CN110108091B - Cryogenic liquefaction system with improved hydrogen separation membrane insertion for STAR propane dehydrogenation - Google Patents
Cryogenic liquefaction system with improved hydrogen separation membrane insertion for STAR propane dehydrogenation Download PDFInfo
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- CN110108091B CN110108091B CN201910284132.4A CN201910284132A CN110108091B CN 110108091 B CN110108091 B CN 110108091B CN 201910284132 A CN201910284132 A CN 201910284132A CN 110108091 B CN110108091 B CN 110108091B
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- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
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Abstract
The invention provides a cryogenic liquefaction system with improved hydrogen separation membrane embedded aiming at a STAR propane dehydrogenation process, and belongs to the technical field of petrochemical industry. The system is from dehydrogenation toStarting from the composition characteristics of the product, a hydrogen membrane separation unit is introduced after a shallow cooling unit, most hydrogen is separated by utilizing the selective permeation of a membrane, and then the hydrogen is further pressurized and liquefied by deep cooling, and propane and propylene are further separated from the rest non-condensable components. By embedding the improved cryogenic liquefaction system in the hydrogen membrane separation unit, the compression load can be obviously reduced while high-concentration hydrogen is obtained, the total compression energy consumption can be reduced by 8-24%, the heat exchange load of the cryogenic unit can be reduced by 80-86%, the purity of the byproduct hydrogen can be improved to 99 mol% from 82 mol%, and the requirements of hydrogen consumption devices such as hydrocracking and the like in a refining enterprise are met. Under the optimal working condition, the 35 ten thousand tons of STAR process can save the compression energy consumption by 1020kW and produce qualified hydrogen 16198Nm3/h。
Description
Technical Field
The invention relates to a cryogenic liquefaction system with improved hydrogen separation membrane embedded aiming at a STAR propane dehydrogenation process, and belongs to the field of petrochemical industry. According to the process, a hydrogen membrane separation unit is embedded between a shallow cooling unit and a cryogenic unit, most hydrogen in reaction products is removed through selective permeation of a membrane, propane and propylene are subjected to non-phase-change concentration, the gas flow is greatly reduced, then pressurization and cryogenic liquefaction are further performed, and the compression energy consumption in the cryogenic liquefaction process is reduced while high-concentration hydrogen is obtained.
Background
Propylene is a basic raw material of three major synthetic materials, such as plastics, synthetic rubber and synthetic fibers. In addition, propylene is widely used for the production of acrylonitrile, isopropyl alcohol, acetone, propylene oxide, and the like. In 2018, the global propylene capacity exceeds 1.4 million tons, and the consumption amount exceeds 1 million tons. In the future 5-10 years, the annual average growth rate of the world propylene capacity and consumption is about 4-5%. The main production routes of propylene can be divided into three types, i.e., oil head (steam cracking, catalytic cracking), coal head (methanol to olefins), and gas head (propane dehydrogenation), according to the type of the raw material. In recent years, with the large-scale exploitation of shale gas resources on a global scale, the yield of propane is continuously increased, the price of the propane is reduced in a water-jumping manner, and the development and industrial application of the propane dehydrogenation process are greatly promoted. In 2018, the total yield of olefin production by propane dehydrogenation exceeds 1200 ten thousand tons, and the method is the most important new added source of propylene.
The technologies for producing propylene by propane dehydrogenation mainly include Oleflex process from UOP company, Catofin process from Lummus company, STAR process from wood company, and PDH process from lind company. Compared to other process technologies, the STAR process converts propane to propylene in two steps, steam reforming dehydrogenation and partial oxidative dehydrogenation, at higher reaction pressures (0.5MPaG), with relatively small reactor volumes and higher per pass conversions. Especially, in the partial oxidative dehydrogenation process, the coupling of hydrogen partial combustion and dehydrogenation reaction is adopted, so that the reaction process can be promoted, the heat required by the reaction can be provided, and the method has more remarkable advantages.
