CN115959683A - Cold-heat-kinetic energy complementary process and system for refining liquid hydrogen and liquid nitrogen and coproducing synthetic ammonia - Google Patents
Cold-heat-kinetic energy complementary process and system for refining liquid hydrogen and liquid nitrogen and coproducing synthetic ammonia Download PDFInfo
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- CN115959683A CN115959683A CN202111176081.7A CN202111176081A CN115959683A CN 115959683 A CN115959683 A CN 115959683A CN 202111176081 A CN202111176081 A CN 202111176081A CN 115959683 A CN115959683 A CN 115959683A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 467
- 239000001257 hydrogen Substances 0.000 title claims abstract description 350
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 350
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 294
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 219
- 239000007788 liquid Substances 0.000 title claims abstract description 168
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 82
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
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- 239000000047 product Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 238000007710 freezing Methods 0.000 claims abstract description 26
- 230000008014 freezing Effects 0.000 claims abstract description 26
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- 238000003860 storage Methods 0.000 claims description 55
- 239000002994 raw material Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 150000002431 hydrogen Chemical group 0.000 claims description 25
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 201000009240 nasopharyngitis Diseases 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
A process and a system for refining liquid hydrogen and liquid nitrogen to coproduce synthetic ammonia by cold-heat-kinetic energy complementation. By using periodic green and peak-staggered electric energy, hydrogen is produced by electrolyzing water and stored in a deep cooling and liquefying manner in a valley period of a power grid every day, and refined liquid hydrogen with the parahydrogen content of 97.2-99.2% and synthetic ammonia products are continuously processed 24 hours every day. The method comprises the steps of boosting liquefied hydrogen to a supercritical refrigerant, carrying out deep cooling refining on a liquid hydrogen product and refined liquid nitrogen in sequence in a temperature range of 24K to 270K, and then carrying out freezing reverse separation to synthesize a reaction product; finally, as a reactant, hydrogen/nitrogen is used for catalytically synthesizing ammonia. The prepared synthetic ammonia is firstly used as the expander working medium to recover the process heat energy and heat power-conversion, and then condensed into a liquid ammonia product to be output. Energy cascade utilization combined production efficiency: the unit consumption of refined liquid hydrogen kg is 53.95kWh (valley period); the unit consumption of synthetic ammonia per ton is 9519kWh of power consumption for hydrogen production (valley period) plus 393.5kWh of power consumption for ammonia production (full period).
Description
Technical Field
The invention relates to a hydrogen energy processing and utilization technology, a cryogenic cooling and air separation technology, a synthetic ammonia manufacturing technology and a heat energy-power conversion and industrial energy-saving technology, in particular to the cross-industry technical field of efficiently and economically utilizing green electric energy to replace fossil energy to manufacture energy chemicals.
Background
By green colourThe production of energy chemicals (including hydrogen and synthetic ammonia) by replacing fossil energy with electric energy is an important technological and economic route for reducing carbon and emission, and is more and more concerned by the whole world and the whole society. The core problem to be solved from the perspective of marketization is the safety, reliability, economy and high efficiency of hydrogen energy. For example, the electrolytic water hydrogen production reaches 4.3kWh/m 3 The energy consumption level of the method is advanced, but the method is limited by the power supply price, large-scale replacement of fossil energy is not achieved economically, the fossil energy is directly supplied to the market, and the acceptable cost is difficult to replace the fossil raw material to manufacture energy chemicals such as synthetic ammonia (he invented et al. Natural gas pyrolysis hydrogen production and water electrolysis hydrogen production process characteristics are compared, fertilizer design is 2020, 2/58: 5-9.). In addition, the volume energy-carrying density of hydrogen is low, and the problem that the hydrogen is remotely transported to the market of users from a hydrogen production place in a way of cryogenic processing into liquid hydrogen products and the like is also a process with high energy consumption (invar and the like, hydrogen liquefaction process design and optimization method research progress, refrigeration bulletin, 2020, 3/41: 1-10.). Liquid hydrogen products are processed in a cryogenic temperature region of 20 to 30K (-253 to-243 ℃), not only high-grade cold energy is consumed to remove liquefaction heat (452 kJ/kg), but also ortho-para state hydrogen conversion reaction heat (670 kJ/kg) with larger decomposition ratio is consumed, so