CRYOGENIC PROCESS FOR CRUDE HELIUM RECOVERY FROM NATURAL GAS
20230391621 · 2023-12-07
Assignee
- COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH (New Delhi, IN)
- ONGC Energy Centre Trust (OECT) (Delhi, IN)
Inventors
- Sunil Kumar (Dehradun, IN)
- Avinash S. Mhetre (Dehradun, IN)
- Ojasvi Sharma (Dehradun, IN)
- Swapnil Diveker (Dehradun, IN)
- Soumen Dasgupta (Dehradun, IN)
- Manoj Srivastava (Dehradun, IN)
- Anjan RAY (Dehradun, IN)
- Aarti Arya (Dehradun, IN)
- Prasenjit Ghosh (Dehradun, IN)
- Bharat S. Mendhe (Delhi, IN)
- Nammi Ramya (Delhi, IN)
Cpc classification
International classification
Abstract
The present invention relates to a cryogenic process to produce crude helium from pretreated natural gas. The pretreated natural gas is processed in two flash stages using the helium free process stream as a stripping agent, and a distillation column with the identified operating conditions and process scheme to ensure 100% helium recovery with reduced capital and operating cost for producing the crude helium. The integration of the cryogenic process with the already known purification system to produce pure helium is demonstrated to ensure high helium recovery in a hybrid process.
Claims
1. A cryogenic process to produce crude helium from pretreated natural gas consisting of 80-98 mole % methane, 3-20 mole % methane plus hydrocarbon, 0.1-5.0 mole % nitrogen %, 0.01-mole % helium, 1-10 ppmv H.sub.2S, 5-50 ppmv water, wherein said process comprising the steps of: a) subjecting the pretreated natural gas (1) to cooler (E1) for its cooling in the temperature range of minus 70-minus 140° C.; b) subjecting a partially condensed gas (2) to throttling device (TD) to reduce its pressure and generating cold and routing a stream (2A) from TD to the first flash stage (FSI) or partially condensed gas (2) direct routing to first flash stage (FSI) for generating an uncondensed gas stream (3) and liquid stream (4); c) subjecting the gas stream (3) for its cooling in a heat exchanger (E2), which uses a cold process liquid streams (7) and external cold utility (ER1) in the temperature range of minus 100-minus 150° C.; d) subjecting a partially condensed gas stream (5) to a second flash stage (FSII), which has 2-6 tray below the feed entry location and use helium free stripping stream (19) to generate a gas stream (6) and liquid stream (7); e) subjecting the gas stream (6) to multi streams heat exchanger (E3) for its heating; f) subjecting a heated gas stream (6A) along the high-pressure purge stream (15D) having pressure in the range of 6-20 bars from purification system (PS) to a compressor (K2) for increasing combined streams pressure in the range of 20-50 bars; g) subjecting a pressurized gas stream (8) to a water or air cooler (E6), subsequently cooling of gas stream (9) to multi stream heat exchanger (E3) using either process cold streams or both process cold stream and external utility, cooling of stream (10) in a heat exchanger E5 and then stream (11) from E5 is again routed to E3 for its cooling and producing stream (12) having a temperature in the range of minus 80-minus 140° C.; h) subjecting a partially condensed gas stream (12) to a distillation column (DC) having multiple trays in its stripping and rectification sections and having the process stream and/or external utility coils cooler (E-6) inside the DC overhead section to generate the in situ liquid for rectification section and/or reflux stream (16) at the top tray; i) cooling a gas stream (13) in a heat exchanger (E4) for its partial condensation; j) subjecting a cooled gas stream (14) to a separating vessel (V1) for generating the crude helium (15) and liquid stream (16) used as reflux stream in top section of DC; k) recycling a purge stream (15C) having pressure in the range of 1-10 bars from the purification system to pressure increasing device (K3) to produce an increased pressure stream (15E), which is further routed to a gas compressor (K2); l) recycling a purge stream (15D) having pressure in the range of 8-20 bars from the purification system to a gas compressor (K2); m) splitting the DC bottom liquid stream (17) into two streams 18 and 20; n) subjecting a stream 18 to throttling valve/expender (PV1) to generate low-pressure stream 18A, which is routed to exchanger E3 for its cold recovery; o) subjecting the stream 20 to throttling valve/expander (PV2) to generate low-pressure stream 20A, which is routed to heat exchanger E4 for its cold recovery; p) subjecting a stream 20B either to a cold utility generation system or to multi streams heat exchanger E3 for its cold recovery; q) subjecting a stream 7C, stream 18B, stream 20B or 20B1 to a cold utility generation system (CUGS) for recovering their cold; r) subjecting a stream 20C to pressure increasing device (K4) with or without 7D; s) subjecting a stream 7E from K4 to a gas compressor (K1) for recycling the hydrocarbon stream for further processing and utilization; t) recycling a streams 18D, 21 and 7D to upstream process for further processing and utilization.