Besides the target product propylene, a large amount of hydrogen and methane are also produced in the propane dehydrogenation process. Due to the combustion consumption of hydrogen in the partial oxidative dehydrogenation process, the STAR process produces far less non-condensable components than other propane dehydrogenation processes. Even so, the STAR reaction product still contains a significant amount of non-condensable components. According to a typical 35 million ton STAR plant of a certain enterprise, the total content of non-condensable components (hydrogen, methane, oxygen, nitrogen, carbon monoxide) of the reaction product after removal of moisture and carbon dioxide is as high as 22.18 mol%. Subject to the existence of a large amount of non-condensable components, the traditional STAR process adopts a cryogenic liquefaction system, needs to be carried out under the conditions of high pressure and low temperature of 3.20MPaG and-78 ℃, and mainly has the following defects: 1) all gaseous reaction products need to be pressurized to 3.20MPaG from about 0.50 MPaG, and the compression energy consumption is very large; 2) the non-condensable components such as methane, nitrogen and the like coexist with hydrogen in the deep cooling process, the concentration of the byproduct crude hydrogen is lower than 90mol%, and the byproduct crude hydrogen cannot be directly used in typical hydrogen consumption processes in refining enterprises such as hydrocracking, hydrofining and the like, and is used as fuel to cause great waste. Taking a typical 35 ten thousand tons STAR propane dehydrogenation process as an example, the energy consumption for compressing dehydrogenation reaction products is up to 6400 kW; the by-product hydrogen is purified to above 99%, and assuming a recovery of 80%, about 1.15 million standard parts of hydrogen can be supplied to the refinery hydrotreater each year.
Hydrogen is the most predominant non-condensable component, based on the composition of a typical STAR propane dehydrogenation product, see table 1. A more efficient hydrogen separation technology is introduced, the high-pressure low-temperature liquefaction working condition is hopefully improved greatly by being coupled with the traditional liquefaction process, the compression power consumption is reduced by staged pressurization/condensation, and meanwhile, the high-concentration hydrogen is byproduct, and the product value is increased. Pressure swing adsorption and membrane separation are two separation technologies independent of the phase equilibrium relationship of separation objects, and are both widely used for hydrogen separation and purification. Compared with pressure swing adsorption, hydrogen membrane separation can concentrate condensation objects such as carbon three (propane and propylene) on the high-pressure retentate side, is beneficial to subsequent pressure rise and condensation liquefaction, and is more suitable for being combined with the STAR propane dehydrogenation process. In conclusion, the invention embeds the hydrogen membrane separation unit after the shallow cooling unit in the STAR propane dehydrogenation process, removes most hydrogen in reaction products through selective permeation, and then further pressurizes and cryogenically liquefies, thereby reducing the compression energy consumption in the cryogenically liquefying process while obtaining high-concentration hydrogen.
Disclosure of Invention
It is an object of the present invention to provide an improved cryogenic liquefaction system for hydrogen separation membrane insertion for the STAR propane dehydrogenation process. The process introduces a hydrogen membrane separation unit after a shallow cooling unit in the STAR propane dehydrogenation process, utilizes selective permeation of membranes to separate most of hydrogen in reaction products, and then further pressurizes and cryoliquefies to further separate carbon three (propane and propylene) from the remaining non-condensable components.
The technical scheme of the invention is as follows:
a cryogenic liquefaction system with improved hydrogen separation membrane embedded aiming at STAR propane dehydrogenation process, wherein a propane dehydrogenation reaction product S1 cooled to normal temperature enters a first cooler 2 after being pressurized by a first compressor 1, the temperature is reduced to normal temperature, and then the propane dehydrogenation reaction product enters a decarburization/dehydration system 13, and meanwhile, a decarburization absorbent S2 also enters the decarburization/dehydration system 13; five material outputs are generated in the decarburization/dehydration system 13, the decarburization absorbent rich liquid S3 and the condensed water S4 are sent out, the first light hydrocarbon condensed liquid S5 is sent to the deethanizer, the dehydrated recycle gas S6 is returned to the inlet of the first compressor 1, and the propane dehydrogenation reaction product S7 after decarburization and dehydration is sent to the first heat exchanger 6;
the decarbonized and dehydrated propane dehydrogenation reaction product S7 sequentially passes through a first heat exchanger 6, a second cooler 4 and a third cooler 7 to be cooled, then enters a first gas-liquid separation tank 9, a second light hydrocarbon condensate S8 is produced at the bottom of the tank, and a first non-condensable gas S9 is produced at the top of the tank;