that common hydrogen (originally containing more than 70 percent of normal hydrogen) prepared in various industrial processes can be converted into para state liquid hydrogen stable at low temperature, and ortho-para state conversion is not generated, so that vaporization loss caused by the ortho-para state conversion reaction in the liquid hydrogen storage and transportation process is avoided. Therefore, all standards of liquid hydrogen products at home and abroad strictly require that the liquid hydrogen product contains over 95-98% of parastate hydrogen, for example, GB/T40061-2021 technical Specification of liquid hydrogen production System requires that the liquid hydrogen product contains the parastate hydrogen>95% of the liquid hydroprocessing processes must accordingly complete the ortho-para conversion reaction at equilibrium temperatures below 33K; the higher the level of secondary hydrogen required, the lower the corresponding liquid hydroprocessing temperature, and obviously the higher the refrigeration energy consumption. To seek to reduce the cryogenic energy consumption from the liquid hydroprocessing process itself, in the temperature region below 33K, the technical and economic feasibility is not great. The technical idea of the invention is that common hydrogen liquefaction and normal-secondary state conversion are carried out in a segmented manner; and the liquefied common hydrogen is divided into two parts, one part is converted into liquid hydrogen product through positive-secondary state conversion, and the other part is used as cryogenic working mediumPressurizing to a supercritical state in a liquid state, utilizing the super-large cold capacity and pressure energy contained in the liquid state, firstly serving as a primary hydrogen refrigerant to provide cold energy for refined liquid hydrogen, then serving as a secondary hydrogen refrigerant for producing liquid nitrogen by cryogenic air separation, and continuing serving as tertiary and quaternary hydrogen refrigerants for a freezing ammonia separation process of an ammonia synthesis process through catalytic reaction of hydrogen and nitrogen, wherein the temperature of the hydrogen refrigerant is higher than that of the primary hydrogen refrigerant, and finally serving as a synthetic ammonia raw material hydrogen to carry all heat absorbed in the 4-stage refrigeration process to enter a synthetic ammonia process ring. The invention provides a process and a system for co-producing synthetic ammonia by refining liquid hydrogen and liquid nitrogen with complementary cold-heat-kinetic energy, wherein the hydrogen production and hydrogen liquefaction process by water electrolysis with high power consumption is carried out in the power grid power supply valley period, the liquid hydrogen production and synthetic ammonia processing by air separation with low power consumption are continuously carried out in the whole time period and long period, the isentropic efficiency of a compressor and an expander is 0.8, and the whole power consumption is distributed to a liquid hydrogen product (with the temperature of 24.5 to 29K and the content of parahydrogen of 97.2 to 99.2 percent) and a synthetic ammonia product: the unit consumption of electricity for hydrogen liquefaction (valley period) is less than 5.782kWh/kg, and the unit consumption of electricity for synthetic ammonia processing (whole period) is less than 393.5 kWh/ton ammonia.
Disclosure of Invention
The invention discloses a process and a system for co-producing synthetic ammonia by refining liquid hydrogen and liquid nitrogen through cold-heat-kinetic energy complementation. The invention is suitable for green (water, wind and light) areas with abundant power resources, in particular to places with large periodic variation amplitude of power load, the processes of hydrogen production and hydrogen liquefaction by water electrolysis are operated in the valley period of the power load (the valley period of power supply of a power grid), the prepared common liquid hydrogen is stored in a liquid hydrogen tank and is divided into two parts for processing liquid hydrogen products and synthetic ammonia products refined in the whole time period, the power consumption cost of the hydrogen production in the valley period of the power grid is reduced by times along with the peak-valley power price ratio, and meanwhile, the stable hydrogen supply is ensured in the two long-period continuous operation processes of positive-state catalytic conversion refined liquid hydrogen and hydrogen/nitrogen catalytic synthesis ammonia in the whole time period. By adopting the method, the sum of the hydrogen production unit consumption by electrolyzing water and the hydrogen liquefaction unit consumption is 53.95kWh/kg, the electricity price at the valley period is 0.25 yuan/kWh, the electricity consumption cost of liquid hydrogen is 13.49 yuan/kg, and the method has market competitiveness; the unit consumption of liquid hydrogen for processing synthetic ammonia by taking liquid hydrogen as a raw material is 176.5 kg/ton ammonia, the reduced trough power consumption is 9520 kWh/ton ammonia, the full-time power consumption allocated by synthetic ammonia processing is 393.5 kWh/ton ammonia, and the power consumption cost of full-electric ammonia production is 2635.6 yuan/ton ammonia calculated by the full-time power price of 0.65 yuan/kWh, so that the market competitiveness is realized.
