be applied. An example of when excess regeneration gas is available is when the feed gas contains relatively low levels of impurities, such as low levels of H2S such that the amount of adsorbent to be heated is reduced as compared to a feed with higher levels of impurities. A typical cycle for a two-bed PTSA unit is described in Table II below.

TABLE-US-00002 TABLE II typical PTSA cycle for two beds Phase # 1 2 3 4 Bed # 1 adsorption adsorption depressurization cool down then then repressurization regeneration 2 depressurization cool down then adsorption adsorption then repressurization regeneration

[0102] While the three bed cycle is a basic approach the technology is not limited by the cycle used. For example where upflow adsorption is used, the velocity of the feed gas can be limited by the fluidization velocity and using two vessels simultaneously for adsorption allows a more optimal process. A typical cycle for a four-bed PTSA unit is described in Table III below.

TABLE-US-00003 TABLE III typical PTSA cycle for four beds Phase # 1 2 3 4 Bed # 1 adsorption adsorption depressurization cool down then then repressurization regeneration 2 cool down then adsorption adsorption depressurization repressurization then regeneration 3 depressurization cool down then adsorption adsorption then repressurization regeneration 4 adsorption depressurization cool down then adsorption then repressurization regeneration

[0103] I will now proceed to describe some process configurations for carrying out the invention described above. One of ordinary skill in the art will recognize that any of the aspects (including alternative embodiments or variations) of the invention described above may be combined with any of the specific process configurations described below.

[0104] As best shown in FIGS. 1 and 1, a stream of raw biogas 1 is fed to a main compressor 3. A PTSA feed gas stream 5 is received from the compressor 3 and fed to one or more adsorbent beds the PTSA unit 7 that are undergoing the repressurization phase and one or more adsorbent beds that are undergoing the adsorption phase. The adsorbent beds of the PTSA unit selectively adsorb, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0105] A PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from one or more beds of the PTSA unit 7 undergoing adsorption and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15.

[0106] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into a second stage permeate stream 19 and a second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0107] A waste stream 23 includes depressurization gas withdrawn from one or more of the beds the PTSA unit 7 that are undergoing depressurization is fed to a treatment unit 25 where it is burned or thermally oxidized to yield a vent gas 27. After the one or more beds undergoing depressurization are suitably depressurized, instead of bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at a heater 29 and fed as a regeneration gas stream 31 to the one or more depressurized adsorbent beds of the PTSA unit 7 that are undergoing regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the one or more beds being regenerated and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0108] The second stage permeate gas stream 19 is fed to one or more beds of the PTSA unit 7 undergoing cool down and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0109] When the one or more beds undergoing cool down reach a suitable temperature, the second stage permeate gas stream 19 is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Alternatively and as shown in FIG. 1, instead of feeding the recycle stream 35 to the suction inlet of the main compressor 3, it is compressed at a secondary compressor 37 and fed to the first gas separation membrane stage 11. Optionally, stream 35 is cooled before being fed to the suction inlet of the main or secondary compressor 3, 37.

[0110] Regardless of whether the recycle stream 35 is fed to the main compressor 3 or secondary compressor 37, simultaneous with this, the PTSA feed gas 5 is also fed to the one or more beds that have been cooled down in order to repressurize them in anticipation of undergoing adsorption in the next phase of the PTSA cycle. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate streams 15, 21.