the first non-condensable gas S9 sequentially passes through a second heat exchanger 14 and a heater 15 to be heated, and then enters a hydrogen membrane separation unit 16, membrane separation permeation gas S18 with concentrated hydrogen is obtained at a low-pressure side, the hydrogen concentration reaches over 99 mol%, membrane separation residual gas S19 with most of hydrogen removed is obtained at a high-pressure side, and the hydrogen concentration is lower than 25 mol% under proper operation pressure;
the membrane separation residual gas S19 is cooled to normal temperature by a fourth cooler 8, then enters a second compressor 3, enters a second heat exchanger 14 for precooling after secondary pressurization, then enters a fifth cooler 17 for further cooling, then enters a second gas-liquid separation tank 11, a third light hydrocarbon condensate S11 is produced at the bottom of the tank, and a second non-condensable gas S12 is produced at the top of the tank; the second non-condensable gas S12 and deethanizing overhead gas S14 are combined to enter a cooling box 10 for further deep cooling, then enter a third gas-liquid separation tank 18, a fourth light hydrocarbon condensate S15 is produced at the bottom of the tank, and a third non-condensable gas S16 is produced at the top of the tank;
the fourth light hydrocarbon condensate S15 is subjected to low-temperature cold recovery by the cold box 10, then is plied with the second light hydrocarbon condensate S8 and the third light hydrocarbon condensate S11, enters the first heat exchanger 6 to recover the low-temperature cold, and finally is sent to the deethanizer; the third non-condensable gas S16 passes through the cold box 10 to recover low-temperature cold, then enters the turbine refrigerating machine 12, and enters the cold box 10 again to recover the low-temperature cold after expansion and temperature reduction; the third noncondensable gas S16 is called as tail gas S17 of the propane dehydrogenation process after cold energy is fully recovered.
The invention has the beneficial effects that: a hydrogen membrane separation unit is embedded between a shallow cooling unit and a deep cooling unit, most hydrogen in reaction products is removed through selective permeation of a membrane, condensable components such as propane, propylene and the like are subjected to non-phase-change concentration, the gas flow is greatly reduced, then pressurization and deep cooling liquefaction are further performed, and the compression energy consumption in the deep cooling liquefaction process is remarkably reduced while high-concentration hydrogen is obtained. Taking a typical 35 ten thousand tons STAR propane dehydrogenation process as an example, a reaction product enters a hydrogen membrane separation unit after being subjected to shallow cooling operation at the temperature of 2.30MPaG and 24 ℃, membrane separation residual gas is subjected to cryogenic liquefaction under the conditions of 3.20MPaG and 78 ℃, the total compression energy consumption is reduced by 16.1%, the hydrogen purity is improved to 99.0mol% from 82.8 mol%, and the recovery rate exceeds 85%. The energy conservation and the hydrogen output are comprehensively considered, and the improved cryogenic liquefaction system embedded in the hydrogen separation membrane has obvious economic advantages.
Drawings
FIG. 1 is a cryogenic liquefaction system in a typical STAR propane dehydrogenation process.
Fig. 2 is a cryogenic liquefaction system with improved hydrogen separation membrane insertion for the STAR propane dehydrogenation process.
In the figure: 1 a first compressor; 2 a first cooler; 3 a second compressor; 4 a second cooler; 5 a decarbonization/dehydration system; 6, a first heat exchanger; 7 a third cooler; 8 a fourth cooler; 9 a first gas-liquid separation tank; 10, cooling the box; 11 a second knock-out pot; 12 a turbo-refrigerator; 13 a decarbonation/dehydration system; 14 a second heat exchanger; 15 a heater; 16 hydrogen membrane separation unit; 17 a fifth cooler; 18 a third knock-out pot; s1 cooled propane dehydrogenation reaction product; s2 decarburization absorbent; s3 decarburization absorbent pregnant solution; s4 condensing water; s5 a first light hydrocarbon condensate; s6 dehydrating the recycle gas; s7 decarbonizing and dehydrating the propane dehydrogenation reaction product; s8 second light hydrocarbon condensate; s9 first non-condensable gas; s10 deethanizing overhead gas; s11 third light hydrocarbon condensate; s12 second non-condensable gas; s13 propane dehydrogenation process tail gas; s14 deethanizing overhead gas; s15 fourth light hydrocarbon condensate; s16 a third non-condensable gas; s17 propane dehydrogenation process tail gas; s18 membrane separation permeation gas; and S19 membrane separation of residual gas.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Example 1 a typical 35 million tons of STAR process propane dehydrogenation reaction product of a certain enterprise is treated by a conventional cryogenic liquefaction system, and the corresponding technical scheme is described as follows:
the propane dehydrogenation reaction product S1 cooled to the normal temperature enters a first cooler 2 after being pressurized to 1.40MPaG by a first compressor 1, then enters a second cooler 4 after being further pressurized to 3.20MPaG by a second compressor 3, the temperature of the material is reduced to the normal temperature, and then enters a decarburization/dehydration system 5, and meanwhile, a decarburization absorbent S2 also enters the decarburization/dehydration system 5; five streams of materials are output in a decarburization/dehydration system 5, a decarburization absorbent rich liquid S3 and condensed water S4 are sent out, a first light hydrocarbon condensed liquid S5 is sent to a deethanizer, dehydrated cycle gas S6 is returned to an inlet of a first compressor 1, and a decarbonized and dehydrated propane dehydrogenation reaction product S7 is sent to a first heat exchanger 6;