As shown in figure 1, a method and a process system for refining liquid hydrogen are disclosed, wherein a raw material hydrogen compressor 1 pressurizes raw material hydrogen with the pressure of 0.12 to 0.25MPa (absolute pressure, the same below) and the temperature of 5 to 35 ℃ to 0.4 to 0.8MPa, the waste heat of the compressed hydrogen is recovered to ensure that the temperature is not higher than 50 ℃, and then the waste heat of the compressed hydrogen is subjected to dehydration purification combination 2, water cooling medium circulation cooling is used for cooling to 5 to 25 ℃, condensed water is separated, and adsorption purification is carried out until the total impurity content is not more than 0.2 x 10 -4 v%, cooling the mixture to an absolute temperature of not higher than 83K by using a nitrogen cooling medium through a raw material hydrogen and nitrogen cooler 3 in a circulating manner, further cooling the mixture to a temperature of not higher than 31K through a raw material hydrogen and nitrogen cooler 4, then feeding the cooled mixture into a raw material hydrogen liquefier 5, performing heat release condensation at a temperature of not higher than 30K to obtain liquid hydrogen, then performing adiabatic expansion through a raw material hydrogen expander 6 to obtain a gas-liquid two-phase common hydrogen mixture with a pressure of 0.11 to 0.25MPa, a temperature of 20.5 to 24.0K and a dryness of not higher than 0.15, feeding the gas-liquid two-phase common hydrogen mixture into a common hydrogen intermediate product storage tank 7, homogenizing, buffering and transiting the mixture to be taken as a refrigerant, leading out the refrigerant through 5 and 4 endothermic vaporization and heating to a temperature of not higher than 81K, the compressed waste heat is absorbed by a refrigerant heat collector 13 and the temperature is raised to 273-295K, then the compressed waste heat is sucked into a refrigerant hydrogen compressor 14 to be pressurized to 1.8-2.5MPa and the temperature is raised to 513-535K, then the heat is released and cooled to not higher than 330K by a refrigerant ammonia cooler 15, the heat is released and cooled to not higher than 300K by a refrigerant water cooler 16, the heat is released and cooled to not higher than 83K by the refrigerant heat collector 13, the heat is released and cooled to not higher than 34K by a refrigerant hydrogen cooler 17, finally the gas-liquid two-phase common hydrogen mixture with the pressure of 0.11-0.25MPa, the temperature of 20.5-24.0K and the dryness of not more than 0.15 is adiabatically expanded by a refrigerant hydrogen expander 27 and returns to a common hydrogen product storage tank 7, and the composition of the normal hydrogen and the secondary hydrogen is as follows: ortho-hydrogen is higher than 70% and para-hydrogen is lower than 30%. The cooling capacity required by the refrigerant hydrogen cooler 17 is provided by an auxiliary hydrogen refrigerant with the outlet pressure of 0.8 to 1.0MPa and the temperature of 30 to 32K of an auxiliary hydrogen expander 18; the mass flow rate of the hydrogen supplement refrigerant circulation is not less than 1.60 times of the mass flow rate of the raw material hydrogen, the refrigerant hydrogen cooler 17 absorbs heat and is heated to be not more than 81K, then the refrigerant hydrogen cooler 19 absorbs heat and is heated to 273-295K, the refrigerant hydrogen is sucked into the hydrogen supplement compressor 20 and is pressurized to 12-15MPa, and the refrigerant hydrogen is cooled to be not more than the mass flow rate of the raw material hydrogen by the heat release of the hydrogen supplement ammonia cooler 21 at the temperature of 513-535K330K, the heat release of rethread auxiliary hydrogen water cooler 22 is cooled down to and is not higher than 300K, continues to release heat through auxiliary hydrogen heat collector 19 and cools down to and is not higher than 110K, cools down to and is not higher than 82K through auxiliary hydrogen nitrogen cooler 29, gets into auxiliary hydrogen expander 18, constitutes the auxiliary hydrogen refrigerant closed cycle. An ammonia