[0111] In two particular embodiments and as best shown in FIGS. 1 and 1, there are three membrane gas separation stages 11, 17, 18 each of which includes one or more gas separation membranes selective for CO.sub.2 over methane. The difference between the embodiments of FIGS. 1 and 1 and the embodiments of FIGS. 1 and 1 is as follows. Instead of heating the first stage permeate gas stream 13 and using it as a regeneration gas stream for the one or more depressurized adsorbent beds of the PTSA unit 7 that are undergoing regeneration, additional amounts of methane are recovered from the first stage permeate gas stream 13 at the third gas separation membrane stage 18. The first permeate gas stream 13 is first compressed at a tertiary compressor 14 to a pressure at or above that of the PTSA product gas stream 9 and subsequently fed to the third gas separation membrane stage 18 where it is separated into a third permeate stream 20 and a third retentate stream 22. The third retentate stream 22 is fed, along with the PTSA product gas stream 9, to the first gas separation membrane stage 11 where some of the methane recovered at the third stage 18 may be recovered in the first retentate gas 15. In this embodiment, the third permeate stream 20 performs the same functions of the first permeate stream 13 in the embodiment of FIGS. 1 and 1. Thus, the regeneration stream 31 is fed to the one or more depressurized adsorbent beds of the PTSA unit 7 that are undergoing regeneration so as to desorb impurities from the one or more beds being regenerated. As with the embodiments of FIG. 1 and I the regeneration stream 31, now containing desorbed impurities, is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27. Finally, the embodiment of FIG. 1 differs from that of FIG. 1 in that, instead of feeding the recycle stream 35 to the suction inlet of the main compressor 3, in the embodiment of FIG. 1 it is compressed at a secondary compressor 37 and fed to the first gas separation membrane stage 11. Optionally, stream 35 is cooled before being fed to the suction inlet of the main or secondary compressor 3, 37.

[0112] In two other particulars embodiments and as best shown in FIGS. 2A-2D and 2A-2D, the PTSA unit 7 includes two adsorbent beds 41, 42 that undergo four phases in the PTSA cycle as shown in Table II above.

[0113] In a first phase of the embodiments of FIGS. 2A-2D and FIGS. 2A-2D and as best shown in FIGS. 2A and 2A, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 is withdrawn from the main compressor 3 and fed to a first adsorbent bed 41 of the PTSA unit 7 (the outlines of which are not illustrated for sake of clarity). The first adsorbent bed 41 undergoes adsorption in the first and second phases where it selectively adsorbs, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0114] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the first adsorbent bed 41 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0115] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0116] A waste stream 23 includes depressurization gas withdrawn from a second adsorption bed 42 of the PTSA unit 7 that is undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the second bed 42 is suitably depressurized, instead of being directly fed to the treatment unit 25 and bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the second adsorbent bed 42 which now undergoes regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the second adsorbent bed and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0117] The second stage permeate gas stream 19 is recycled to the suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Alternatively and as illustrated in FIG. 2A, the second stage permeate gas stream 19 may be recycled to a suction inlet of a secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11.

[0118] In a second phase of the embodiment of FIGS. 2A-2D and 2A-2D and as best shown in FIGS. 2B and 2B, the raw biogas stream 1 is continued to be fed to and compressed by the main compressor 3 and the PTSA feed gas stream 5 continues to be withdrawn from the main compressor 3 and fed to the first adsorbent bed 41 of the PTSA unit 7 as explained above. The first adsorbent bed 41 continues to undergoes adsorption as explained above.

[0119] Similarly, the PTSA product gas 9 is withdrawn from the first adsorbent bed 41 and fed to the first gas separation membrane stage 11 where it is separated into a first stage permeate gas stream 13 and a first stage retentate gas stream 15.

[0120] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into a second stage permeate stream 19 and a second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0121] Instead of being fed to the second adsorbent bed 42 as a regeneration gas, the first stage permeate gas stream 13 is fed to the treatment unit 25. The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17 where it is separated into a second stage permeate stream 19 and the second stage retentate stream 21.

[0122] The second stage permeate gas stream 19 is fed to the second adsorbent bed 42 (which is now undergoing cool down) and recycled as a recycle stream 35 (containing the gas of the second stage permeate gas plus impurities desorbed from the second adsorbent bed 42) to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0123] When the second adsorbent bed 42 reaches a suitable temperature, the second stage permeate gas stream 19 bypasses the second adsorbent bed 42 and is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the second adsorbent bed 42 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0124] Alternatively and as shown in FIG. 2B, instead of feeding the bypassing second stage permeate gas stream 19 to the suction inlet of the main compressor 3, it is compressed at the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0125] I note that, although streams 19 and 35 are illustrated as being contiguous along a common terminal branch in FIGS. 2B, 2B, 2D, 2D, 3A-3C, 3A-3C, 4A-4D, and 4A-4D, the skilled artisan will recognize that the flows of gas may be directed through a common section of piping or different piping terminating at the main compressor 3.

[0126] In a third phase of the embodiment of FIGS. 2A-2D and 2A-2D and as best shown in FIGS. 2C and 2C, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 is withdrawn from the main compressor 3 and is now fed to the second adsorbent bed 42 instead of the first adsorbent bed 41. The second adsorbent bed 42 undergoes adsorption in the third and fourth phases where it selectively adsorbs, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0127] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the second adsorbent bed 42 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0128] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas as described above.