the decarbonized and dehydrated propane dehydrogenation reaction product S7 sequentially passes through a first heat exchanger 6, a third cooler 7 and a fourth cooler 8 to be cooled, then enters a first gas-liquid separation tank 9, a second light hydrocarbon condensate S8 is produced at the bottom of the tank, and a first non-condensable gas S9 is produced at the top of the tank; the first non-condensable gas S9 and deethanizing overhead gas S10 are combined to enter a cooling box 10 for further deep cooling, then enter a second gas-liquid separation tank 11, a third light hydrocarbon condensate S11 is produced at the bottom of the tank, and a second non-condensable gas S12 is produced at the top of the tank;
the third light hydrocarbon condensate S11 is subjected to low-temperature cold recovery by the cold box 10, then is plied with the second light hydrocarbon condensate S8, enters the first heat exchanger 6 to recover the medium-low-temperature cold, and finally is sent to the deethanizer; the second non-condensable gas S12 passes through the cold box 10 to recover low-temperature cold, then enters the turbine refrigerating machine 12, and enters the cold box 10 again to recover the low-temperature cold after expansion and temperature reduction; the second noncondensable gas S12 is called as tail gas S13 of the propane dehydrogenation process after cold energy is fully recovered.
In this embodiment, the power consumption of the first compressor 1 and the second compressor 3 is the most dominant utility consumption, total installed power 6350 kW. The cold box 10 is the most critical cold exchange equipment, and the condensation amount of light hydrocarbon in the cold box reaches 5782 kg/h. The concentration of the by-product hydrogen is only 82.82 mol%, and the by-product hydrogen cannot be directly used in hydrogen consumption devices such as hydrocracking of refining enterprises.
Example 2
as shown in fig. 2, the propane dehydrogenation reaction product S1 cooled to the normal temperature is pressurized to 1.90MPaG by the first compressor 1, enters the first cooler 2, is cooled to the normal temperature, and then enters the decarburization/dehydration system 13, and at the same time, the decarburization absorbent S2 also enters the decarburization/dehydration system 13; five streams of materials are output in the decarburization/dehydration system 13, the decarburization absorbent rich liquid S3 and the condensed water S4 are sent out, the first light hydrocarbon condensed liquid S5 is sent to the deethanizer, the dehydrated circulating gas S6 is returned to the inlet of the first compressor 1, and the decarbonized and dehydrated propane dehydrogenation reaction product S7 is sent to the first heat exchanger 6;
the decarbonized and dehydrated propane dehydrogenation reaction product S7 sequentially passes through a first heat exchanger 6, a second cooler 4 and a third cooler 7 to be cooled, then enters a first gas-liquid separation tank 9, a second light hydrocarbon condensate S8 is produced at the bottom of the tank, and a first non-condensable gas S9 is produced at the top of the tank; the first non-condensable gas S9 sequentially passes through a second heat exchanger 14 and a heater 15 to be heated, and then enters a hydrogen membrane separation unit 16, membrane separation permeation gas S18 with concentrated hydrogen is obtained at the low-pressure side, the hydrogen concentration reaches over 99 mol%, membrane separation residual gas S19 with most of hydrogen removed is obtained at the high-pressure side, and the hydrogen concentration is lower than 35 mol%;
the membrane separation residual gas S19 is cooled to normal temperature by a fourth cooler 8, then enters a second compressor 3, is secondarily pressurized to 3.20MPaG, enters a second heat exchanger 14 for precooling, then enters a fifth cooler 17 for further cooling, then enters a second gas-liquid separation tank 11, a third light hydrocarbon condensate S11 is produced at the bottom of the tank, and a second non-condensable gas S12 is produced at the top of the tank; the second non-condensable gas S12 and deethanizing overhead gas S14 are combined to enter a cooling box 10 for further deep cooling, then enter a third gas-liquid separation tank 18, a fourth light hydrocarbon condensate S15 is produced at the bottom of the tank, and a third non-condensable gas S16 is produced at the top of the tank;
the fourth light hydrocarbon condensate S15 is subjected to low-temperature cold recovery by the cold box 10, then is plied with the second light hydrocarbon condensate S8 and the third light hydrocarbon condensate S11, enters the first heat exchanger 6 to recover the low-temperature cold, and finally is sent to the deethanizer; the third non-condensable gas S16 passes through the cold box 10 to recover low-temperature cold, then enters the turbine refrigerating machine 12, and enters the cold box 10 again to recover the low-temperature cold after expansion and temperature reduction; the third noncondensable gas S16 is called as tail gas S17 of the propane dehydrogenation process after cold energy is fully recovered.