expansion machine 25, a refrigerant ammonia condensation storage tank 9, a liquid ammonia booster pump 23 and a refrigerant ammonia cooler 15 form a cold/heat/kinetic conversion chain of refrigerant hydrogen, wherein the ammonia expansion machine 25 enables supercritical ammonia which is heated to the temperature of not more than 535K through the refrigerant ammonia cooler 15 to adiabatically expand from 12 to 169pa until the pressure is not lower than 0.8MPa, the supercritical ammonia enters the refrigerant ammonia condensation storage tank 9 and is cooled and liquefied by a water cooling medium, then the supercritical ammonia is pressurized to 12 to 169pa through the liquid ammonia booster pump 23 and enters the cold/heat/kinetic conversion chain of the refrigerant hydrogen for closed circulation, and the mass flow of the circulating ammonia is not less than 2.64 times of the mass flow of the raw material hydrogen. The cold/heat/dynamic conversion chain of the hydrogen-assisted refrigerant is formed by an ammonia expansion machine 26, a refrigerant ammonia condensation storage tank 9, a liquid ammonia pressure pump 24 and a hydrogen-assisted ammonia cooler 21, wherein the ammonia expansion machine 26 enables supercritical ammonia heated to the temperature of not more than 535K by the hydrogen-assisted ammonia cooler 21 to be adiabatically expanded from 12 to 169mpa to the pressure of not less than 0.8MPa, the supercritical ammonia enters the shared refrigerant ammonia condensation storage tank 9 and is cooled and liquefied by a water-cooling medium, then the supercritical ammonia is pressurized to 12 to 169mpa by the liquid ammonia pressure pump 24 and enters the cold/heat/dynamic conversion chain of the hydrogen-assisted refrigerant for closed circulation, and the mass flow of the circulating ammonia is not less than 4.40 times of the mass flow of the raw material hydrogen.
Liquid ordinary hydrogen with the pressure of 0.11 to 0.25MPa and the temperature of 20.5 to 24.0K in the storage tank 7 is pressurized to 0.8 to 0.9MPa by a primary liquid hydrogen pump 11 to be used as a primary hydrogen refrigerant, and the primary hydrogen refrigerant is heated to be not higher than 31K in a cold pipe of a hydrogen refining combination 10 consisting of a catalytic conversion section and a liquefaction section, and then is pressurized to be 4.0 to 6.0MPa by a secondary liquid hydrogen pump 110 to be returned to the combination 10 to be continuously heated to be not higher than 60K to be used as a supercritical secondary hydrogen refrigerant for output. Drawing a common hydrogen gas-liquid two-phase mixture (dryness is 0-0.95) with the pressure of 0.11-0.25MPa and the temperature of 20.5-24.0K in a storage tank 7 by a hydrogen refining pressurizer 12, performing endothermic vaporization in a combined 10 cold tube, raising the temperature to no more than 78K, then pressurizing to 0.3-0.7MPa and raising the temperature to 128-158K, cooling to below 82K by a hydrogen conversion nitrogen cooler 28, returning to a combined 10 hydrogen conversion catalyst particle layer for performing a refining process of converting the normal hydrogen into the secondary hydrogen, and transferring conversion heat to a 31-60K primary hydrogen refrigerant flowing in the tube and the common hydrogen gas-liquid two-phase mixture (0.11-0.25MPa-0.11 MPa) with the endothermic vaporization below 78K through a cooling tube wall distributed on the catalyst particle layer to perform heat conversion. The temperature of hydrogen at the end of the refining reaction is 24.5 to 29K, the composition of parahydrogen is 97.2 to 99.2%, the refined hydrogen releases heat to the outer surface of a cooling pipe with the outer wall temperature of 21 to 27K through a liquefying section of a combination 10 and is condensed, and then the refined hydrogen is stored in a refined liquid hydrogen product storage tank 8 with the pressure not higher than 0.7MPa and the temperature not higher than 29K. The mass flow ratio of the primary or supercritical secondary hydrogen refrigerant to the refined liquid hydrogen product is not less than 1.0.