2. The process as claimed in claim 1, wherein the methane plus hydrocarbon is selected from ethane, propane, butane, isobutene, pentane, iso-pentane and hexane in any proportion.
3. The process as claimed in claim 1, wherein the distillation column (DC) is operating, preferably in the pressure range of 20-50 bars and most preferably in the temperature range of 20-40 bars.
4. The process as claimed in claim 1, wherein in another embodiment of the present invention, the throttling device (TD) is represented by throttling valve or expansion valve or similar device and the pressure increasing device (K3) is represented by a compressor or ejector using compressing process stream (6A), wherein K3 may be single-stage or multistage with inter stage cooling pressure increasing device.
5. The process as claimed in claim 1, wherein the pressure increasing device (K4) is represented by a compressor for compressing the 20C stream or ejector using compressing process stream (7D).
6. The process as claimed in claim 1, wherein the crude helium stream (15) after its cold recovery in a cold utility generation system (CUGS) is subjected to a known purification system (PS) for producing the pure helium stream (15B).
7. The process as claimed in claim 6, wherein the purification system (PS) is either membranes or pressure swing adsorption or vacuum swing adsorption or a combination of thereof.
8. The process as claimed in claim 1, wherein the gas stream (13) from the top of DC is cooled in a heat exchanger (E4) using either process cold streams (20A) and external refrigeration stream (ER2) in the temperature range of minus 150-minus 185° C. (or process cold streams (20A) in the temperature range of minus 140-minus 165° C.
9. The process as claimed in claim 1, wherein stream 20B is subjected to heat exchanger E3 for its cold recovery prior to its routing to CUGS.
10. The process as claimed in claim 1, wherein external cold utility stream (ER1A) (
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0054]
[0055]
DETAILED DESCRIPTION OF THE INVENTION
[0056] The foregoing detailed description of the disclosure is elaborated to provide a clear understanding to the person who is skilled in the art. Additional features, embodiments and advantages of the invention will be described hereinafter which form the subject of the claims of the disclosure, However, the set forth disclosure provide in the specification will best be understood in conjunction with the appended claims and figures as provide heretofore. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent processes do not depart from the spirit and scope of the disclosure as set forth in the appended claims. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, and designed in a wide variety of different configurations, all of which are explicitly contemplated and make part of this disclosure.
[0057] While the invention has been disclosed with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the invention. In addition, many modifications may be made to adapt to a particular situation or material to the teachings of the invention without departing from its scope.
[0058] Throughout the specification and claims, the following terms take the meanings explicitly associated herein unless the context clearly dictates otherwise. The meaning of “a”, “an”, and “the” include plural references. The meaning of “in” includes “in” and “on.” Referring to the drawings, like numbers indicate like parts throughout the views. Additionally, a reference to the singular includes a reference to the plural unless otherwise stated or inconsistent with the disclosure herein. In line with the above objectives, present invention relates to a cryogenic process for natural gas to produce the crude helium with 100% helium recovery and to enhance helium recovery in a hybrid process consisting of a cryogenic process of the present invention and a known purification system to produce pure helium to overcome the disadvantages of prior art processes.