In this embodiment, the power consumption of the first compressor 1 and the second compressor 3 is the most significant utility consumption, with a total installed power of 4820 kW, a 24% savings over the conventional cryogenic liquefaction system of example 1. The cold box 10 is the most critical cold exchange equipment, the condensation amount of light hydrocarbon is 1115 kg/h, and compared with the traditional cryogenic liquefaction system in the embodiment 1, the load is reduced by 80.7%. The concentration of the hydrogen produced by the membrane separation reaches 99.0mol percent, the requirements of hydrogen consumption devices in the refinery, hydrocracking and the like are met, the recovery rate of the hydrogen reaches 83.7 percent, and the yield of the hydrogen is 15159 Nm3/h。
Example 3
as shown in fig. 2, the propane dehydrogenation reaction product S1 cooled to the normal temperature is pressurized to 2.30MPaG by the first compressor 1, enters the first cooler 2, is cooled to the normal temperature, and then enters the decarburization/dehydration system 13, and at the same time, the decarburization absorbent S2 also enters the decarburization/dehydration system 13; five streams of materials are output in the decarburization/dehydration system 13, the decarburization absorbent rich liquid S3 and the condensed water S4 are sent out, the first light hydrocarbon condensed liquid S5 is sent to the deethanizer, the dehydrated circulating gas S6 is returned to the inlet of the first compressor 1, and the decarbonized and dehydrated propane dehydrogenation reaction product S7 is sent to the first heat exchanger 6;
the decarbonized and dehydrated propane dehydrogenation reaction product S7 sequentially passes through a first heat exchanger 6, a second cooler 4 and a third cooler 7 to be cooled, then enters a first gas-liquid separation tank 9, a second light hydrocarbon condensate S8 is produced at the bottom of the tank, and a first non-condensable gas S9 is produced at the top of the tank; the first non-condensable gas S9 sequentially passes through a second heat exchanger 14 and a heater 15 to be heated, and then enters a hydrogen membrane separation unit 16, membrane separation permeation gas S18 with concentrated hydrogen is obtained at the low-pressure side, the hydrogen concentration reaches over 99 mol%, membrane separation residual gas S19 with most of hydrogen removed is obtained at the high-pressure side, and the hydrogen concentration is lower than 25 mol%;
the membrane separation residual gas S19 is cooled to normal temperature by a fourth cooler 8, then enters a second compressor 3, is subjected to secondary pressurization to 3.20MPaG, then enters a second heat exchanger 14 for precooling, then enters a fifth cooler 17 for further cooling, then enters a second gas-liquid separation tank 11, third light hydrocarbon condensate S11 is produced at the bottom of the tank, and second non-condensable gas S12 is produced at the top of the tank; the second non-condensable gas S12 and deethanizing overhead gas S14 are combined to enter a cooling box 10 for further deep cooling, then enter a third gas-liquid separation tank 18, a fourth light hydrocarbon condensate S15 is produced at the bottom of the tank, and a third non-condensable gas S16 is produced at the top of the tank;
the fourth light hydrocarbon condensate S15 is subjected to low-temperature cold recovery by the cold box 10, then is plied with the second light hydrocarbon condensate S8 and the third light hydrocarbon condensate S11, enters the first heat exchanger 6 to recover the low-temperature cold, and finally is sent to the deethanizer; the third non-condensable gas S16 passes through the cold box 10 to recover low-temperature cold, then enters the turbine refrigerating machine 12, and enters the cold box 10 again to recover the low-temperature cold after expansion and temperature reduction; the third noncondensable gas S16 is called as tail gas S17 of the propane dehydrogenation process after cold energy is fully recovered.