As shown in attached figure 2, a method and a process system for producing liquid nitrogen are disclosed, wherein a secondary hydrogen refrigerant with a supercritical pressure of 4.0-6.0 MPa and a temperature of not higher than 60K is subjected to heat absorption and temperature rise to be not lower than 78K through a liquid nitrogen condenser combination 30 arranged at the top of an upper tower 31 of an air separation rectification tower, then is subjected to adiabatic expansion and temperature reduction to be not lower than 58K outside the tower, enters the condenser combination again to absorb heat to be not lower than 78K and then is subjected to adiabatic expansion and temperature reduction to be not lower than 58K outside the tower, the processes are repeated for at least 3 times, and the 58-78K cold energy of not less than 980kJ/kg-H is provided for the condenser combination 30 2 And the refrigerant is continuously output to the synthesis gas freezing ammonia separation combination 42 as a tertiary hydrogen refrigerant until the pressure of the refrigerant is reduced to be not lower than 0.35MPa and the temperature is not higher than 78K. The upper tower condensation combination 30 of the air separation tower utilizes the cold energy provided by the secondary hydrogen refrigerant to obtain the pure liquid nitrogen capacity (based on the hydrogen of the refrigerant of unit mass) of not less than 2.4kg-N with the pressure of not less than 0.137MPa, the temperature of not less than 80K, the concentration of more than 99.99 percent 2 /kg-H 2 And ensures that the reflux ratio of the rectifying tower operation is not less than 1.2. Through the evaporation-condenser connecting the tower bottom of the upper tower 31 of the air separation tower and the tower top of the lower tower 32 of the air separation rectification tower, oxygen-enriched gas (O) with the oxygen concentration not lower than 95.5v%, the temperature not higher than 93K and the pressure not higher than 0.145MPa is generated at the bottom of the upper tower 2+ ) Not less than 1.45kg-O 2+ /kg-H 2 After leaving the tower, the oxygen-enriched air passes through the oxygen-enriched air recooling device 40 to absorb the heat of the air entering the tower, and the temperature is raised to be not lower than 290K to be output to the system; simultaneously, pure liquid nitrogen with the pressure not lower than 0.50MPa, the temperature not lower than 94K and the concentration higher than 99.99 percent (v percent) is obtained at the lower tower top, and the capacity (based on the unit mass of the refrigerant hydrogen) of the pure liquid nitrogen is not less than 2.3kg-N 2 /kg-H 2 (ii) a The liquid nitrogen generated at the top of the upper tower is stored in a liquid nitrogen storage tank 35The top of the storage tank is lower than the bottom of the upper tower of the air separation rectifying tower, and the gas phase pressure of the storage tank is balanced with the gas phase pressure of the top of the upper tower of the air separation rectifying tower through a balance pipe; the liquid nitrogen produced at the bottom of the column passes through a liquid nitrogen expansion valve 34 and is stored in a liquid nitrogen storage tank 35. The liquid nitrogen in the storage tank 35 is pressurized to supercritical cold nitrogen with the operating pressure 0.3-0.5 MPa higher than that of the ammonia synthesis tower 45 and the temperature not more than 90K by a liquid nitrogen pressurization pump 36, firstly, the liquid nitrogen is used as a primary nitrogen refrigerant, the air entering the tower is cooled to the temperature not higher than 105K by a cold nitrogen recooler 41, the temperature of the primary nitrogen refrigerant is raised to not higher than 200K, and the liquid nitrogen is continuously used as a secondary nitrogen refrigerant and enters a synthesis gas freezing ammonia separation combination 42. The air of the raw material needed by air separation is pressurized to 0.5 to 0.8MPa by an air compressor 37, heated to 180 to 200 ℃, released and cooled to be not less than 60 ℃ by a compression heat recoverer 38, and cooled to be not more than 300K by an air dehydration/purification combination 39, and the total impurity content is not more than 0.2 multiplied by 10 -4 And v%, continuously cooling to 260K or below through the oxygen-enriched gas recooler 40, cooling to 105K or below through the cold nitrogen recooler 41, entering the air separation lower tower 32 for rectification and separation, obtaining a pure liquid nitrogen product from the lower tower top, collecting oxygen-enriched liquid air at the lower tower bottom, cooling and depressurizing through the liquid air expansion valve 33, entering the air upper tower boiling point feed inlet for further rectification and separation, obtaining a pure liquid nitrogen product from the upper tower top, and generating oxygen-enriched gas at the upper tower bottom as described above.