[0129] A waste stream 23 includes depressurization gas withdrawn from the first adsorption bed 41 which is now undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the first bed 41 is suitably depressurized, instead of being directly fed to the treatment unit 25, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the first adsorbent bed 41 which is now undergoing regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the first adsorbent bed 41 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0130] The second stage permeate gas stream 19 is recycled to the suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Alternatively and as shown in FIG. 2C, the second stage permeate gas stream 19 is fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0131] In a fourth phase of the embodiment of FIGS. 2A-2D and 2A-2D and as best shown in FIGS. 2D and 2D, the raw biogas stream 1 is continued to be fed to and compressed by the main compressor 3 and the PTSA feed gas stream 5 continues to be withdrawn from the main compressor 3 and fed to the second adsorbent bed 42 as explained above. The first adsorbent bed 42 continues to undergoes adsorption as explained above.

[0132] Similarly, the PTSA product gas 9 is withdrawn from the second adsorbent bed 42 and fed to the first gas separation membrane stage 11 where it is separated into a first stage permeate gas stream 13 and a first stage retentate gas stream 15.

[0133] Instead of being fed to the first adsorbent bed 41 as a regeneration gas, the first stage permeate gas stream 13 is fed to the treatment unit 25. The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17 where it is separated into a second stage permeate stream 19 and the second stage retentate stream 21.

[0134] The second stage permeate gas stream 19 is fed to the first adsorbent bed 41 (which is now undergoing cool down) and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0135] When the first adsorbent bed 41 reaches a suitable temperature, the second stage permeate gas stream 19 bypasses the first adsorbent bed 41 and is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the first adsorbent bed 41 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0136] Alternatively and as shown in FIG. 2D, instead of feeding the bypassing second stage permeate gas stream 19 to the suction inlet of the main compressor 3, it is fed to the suction inlet of the secondary compressor 37, compressed thereat, and fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0137] In two particular other embodiments illustrated in FIGS. 2A-2D and 2A-2D, there are three membrane gas separation stages 11, 17, 18 each of which includes one or more gas separation membranes selective for CO.sub.2 over methane. The difference between the embodiments of FIGS. 2A-2D/2A-2D and the embodiments of 2A-2D/2A-2D is as follows. Instead of heating the first stage permeate gas stream 13 and using it as a regeneration gas stream for one of the adsorbent beds 41, 42 which have undergone depressurization, additional amounts of methane are recovered from the first stage permeate gas stream 13 at the third gas separation membrane stage 18. The first permeate gas stream 13 is first compressed at a tertiary compressor 14 to a pressure at or above that of the PTSA product gas stream 9 and subsequently fed to the third gas separation membrane stage 18 where it is separated into a third permeate stream 20 and a third retentate stream 22. The third retentate stream 22 is fed, along with the PTSA product gas stream 9, to the first gas separation membrane stage 11 where some of the methane recovered at the third stage 18 may be recovered in the first retentate gas 15. In this embodiment, the third permeate stream 20 performs the same functions of the first permeate stream 13 in the embodiment of FIGS. 2A-2D and 2A-2D. Thus, the regeneration stream 31 is fed to the adsorbent bed 41, 42 (which has undergone regeneration) so as to desorb impurities from the one or more beds being regenerated. As with the embodiments of FIGS. 2A-2D and 2A-2D, the regeneration stream 31, now containing desorbed impurities, is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27. Finally, the embodiment of FIGS. 2A-2D differs from that of FIGS. 2A-2D in that, instead of feeding the recycle stream 35 to the suction inlet of the main compressor 3, in the embodiment of FIGS. 2A-2D it is compressed at a secondary compressor 37 and fed to the first gas separation membrane stage 11. Optionally, stream 35 is cooled before being fed to the suction inlet of the main or secondary compressor 3, 37.

[0138] In another embodiment and as best shown in FIGS. 3A-3C and 3A-3C, the PTSA unit 7 includes three adsorbent beds 41, 42, 43 that undergo three phases in the PTSA cycle as shown in Table I above.