[0059] For the purpose of illustrating the invention, drawings constructed in accordance with the preferred embodiments of the present invention are conceptualized. The same numeral is used in drawings to refer to the same or similar stream, column, vessel, and other elements. It is important to note that invention is not limited to the precise arrangements of apparatus shown in drawings. The reference to
[0060] Referring to
[0061] The DC bottom liquid stream (17) is splitted into two streams 18 and 20. Stream 18 is routed to the throttling valve/expender (PV1) to generate low-pressure stream 18A, which is routed to exchanger E3 for its cold recovery. The stream 20 to throttling valve/expander (PV2) to generate low-pressure stream 20A which is routed to exchanger E4 for its cold recovery. The FS1 liquid stream (4) and stream (7A) are mixed to form stream (7B), which is routed to a heat exchanger (E1) for recovering its cold by cooling the feed stream (1). Stream 7C, stream 18B, and stream 20B are routed to the cold utility generation system (CUGS) for recovering their cold and reducing the CAPEX and OPEX of CUGS. The stream 20C from CUGS is routed to pressure increasing device (K4). The pressure increasing device (K4) can be represented by either compressor or ejector using the process stream (7D). The compressed stream (7E) from K4 is routed to a compressor (K1) for increasing the pressure to the required value for recycling the hydrocarbon stream (21) for further processing and utilization. Stream 18D and steam 7D can be recycled to the upstream process for further processing and utilization with or without compression.
[0062] Referring to
[0063] In most cryogenic processes, crude helium from nitrogen and methane-rich natural gas is produced as one of the products, along with liquefied natural gas (LNG) and fuel gas. The existing cryogenic processes are mostly designed to process high-pressure natural gas helium resources. There is a significant increase in the price and demand of helium with time, whereas helium resources are limited. The low-pressure natural gas resources containing a small concentration of helium (0.02-0.50%) and nitrogen (0.1-5.0%) are also now getting attention to recover the helium. Thus, there is a need for helium recovery from all kinds of natural gas resources containing helium. The cryogenic processing schemes used for crude helium recovery from the high-pressure natural gas use high pressure of natural gas to generate cold in the process itself using throttling through a valve or expander. Thus, applying these schemes for crude helium recovery from low-pressure natural gas will require compression of the total natural gas feed stream to high pressure. This will result in huge compression duty and capital cost requirements for helium recovery from low-pressure natural gas using the process developed for high-pressure natural gas. Moreover, high pressure and low-temperature conditions used in hydrocarbon and nitrogen rejection separation stages in high-pressure cryogenic processes lead to the dissolution of helium in product streams other than crude helium and results in helium loss which is undesirable in the context of helium's high price and limited resources availability. It is also observed that the crude helium produced from cryogenic processes contains more than two components, typically three components i.e. helium, nitrogen, and methane. Moreover, the cold generation using the feed stream expansion in these processes also generates a low-pressure fuel gas and other product streams, which need to be further compressed in case of high pressure of their further processing and utilization destinations.
[0064] Moreover, the person skilled in the art understand that the feed to the purification process will be around 0.25-1.0% of the total feed to cryogenic process depending upon the helium concentration in feed and crude helium generated in the cryogenic process. This implies that the process economics of a cryogenic integrated hybrid process to produce pure helium will be mostly governed by the crude helium production process economics. Therefore, it seems very important to develop an energy and capital-efficient cryogenic process which can provide maximum helium recovery, use minimum compression energy and cost for feed and product streams, produce binary components bearing crude helium to simplify the design of purification system for developing a hybrid process to make the production of pure helium from natural gas having low pressure and very low helium concentration feasible in a cost-effective manner.
[0065] The novelty of the present invention resides in developing an innovative processing scheme of a cryogenic process to produce the crude helium with 100% helium recovery and to provide more than 99% helium recovery in a hybrid process consisting of a cryogenic process of the present invention and a known purification system to produce pure helium production to overcome the disadvantages of prior art processes. Further, the proposed cryogenic process in the present invention involves the compression of 4-8% of the feed to high pressure in the pressure range of bars against the total feed gas compression requirement in the cryogenic processes developed for the high-pressure feed stream. The pressure loss between the supply feed to the process and products discharged from the process for further use is also significantly lower in the cryogenic process of the present invention compared to the cryogenic developed for high-pressure feed stream with feed stream throttling. Thus, the cryogenic process of the present invention has an opportunity to minimize the overall compression energy and cost to produce crude helium. The lower operating pressure in the first separation stage (FSI) and lower operating pressure and the use of helium free process stripping steams in the second separation stage (FSII) in the cryogenic process of the present invention ensure the 100% helium recovery in crude helium stream. The low operating pressure in most of the pieces of equipment for the cryogenic process of the present invention provides an opportunity to reduce the process's equipment capital cost. The recycling of high and low-pressure purge streams from the purification system to the cryogenic process at a location matching with process pressure profile ensures the high (≥99%) recovery of helium in the hybrid process consisting of the cryogenic process of the present invention.