As shown in figure 2, the method and the process system for co-producing synthetic ammonia, a tertiary hydrogen refrigerant and a secondary nitrogen refrigerant enter a synthetic gas freezing ammonia separation combination 42, and together with synthetic recycle gas which returns from a synthetic gas-liquid ammonia separator 50 and has the temperature not higher than-60 ℃ and also serves as a refrigerant, the ammonia-containing synthetic gas which is cooled to the temperature not higher than 30 ℃ by a synthetic gas cooler 49 is cooled to the temperature lower than-60 ℃ and enters a gas-liquid ammonia separator 50 to complete liquid phase ammonia separation, so that the gas phase equilibrium ammonia-containing concentration of the returned synthetic recycle gas is less than 0.34% (v%). The tertiary hydrogen refrigerant absorbs heat in the synthesis gas ammonia freezing separation combination 42, when the temperature is gradually increased from 78K to no higher than 27 ℃ (300K), adiabatic expansion is carried out to reduce the temperature to no higher than-51 ℃, and the pressure is reduced to no lower than 0.125MPa, the generated cold quantity is provided for the synthesis gas ammonia freezing separation combination 42, so that the temperature of the quaternary hydrogen refrigerant is increased to over 27 ℃ again, the quaternary hydrogen refrigerant is compressed in multiple stages through a hydrogen pressurizing unit 43 and transmits heat to a compression heat recovery device 38 step by step to reach the pressure of 4.0 to 5.0MPa and the temperature of 60 to 65 ℃, the quaternary hydrogen refrigerant enters a hydrogen pressurizing unit 44 to be pressurized to 10 to 20MPa, the temperature is increased to 180 to 240 ℃, the secondary nitrogen refrigerant serving as the synthesis ammonia raw material nitrogen after being reheated and the synthesis ammonia raw material hydrogen and the synthesis recycle gas are converged, and enter a synthesis tower 45 to carry out catalytic reaction. The process of reheating the secondary nitrogen refrigerant comprises the steps of absorbing heat with the synthetic cycle gas through the synthetic gas ammonia freezing separation combination 42 and heating to over 295K, and absorbing heat with the synthetic cycle gas pressurized by the supercharger 51 through the cycle gas cold heat exchange combination 47 and heating to 200-230 ℃. The molar flow ratio of hydrogen to nitrogen which is taken as a synthetic ammonia raw material and enters a synthesis tower is 3.0, the mixture is converged with synthetic recycle gas, the temperature is 200-230 ℃, the ammonia concentration is not higher than 0.16% (v%), ammonia synthesis reaction in a temperature range of 400-500 ℃ is completed through a built-in heat exchange tube type catalyst layer in the synthesis tower 45 under the pressure of 10-20MPa, the ammonia concentration of the synthesis gas discharged from the synthesis tower reaches 16-18% (v%), the temperature is 480-500 ℃, and after the processes of cooling and condensation separation of ammonia are carried out in the following sequence, non-condensable hydrogen and nitrogen are returned to the synthesis tower as synthetic recycle gas: the synthesis gas discharged from the tower is firstly released and cooled to 230 to 250 ℃ through a reaction heat recoverer 46, then released and cooled to be not lower than 65 ℃ (higher than