In this embodiment, the power consumption of the first compressor 1 and the second compressor 3 is the most significant utility consumption, and the total installed power is 5330 kW, which is a 16% savings over the conventional cryogenic liquefaction system of example 1. The cold box (15) is the most critical cold exchange equipment, the condensation amount of light hydrocarbon is 799 kg/h, and compared with the traditional cryogenic liquefaction system in the embodiment 1, the load is reduced by 86.2 percent. The concentration of the hydrogen generated by the membrane separation reaches 99.0mol percent, the requirements of hydrogen consumption devices in the refinery, hydrocracking and the like are met, the recovery rate of the hydrogen reaches 86.0 percent, and the yield of the hydrogen is 16198Nm3/h。
Example 4
as shown in fig. 2, the propane dehydrogenation reaction product S1 cooled to the normal temperature is pressurized to 2.70MPaG by the first compressor 1, enters the first cooler 2, is cooled to the normal temperature, and then enters the decarburization/dehydration system 13, and at the same time, the decarburization absorbent S2 also enters the decarburization/dehydration system 13; five streams of materials are output in the decarburization/dehydration system 13, the decarburization absorbent rich liquid S3 and the condensed water S4 are sent out, the first light hydrocarbon condensed liquid S5 is sent to the deethanizer, the dehydrated circulating gas S6 is returned to the inlet of the first compressor 1, and the decarbonized and dehydrated propane dehydrogenation reaction product S7 is sent to the first heat exchanger 6;
the decarbonized and dehydrated propane dehydrogenation reaction product S7 sequentially passes through a first heat exchanger 6, a second cooler 4 and a third cooler 7 to be cooled, then enters a first gas-liquid separation tank 9, a second light hydrocarbon condensate S8 is produced at the bottom of the tank, and a first non-condensable gas S9 is produced at the top of the tank; the first non-condensable gas S9 sequentially passes through a second heat exchanger 14 and a heater 15 to be heated, and then enters a hydrogen membrane separation unit 16, membrane separation permeation gas S18 with concentrated hydrogen is obtained at the low-pressure side, the hydrogen concentration reaches over 99 mol%, membrane separation residual gas S19 with most of hydrogen removed is obtained at the high-pressure side, and the hydrogen concentration is lower than 22 mol%;
the membrane separation residual gas S19 is cooled to normal temperature by a fourth cooler 8, then enters a second compressor 3, is subjected to secondary pressurization to 3.20MPaG, then enters a second heat exchanger 14 for precooling, then enters a fifth cooler 17 for further cooling, then enters a second gas-liquid separation tank 11, third light hydrocarbon condensate S11 is produced at the bottom of the tank, and second non-condensable gas S12 is produced at the top of the tank; the second non-condensable gas S12 and deethanizing overhead gas S14 are combined to enter a cooling box 10 for further deep cooling, then enter a third gas-liquid separation tank 18, a fourth light hydrocarbon condensate S15 is produced at the bottom of the tank, and a third non-condensable gas S16 is produced at the top of the tank;
the fourth light hydrocarbon condensate S15 is subjected to low-temperature cold recovery by the cold box 10, then is plied with the second light hydrocarbon condensate S8 and the third light hydrocarbon condensate S11, enters the first heat exchanger 6 to recover the low-temperature cold, and finally is sent to the deethanizer; the third non-condensable gas S16 passes through the cold box 10 to recover low-temperature cold, then enters the turbine refrigerating machine 12, and enters the cold box 10 again to recover the low-temperature cold after expansion and temperature reduction; the third noncondensable gas S16 is called as tail gas S17 of the propane dehydrogenation process after cold energy is fully recovered.