EXAMPLES
[0066] The following two examples are given by way of illustration to substantiate the invention and, therefore, should not be construed to limit the scope of the invention. The properties of natural gas used in illustrative examples are given in Table 1. The embodiments of the present invention were simulated by using computational means.
TABLE-US-00001 TABLE 1 Composition of pretreated natural gas. S. No. Component Name Mole % 1 Methane 86.75 2 Ethane 7.00 3 Propane 3.00 4 i-Butane 0.6 5 n-Butane 1.0 6 i-Pentane 0.20 7 n-Pentane 0.20 8 n-Hexane 0.20 9 Nitrogen 1.00 10 Helium 0.050
EXAMPLES
[0067] The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purpose of illustrative discussion of preferred embodiments of the invention.
[0068] Example 1: This example is constructed in accordance with an embodiment of the present invention substantially as illustrated in
TABLE-US-00002 TABLE 2 Process conditions, mole and mass balances of key streams. Name 1 2 5 6A 8 9 12 15 15B Vapour Fraction 1.00 0.40 0.10 1.00 1.00 1.00 0.20 1.00 1.00 Temperature [C.] 35.00 −127.00 −134.35 10.00 108.06 55.00 −114.94 −177.46 30.38 Pressure [kg/cm2] 7.50 7.40 7.00 6.80 25.50 25.30 25.00 24.20 23.80 Molar Flow [kgmole/h] 33.46 33.46 13.31 1.83 1.86 1.86 1.86 0.05 0.02 Mass Flow [kg/h] 636.35 636.35 217.35 31.55 32.02 32.02 32.02 0.53 0.07 Mole fraction 2 5 6A 8.00 9 12 15 15B Methane 0.86750 0.86750 0.97423 0.88283 0.87 0.86812 0.86812 0.00000 0.00000 Ethane 0.07000 0.07000 0.00193 0.00003 0.00 0.00003 0.00003 0.00000 0.00000 Propane 0.03000 0.03000 0.00003 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 i-Butane 0.00600 0.00600 0.00000 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 n-Butane 0.01000 0.01000 0.00000 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 i-Pentane 0.00200 0.00200 0.00000 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 n-Pentane 0.00200 0.00200 0.00000 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 n-Hexane 0.00200 0.00200 0.00000 0.00000 0.00 0.00000 0.00000 0.00000 0.00000 Nitrogen 0.01000 0.01000 0.02255 0.10802 0.11 0.11391 0.11391 0.30000 0.00001 Helium 0.00050 0.00050 0.00125 0.00912 0.02 0.01794 0.01794 0.70000 0.99999 15C 18 18D 19 20 20A 20B 20C 21 Name Vapour Fraction 1.00 0.00 1.00 1.00 0.00 0.42 0.69 1.00 1.00 Temperature [C.] 30.38 −114.43 25.00 25.00 −114.43 −162.01 −161.20 25.00 62.86 Pressure [kg/cm2] 1.10 24.80 8.30 8.30 24.80 1.30 1.25 1.20 8.00 Molar Flow [kgmole/h] 0.03 1.40 1.10 0.30 0.41 0.41 0.41 0.41 32.41 Mass Flow [kg/h] 0.47 24.37 19.17 5.20 7.11 7.11 7.11 7.11 618.34 Mole fraction Methane 0.00000 0.89096 0.89096 0.89096 0.89096 0.89096 0.89096 0.89096 0.86724 Ethane 0.00000 0.00003 0.00003 0.00003 0.00003 0.00003 0.00003 0.00003 0.07227 Propane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.03097 i-Butane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00619 n-Butane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.01032 i-Pentane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00206 n-Pentane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00206 n-Hexane 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00206 Nitrogen 0.46154 0.10902 0.10902 0.10902 0.10902 0.10902 0.10902 0.10902 0.00680 Helium 0.53846 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
[0069] The purifying system to produce the pure helium with 50% helium recovery is used in the simulation of the scheme. It shall be noted that there is no helium present in the hydrocarbon byproduct streams (21 and 18D) from the process. This ensures the 100% recovery of helium from natural gas into crude helium. Moreover, the hybrid system based on the cryogenic process of the present invention will ensure the maximum helium recovery except for some helium loss in normally not flow gas purge streams from the purification system. There is a need for 22813.5 watts of external cold utility (ER1) at a temperature of minus 137° C. and 638.1 watts of external cold utility (ER21) at a temperature of minus 180° C. in the process scheme given in