[0139] In a first phase of the embodiment of FIGS. 3A-3C and 3A-3C and as best shown in FIGS. 3A and 3A, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 is withdrawn from the main compressor 3 and fed to a first adsorbent bed 41 of the PTSA unit 7 (the outlines of which are not illustrated for sake of clarity). The first adsorbent bed 41 undergoes adsorption in the first and second phases where it selectively adsorbs, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0140] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the first adsorbent bed 41 and fed to a feed gas inlet of the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13, withdrawn from a permeate gas outlet of the first gas separation membrane stage, is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0141] The first stage retentate gas stream 15, withdrawn from a retentate gas outlet of the first gas separation membrane stage, is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0142] A waste stream 23 includes depressurization gas withdrawn from the third adsorption bed 43 of the PTSA unit 7 that is undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the third bed 43 is suitably depressurized, instead of being directly fed to the treatment unit 25 and bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the third adsorbent bed 42 which now undergoes regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the third adsorbent bed and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0143] The second stage permeate gas stream 19 is fed to the second adsorbent bed 42 which is undergoing cool down and recycled as a recycle stream 35 (containing the gas of the second stage permeate gas plus impurities desorbed from the second adsorbent bed 42) to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0144] When the second adsorbent bed reaches a suitable temperature, the second stage permeate gas stream 19 is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas 5 is also fed to the second adsorbent bed 42 in order to repressurize it in anticipation of undergoing adsorption in the next phase of the PTSA cycle. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0145] Alternatively and as shown in FIG. 3A, instead of feeding the recycle stream 35 or the second stage permeate gas stream 19 to the suction inlet of the main compressor 3, each may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0146] In a second phase of the embodiment of FIGS. 3A-3C and 3A-3C and as best shown in FIGS. 3B and 3B, the raw biogas stream 1 is continued to be fed to and compressed by the main compressor 3, but the PTSA feed gas stream 5 withdrawn from the main compressor 3 is now fed to the second adsorbent bed 42 as explained above.

[0147] The PTSA product gas 9 is withdrawn from the second adsorbent bed 42 and fed to the first gas separation membrane stage 11 where it is separated into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0148] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0149] A waste stream 23 includes depressurization gas withdrawn from the first adsorption bed 41 of the PTSA unit 7 that is undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the first bed 41 is suitably depressurized, instead of being directly fed to the treatment unit 25 and bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the first adsorbent bed 41 which now undergoes regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the first adsorbent bed 41 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0150] The second stage permeate gas stream 19 is fed to the third adsorbent bed 43 (which is now undergoing cool down) and recycled as a recycle stream 35 (containing the gas of the second stage permeate gas plus impurities desorbed from the third adsorbent bed 43) to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0151] When the third adsorbent bed 43 reaches a suitable temperature, the second stage permeate gas stream 19 bypasses the third adsorbent bed 43 and is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the third adsorbent bed 43 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0152] Alternatively and as shown in FIG. 3B, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0153] In a third phase of the embodiment of FIGS. 3A-C and 3A-3C and as best shown in FIG. 3C and FIG. 3C, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 is withdrawn from the main compressor 3 and is now fed to the third adsorbent bed 43 instead of the second adsorbent bed 42. The third adsorbent bed 43 undergoes adsorption in the third and fourth phases where it selectively adsorbs, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0154] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the third adsorbent bed 43 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0155] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas as described above.

[0156] A waste stream 23 includes depressurization gas withdrawn from the second adsorption bed 42 which is now undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the second bed 42 is suitably depressurized, instead of being directly fed to the treatment unit 25, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the second adsorbent bed 42 which is now undergoing regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the second adsorbent bed 42 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0157] The second stage permeate gas stream 19 is fed to the first adsorbent bed 41 (which is now undergoing cool down) and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0158] When the first adsorbent bed 41 reaches a suitable temperature, the second stage permeate gas stream 19 bypasses the first adsorbent bed 41 and is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the first adsorbent bed 41 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0159] Alternatively and as shown in FIG. 3C, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11.

[0160] In two particular other embodiments illustrated in FIGS. 3A-3C and 3A-3C, there are three membrane gas separation stages 11, 17, 18 each of which includes one or more gas separation membranes selective for CO.sub.2 over methane.