the dew point temperature of gas phase ammonia) through a circulation air cooling heat exchange combination 47, then released and cooled to be not lower than 45 ℃ through a synthesis gas ammonia cooler 48, the gas phase ammonia is condensed along with the temperature reduction, the temperature reduction and ammonia condensation process is continued to be not lower than 30 ℃ through a synthesis gas water cooler 49, then cooled to be not higher than-60 ℃ through a synthesis gas ammonia freezing separation combination 42, enters a gas-liquid separator 50 to complete an ammonia separation process, liquid ammonia separated at the temperature is stored in a high-pressure liquid ammonia storage tank 52, the saturated ammonia concentration of returned synthesis circulation gas (hydrogen and nitrogen) is not higher than 0.34% (v%), circulated and returned and reheated to be more than 20 to 25 ℃ through the synthesis gas ammonia freezing separation combination 42, is boosted through a circulation booster 51, is further reheated to be 200 to 230 ℃ through a circulation air cooling heat exchange combination 47, and then enters the synthesis tower together with the nitrogen and the hydrogen as the raw materials of the synthesis ammonia. The heat generated by the process system is converted into power through a supercritical ammonia working medium thermal-dynamic circulation ring to be output: a high-pressure liquid ammonia storage tank 52 is also used as a liquid supply tank of a supercritical ammonia working medium circulation loop, the operating pressure in the tank is 10-20MPa (the same as that of a gas-liquid separator 50 of an ammonia synthesis loop), the working medium temperature is lower than 35 ℃, the liquid flows through a synthesis gas ammonia cooler 48 to absorb heat and raise the temperature to be not lower than 55 ℃ under the action of the pressure in the tank, then flows through a compression heat recoverer 38 to absorb heat and raise the temperature to be not lower than 125 ℃, flows through a reaction heat recoverer 46 to absorb heat and raise the temperature to be not lower than 280 ℃, is adiabatically expanded to the pressure of not lower than 1.0MPa through an ammonia working medium expander 53 to the temperature of not lower than 26 ℃, produces an isentropic power of not less than 500 kJ/kg-ammonia working medium, is condensed into liquid ammonia through an ammonia working medium condenser 54, is stored in a medium-pressure liquid ammonia storage tank 55, is pressurized to a supercritical state by a pressure pump 56, is buffered through the high-pressure liquid ammonia tank 52, enters the supercritical ammonia working medium heat-motive circulation loop, and the mass flow of the supercritical ammonia is not less than 2.55 times of the ammonia yield. The liquid ammonia product separated from the ammonia synthesis process system is circulated by a supercritical ammonia working medium thermal-dynamic circulation loop, and then the liquid ammonia product is output by a medium-pressure liquid ammonia storage tank 55.
The temperature difference between the heat absorption process and the heat release process is not less than 2 ℃.
Drawings
The attached figures 1 and 2 are schematic diagrams of a process and a system for co-producing synthetic ammonia by refining liquid hydrogen and liquid nitrogen through cold-heat-kinetic energy complementation.