In this embodiment, the power consumption of the first compressor 1 and the second compressor 12 is the most significant utility consumption, 6230kW total installed power, which is 8% less than the conventional cryogenic liquefaction system of example 1. The cold box (15) is the most critical cold exchange equipment, the condensation amount of light hydrocarbon is 799 kg/h, and compared with the traditional cryogenic liquefaction system in the embodiment 1, the load is reduced by 86.2 percent. Concentration of hydrogen produced by membrane separationThe degree reaches 99.0mol%, the requirements of hydrogen consumption devices in the refinery, such as hydrocracking and the like are met, the hydrogen recovery rate reaches 87.2%, and the hydrogen yield is 16356 Nm3/h。
Claims (1)
1. A cryogenic liquefaction system with improved hydrogen separation membrane intercalation for STAR propane dehydrogenation process is characterized in that,
the propane dehydrogenation reaction product (S1) cooled to the normal temperature enters a first cooler (2) after being pressurized by a first compressor (1), the temperature is reduced to the normal temperature, and then the propane dehydrogenation reaction product enters a decarburization/dehydration system (13), and meanwhile, a decarburization absorbent (S2) also enters the decarburization/dehydration system (13); five streams of materials are output in a decarburization/dehydration system (13), a decarburization absorbent rich liquid (S3) and condensed water (S4) are sent out, a first light hydrocarbon condensate liquid (S5) is sent to a deethanizer, dehydrated cycle gas (S6) returns to an inlet of a first compressor (1), and a propane dehydrogenation reaction product (S7) after decarburization and dehydration is sent to a first heat exchanger (6);
the decarbonized and dehydrated propane dehydrogenation reaction product (S7) sequentially passes through a first heat exchanger (6), a second cooler (4) and a third cooler (7) to be cooled, then enters a first gas-liquid separation tank (9), a second light hydrocarbon condensate (S8) is produced at the bottom of the tank, and a first non-condensable gas (S9) is produced at the top of the tank;
the first non-condensable gas (S9) sequentially passes through a second heat exchanger (14) and a heater (15) to be heated, then enters a hydrogen membrane separation unit (16), membrane separation permeation gas with concentrated hydrogen is obtained at a low-pressure side (S18), the hydrogen concentration reaches over 99 mol%, membrane separation permeation residual gas with most of hydrogen removed is obtained at a high-pressure side (S19), and the hydrogen concentration is lower than 25 mol% under proper operating pressure;
the membrane separation residual gas (S19) is cooled to normal temperature by a fourth cooler (8), then enters a second compressor (3), enters a second heat exchanger (14) for precooling after secondary pressurization, then enters a fifth cooler (17) for further cooling, then enters a second gas-liquid separation tank (11), third light hydrocarbon condensate (S11) is produced at the bottom of the tank, and second non-condensable gas (S12) is produced at the top of the tank; the second non-condensable gas (S12) and deethanizer overhead gas (S14) are combined and enter a cooling box (10) for further deep cooling, then enter a third gas-liquid separation tank (18), fourth light hydrocarbon condensate (S15) is produced at the bottom of the tank, and third non-condensable gas (S16) is produced at the top of the tank;
the fourth light hydrocarbon condensate (S15) is subjected to low-temperature cold recovery by a cold box (10), then is combined with the second light hydrocarbon condensate (S8) and the third light hydrocarbon condensate (S11), enters a first heat exchanger (6) to recover medium-low-temperature cold, and finally is sent to a deethanizer; the third non-condensable gas (S16) passes through the cold box (10) to recover low-temperature cold energy, then enters the turbine refrigerating machine (12), and enters the cold box (10) again to recover the low-temperature cold energy after expansion and temperature reduction; the third noncondensable gas (S16) is called as tail gas of the propane dehydrogenation process (S17) after cold energy is fully recovered.
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| US5243122A (en) * | 1991-12-30 | 1993-09-07 | Phillips Petroleum Company | Dehydrogenation process control |
| DE102004061772A1 (en) * | 2004-12-22 | 2006-07-06 | Basf Ag | Process for the preparation of propene from propane |
| US8013201B2 (en) * | 2008-07-30 | 2011-09-06 | Lummus Technology Inc. | High energy reduction in a propane dehydrogenation unit by utilizing a high pressure product splitter column |
| DE102009034464A1 (en) * | 2009-07-22 | 2011-08-18 | Uhde GmbH, 44141 | Process and apparatus for the dehydrogenation of alkanes with a homogenization of the product composition |
| CN102795956B (en) * | 2012-08-30 | 2015-01-07 | 惠生工程（中国）有限公司 | Method for separating reaction products produced during preparation of propylene by dehydrogenating propane |
| CN105439793B (en) * | 2015-12-08 | 2017-12-05 | 杭州杭氧股份有限公司 | A kind of ice chest low temperature separating methods for PDH projects |
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2019
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