[0161] The difference between the embodiments of FIGS. 3A-3C/3A-3C and the embodiments of 3A-3C/3A-3C is as follows. Instead of heating the first stage permeate gas stream 13 and using it as a regeneration gas stream for one of the adsorbent beds 41, 42, 43 which have undergone depressurization, additional amounts of methane are recovered from the first stage permeate gas stream 13 at the third gas separation membrane stage 18. The first permeate gas stream 13 is first compressed at a tertiary compressor 14 to a pressure at or above that of the PTSA product gas stream 9 and subsequently fed to the third gas separation membrane stage 18 where it is separated into a third permeate stream 20 and a third retentate stream 22. The third retentate stream 22 is fed, along with the PTSA product gas stream 9, to the first gas separation membrane stage 11 where some of the methane recovered at the third stage 18 may be recovered in the first retentate gas 15. In this embodiment, the third permeate stream 20 performs the same functions of the first permeate stream 13 in the embodiment of FIGS. 3A-3C and 3A-3C. Thus, the regeneration stream 31 is fed to the adsorbent bed 41, 42, 43 (which has undergone regeneration) so as to desorb impurities from the one or more beds being regenerated. As with the embodiments of FIGS. 3A-3C and 3A-3C, the regeneration stream 31, now containing desorbed impurities, is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27. Finally, the embodiment of FIGS. 3A-3C differs from that of FIGS. 3A-3C in that, instead of feeding the recycle stream 35 to the suction inlet of the main compressor 3, in the embodiment of FIGS. 3A-3C it is compressed at a secondary compressor 37 and fed to the first gas separation membrane stage 11. Optionally, stream 35 is cooled before being fed to the suction inlet of the main or secondary compressor 3, 37.

[0162] In another embodiment and as best shown in FIGS. 4A-4D and 4A-4D, the PTSA unit 7 includes four adsorbent beds 41, 42, 43, 44 that undergo three phases in the PTSA cycle as shown in Table III above.

[0163] In a first phase of the embodiment of FIGS. 4A-4D and 4A-4D and as best shown in FIGS. 4A and 4A, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 is withdrawn from the main compressor 3 and fed to the first and fourth adsorbent beds 41, 44 of the PTSA unit 7 (the outlines of which are not illustrated for sake of clarity) which selectively adsorb, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0164] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the first and fourth adsorbent beds 41, 44 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0165] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0166] A waste stream 23 includes depressurization gas withdrawn from the third adsorption bed 43 of the PTSA unit 7 that is undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the third bed 43 is suitably depressurized, instead of being directly fed to the treatment unit 25 and bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the third adsorbent bed 43 which now undergoes regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the third adsorbent bed and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0167] The second stage permeate gas stream 19 is fed to the second adsorbent bed 42 which is undergoing cool down and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0168] When the second adsorbent bed reaches a suitable temperature, the second stage permeate gas stream 19 is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas 5 is also fed to the second adsorbent bed 42 in order to repressurize it in anticipation of undergoing adsorption in the next phase of the PTSA cycle. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0169] Alternatively and as shown in FIG. 4A, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0170] In a second phase of the embodiment of FIGS. 4A-4D and 4A-4D and as best shown in FIGS. 4B and 4B, the raw biogas stream 1 is continued to be fed to and compressed by the main compressor 3, and the PTSA feed gas stream 5 withdrawn from the main compressor 3 is still fed to the first adsorbent bed 41. In this second phase, however, the PTSA feed gas stream 5 withdrawn from the main compressor 3 is no longer fed to the fourth adsorbent bed 44 but is instead fed to the second adsorbent bed 42. Thus, the first and second adsorbent beds 41, 42 undergo adsorption where they selectively adsorb, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0171] The PTSA product gas 9 is withdrawn from the first and second adsorbent beds 41, 42 and fed to the first gas separation membrane stage 11 where it is separated into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0172] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas that is suitable for on-site use in generators or meets typical pipeline specifications for sale (as described above).