[0070] Example 2: This example is constructed in accordance with an embodiment of the present invention substantially as illustrated in
TABLE-US-00003 1 2 5 6A 8 9 12 15 15B Name Vapour Fraction 1.00 0.40 0.10 1.00 1.00 1.00 0.15 1.00 1.00 Temperature [C.] 35.00 −127.00 −134.35 10.00 126.13 55.00 −114.16 −162.83 30.62 Pressure [kg/cm2] 7.50 7.40 7.00 6.80 30.00 29.80 29.50 29.00 23.80 Molar Flow [kgmole/h] 33.46 33.46 13.31 1.83 1.91 1.91 1.91 0.10 0.02 Mass Flow [kg/h] 636.35 636.35 217.35 31.55 33.36 33.36 33.36 1.87 0.07 Mole fraction Methane 0.8675 0.8675 0.9742 0.8828 0.8465 0.8465 0.8465 0.0000 0.0000 Ethane 0.0700 0.0700 0.0019 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Propane 0.0300 0.0300 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 i-Butane 0.0060 0.0060 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 n-Butane 0.0100 0.0100 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 i-Pentane 0.0020 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 n-Pentane 0.0020 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 n-Hexane 0.0020 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Nitrogen 0.0100 0.0100 0.0226 0.1080 0.1360 0.1360 0.1360 0.6500 0.0000 Helium 0.0005 0.0005 0.0013 0.0091 0.0175 0.0175 0.0175 0.3500 1.0000 15C 18 18D 19 20 20A 20B 20C 21 Name Vapour Fraction 1.00 0.00 1.00 1.00 0.00 0.50 0.96 1.00 1.00 Temperature [C.] 30.62 −108.99 25.00 25.00 −108.99 −165.22 −164.51 25.00 67.58 Pressure [kg/cm2] 1.1 29.30 8.30 8.30 29.30 0.95 0.90 0.85 8.00 Molar Flow [kgmole/h] 0.08 0.71 0.41 0.30 1.10 1.10 1.10 1.10 33.10 Mass Flow [kg/h] 1.80 12.40 7.20 5.20 19.08 19.08 19.08 19.08 630.31 Mole fraction Methane 0.0000 0.8910 0.8910 0.8910 0.8910 0.8910 0.8910 0.8910 0.8677 Ethane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0708 Propane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0303 i-Butane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0061 n-Butane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0101 i-Pentane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0020 n-Pentane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0020 n-Hexane 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0020 Nitrogen 0.7879 0.1090 0.1090 0.1090 0.1090 0.1090 0.1090 0.1090 0.0089 Helium 0.2121 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
[0071] The purifying system to produce the pure helium with 50% helium recovery from crude helium is used in the simulation of the scheme given in
Advantages of Invention
[0072] The several advantages of the present process are: [0073] The process provides 100% helium recovery from natural gas to produce crude helium. [0074] The hybrid process based on the cryogenic process of the present invention ensures high overall helium recovery to produce pure helium. [0075] The cryogenic process of the present invention needs compression of 4-8% of the natural gas feed to high pressure using the multistage compression against the total feed gas compression requirement for cryogenic processes developed for high-pressure natural gas feed stream. Moreover, the pressure drop between the feed stream and product streams consisting of most of the hydrocarbons is much lower than reported in cryogenic processes developed for high-pressure natural gas feed streams. Thus the process of the present invention has an opportunity to minimize the overall compression energy and cost to produce crude helium. [0076] Lower operating pressure in most of the pieces of equipment of the cryogenic process of the present invention may provide the opportunity to reduce the process's equipment capital cost. [0077] Lower GHG emissions to the environment will help to make helium recovery from natural gas cleaner and greener.