[0173] A waste stream 23 includes depressurization gas withdrawn from the fourth adsorption bed 44 of the PTSA unit 7 that is undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the first bed 44 is suitably depressurized, instead of being directly fed to the treatment unit 25 and bypassing the PTSA unit 7, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the fourth adsorbent bed 44 which now undergoes regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the fourth adsorbent bed 44 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0174] The second stage permeate gas stream 19 is fed to the third adsorbent bed 43 (which is now undergoing cool down) and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0175] When the third adsorbent bed 43 reaches a suitable temperature, the second stage permeate gas stream 19 bypasses the third adsorbent bed 43 and is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the third adsorbent bed 43 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0176] Alternatively and as shown in FIG. 4B, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0177] In a third phase of the embodiment of FIGS. 4A-D and 4A-3D and as best shown in FIG. 4C and FIG. 4C, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 continues to be withdrawn from the main compressor 3 and fed to the second adsorbent bed 42. In this third phase, however, instead of also feeding the PTSA feed gas stream 5 to the first adsorbent bed 41, it is now fed to the third adsorbent bed 43. Thus, the second and third adsorbent beds 42, 43 undergo adsorption where they selectively adsorbs, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0178] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the second and third adsorbent beds 42, 43 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0179] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas as described above.

[0180] A waste stream 23 includes depressurization gas withdrawn from the first adsorption bed 41 which is now undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the first bed 41 is suitably depressurized, instead of being directly fed to the treatment unit 25, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the first adsorbent bed 41 which is now undergoing regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the first adsorbent bed 41 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0181] The second stage permeate gas stream 19 is fed to the fourth adsorbent bed 44 (which is now undergoing cool down) and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0182] When the fourth adsorbent bed 44 reaches a suitable temperature, the second stage permeate gas stream 19 is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the fourth adsorbent bed 44 in order to repressurize it in anticipation of undergoing adsorption in the fourth phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0183] Alternatively and as shown in FIG. 4C, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0184] In a fourth phase of the embodiment of FIGS. 4A-D and 4A-4D and as best shown in FIG. 4D and FIG. 4D, the raw biogas stream 1 is fed to and compressed by the main compressor 3. The PTSA feed gas stream 5 continues to be withdrawn from the main compressor 3 and fed to the third adsorbent bed 43. In this fourth phase, however, instead of also feeding the PTSA feed gas stream 5 to the second adsorbent bed 42, it is now fed to the fourth adsorbent bed 44. Thus, the third and fourth adsorbent beds 43, 44 undergo adsorption where they selectively adsorb, from the pressurized gas of the PTSA feed gas stream 5, H.sub.2S, water, and VOCs (and optionally siloxanes) over methane and H.sub.2S over CO.sub.2.

[0185] The PTSA product gas 9 deficient in H.sub.2S, water, and VOCs (and optionally siloxanes) and enriched in CH.sub.4 and CO.sub.2 in comparison to the PTSA feed gas stream 5 is withdrawn from the third and fourth adsorbent beds 43, 44 and fed to the first gas separation membrane stage 11. The first gas separation membrane stage 11, including one or more gas separation membranes selective for CO.sub.2 over methane separate the PTSA product gas stream 9 into a first stage permeate gas stream 13 and a first stage retentate gas stream 15. The first stage permeate gas stream 13 is initially fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27.

[0186] The first stage retentate gas stream 15 is fed to the second gas separation membrane stage 17. The second gas separation membrane stage, including one or more gas separation membranes selective for CO.sub.2 over methane separate the first stage retentate stream 15 into the second stage permeate stream 19 and the second stage retentate stream 21. The second stage retentate stream 21 is the product gas as described above.

[0187] A waste stream 23 includes depressurization gas withdrawn from the second adsorption bed 42 which is now undergoing depressurization. The waste stream 23 is fed to the treatment unit 25 where it is burned or thermally oxidized to yield the vent gas 27. After the second bed 42 is suitably depressurized, instead of being directly fed to the treatment unit 25, the first stage permeate gas stream 13 is heated at the heater 29 and fed as a regeneration gas stream 31 to the second adsorbent bed 42 which is now undergoing regeneration. Thus, the waste stream 23 now includes the gas of the regeneration stream 31 plus impurities desorbed from the second adsorbent bed 42 and is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27.

[0188] The second stage permeate gas stream 19 is fed to the first adsorbent bed 41 (which is now undergoing cool down) and recycled as a recycle stream 35 to a suction inlet of the main compressor 3 where it is combined and compressed with the raw biogas stream 1 to yield the PTSA feed gas stream 5. Optionally, the recycle stream 35 may be cooled before being fed to the suction inlet of the main compressor 3.

[0189] When the first adsorbent bed 41 reaches a suitable temperature, the second stage permeate gas stream 19 is instead fed to the suction inlet of the main compressor 3 where it combined and compressed with the raw biogas stream 1 to produce the PTSA feed gas stream 5. Simultaneous with this, the PTSA feed gas stream 5 is also fed to the first adsorbent bed 41 in order to repressurize it in anticipation of undergoing adsorption in the third phase. Optionally, repressurization is conducted with PTSA product gas and/or the first or second gas separation membrane stage retentate gas streams 15, 21.

[0190] Alternatively and as shown in FIG. 4D, instead of feeding the second stage permeate gas stream 19 or the recycle stream 35 to the suction inlet of the main compressor 3, both may be fed to the suction inlet of the secondary compressor 37, compressed thereat, and subsequently fed to the first gas separation membrane stage 11. Optionally the recycle stream 35 may be cooled before being fed to the suction inlet of the secondary compressor 37.

[0191] In two particular other embodiments illustrated in FIGS. 4A-4D and 4A-4D, there are three membrane gas separation stages 11, 17, 18 each of which includes one or more gas separation membranes selective for CO.sub.2 over methane. The difference between the embodiments of FIGS. 4A-4D/4A-4D and the embodiments of 4A-4D/4A-4D is as follows. Instead of heating the first stage permeate gas stream 13 and using it as a regeneration gas stream for one of the adsorbent beds 41, 42, 43 which have undergone depressurization, additional amounts of methane are recovered from the first stage permeate gas stream 13 at the third gas separation membrane stage 18. The first permeate gas stream 13 is first compressed at a tertiary compressor 14 to a pressure at or above that of the PTSA product gas stream 9 and subsequently fed to the third gas separation membrane stage 18 where it is separated into a third permeate stream 20 and a third retentate stream 22. The third retentate stream 22 is fed, along with the PTSA product gas stream 9, to the first gas separation membrane stage 11 where some of the methane recovered at the third stage 18 may be recovered in the first retentate gas 15. In this embodiment, the third permeate stream 20 performs the same functions of the first permeate stream 13 in the embodiment of FIGS. 4A-4D and 4A-4D. Thus, the regeneration stream 31 is fed to the adsorbent bed 41, 42, 43 (which has undergone regeneration) so as to desorb impurities from the one or more beds being regenerated. As with the embodiments of FIGS. 4A-4D and 4A-4D, the regeneration stream 31, now containing desorbed impurities, is fed to the treatment unit 25 for burning or thermal oxidization to yield the vent gas 27. Finally, the embodiment of FIGS. 4A-4D differs from that of FIGS. 4A-4D in that, instead of feeding the recycle stream 35 to the suction inlet of the main compressor 3, in the embodiment of FIGS. 4A-4D it is compressed at a secondary compressor 37 and fed to the first gas separation membrane stage 11. Optionally, stream 35 is cooled before being fed to the suction inlet of the main or secondary compressor 3, 37.

[0192] I note that, for the sake of clarity, heater 29 is not illustrated in any of FIGS. 2A-2D, 2A-2D, 2A-2D, 2A-2D, 3A-3C, 3A-3C, 3A-3C, 3A-3C, 4A-4D, 4A-D, 4A-4D, or 4A-D, but it should be understood as present in each of those schemes for the purpose of heating the first stage permeate stream 13 as discussed above.

[0193] Finally, I note that aspects of the invention are not limited to the use of first and/or second gas separation membrane stage retentate gas streams 15, 21 for use as the regeneration and cool down gases. Indeed, any permutation of three or more gas separation membrane stages may be used in which any one or more of the permeate streams (the entirety of a stream or only a portion of a stream) may be used as the regeneration gas and/or cool down gas.

[0194] While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.

[0195] The singular forms a, an and the include plural referents, unless the context clearly dictates otherwise.

[0196] Comprising in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing i.e. anything else may be additionally included and remain within the scope of comprising. Comprising is defined herein as necessarily encompassing the more limited transitional terms consisting essentially of and consisting of; comprising may therefore be replaced by consisting essentially of or consisting of and remain within the expressly defined scope of comprising.

[0197] Providing in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.

[0198] Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.

[0199] Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.

[0200] All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.