In the attached figure 1: 1-feedstock hydrogen compressor; 2-dehydration and purification combination; 3-raw material hydrogen nitrogen cooler; 4-raw material hydrogen cooler; 5-feedstock hydrogen liquefier; 6-raw material hydrogen expander; 7-common hydrogen product storage tank; 8-refined liquid hydrogen product storage tank; 9-refrigerant ammonia condensation storage tank; 10-hydrogen refining combination; 11-primary liquid hydrogen pump; 12-hydrogen refining pressurizer; 13-refrigerant heat collector; 14-refrigerant hydrogen compressor; 15-cooling medium ammonia cooler; 16-coolant water cooler; 17-refrigerant hydrogen cooler; 18-an auxiliary hydrogen expander; 19-an auxiliary hydrogen heat collector; 20-an auxiliary hydrogen compressor; 21-an auxiliary hydrogen ammonia cooler; 22-auxiliary hydrogen water cooler; 23. 24-liquid ammonia pressure pump; 25. 26-an ammonia expander; 27-refrigerant hydrogen expander; 28-hydroconversion nitrogen cooler; 29-hydrogen-assisted nitrogen cooler; 110-secondary liquid hydrogen pump;
in the attached figure 2: 30-liquid nitrogen condenser combination; 31-upper column of the air separation rectification column; 32-a lower column of a space division rectifying column; 33-liquid air expansion valve; 34-a liquid nitrogen expansion valve; 35-a liquid nitrogen storage tank; 36-liquid nitrogen pressure pump; 37-an air compressor; 38-compression heat recovery; 39-air dehydration/purification combination; 40-oxygen-enriched air recooler; 41-cold nitrogen recooler; 42-synthesis gas freezing combination; 43-a hydrogen booster set; 44-hydrogen pressurization single machine; a 45-ammonia converter; 46-reaction heat recoverer; 47-cycle air cooling heat exchange combination; 48-ammonia cooler of synthesis gas; 49-synthetic gas water cooler; 50-a gas-liquid separator; 51-circulation supercharger; 52-high pressure liquid ammonia storage tank; 53-ammonia working medium expander; 54-ammonia working medium condenser; 55-medium pressure liquid ammonia storage tank; 56-liquid ammonia pressure pump.
The following is further illustrated with reference to the examples.
Detailed Description
Example (b): the periodic power grid uses the ordinary hydrogen intermediate product of liquid and gas-liquid mixture of the valley period system, couples the technological system and process of liquid hydrogen, liquid nitrogen, coproduction synthetic ammonia of continuous refining.
Cycle duration for producing a common hydrogen intermediatetNot less than 8 hours per day (24 hours); process system for long-period continuous refining of liquid hydrogen, liquid nitrogen and coproduction of synthetic ammonia by using common hydrogen intermediate product as raw material and taking hour load of intermediate productm(kg/h) production capacity as an intermediate productpThe base of the product of (kg/h) and the cycle length is averaged over 24 hours,m=(p×t) And/24, the fluctuation is not more than 20 percent. In the embodiment, 2800kg/h of a common hydrogen intermediate product is prepared by using electrolytic water to prepare hydrogen as a raw material in the power grid power consumption valley period from 23 nights per day to 7 nights per day. Continuously processing the intermediate product 24 hours a day to prepare 460kg/h of refined liquid hydrogen product with the pressure of 0.3-0.4 MPa, the temperature of 25-26K and the parahydrogen component of more than 98.5 percent, and coproducing 2680kg/h of synthetic ammonia product. The isentropic efficiency of a compressor and an expander adopted by the system is not lower than 0.8, and the temperature difference between the cold exchanger and the heat exchanger is not lower than 2 ℃. The auxiliary raw material is ambient air 2300Nm 3 H, the byproduct is oxygen-enriched gas 480 Nm with oxygen concentration more than 93 percent (v percent) 3 /h。
As shown in figure 1, the power consumption valley period is periodicThe process for preparing liquid common hydrogen by using electrolyzed water to prepare hydrogen as a raw material comprises the following steps: a raw material hydrogen compressor 1 feeds a raw material hydrogen of 31360Nm and 0.12 to 0.25MPa and 5 to 35 DEG C 3 Pressurizing to 0.4 to 0.8MPa in/h (2800 kg/h), heating to 220 to 240 ℃, recovering the heat of compressed hydrogen through ammonia working medium supercritical heat-kinetic conversion to reduce the temperature to not higher than 50 ℃, cooling to 5 to 25 ℃ with water, separating condensed water, adsorbing and purifying to ensure that the total impurity content is not more than 0.2 x 10 -4 v%, cooling the mixture to an absolute temperature of not higher than 83K by using a nitrogen cooling medium in a circulating manner, further cooling the cooled mixture to a temperature of not higher than 31K by using a hydrogen cooler 4, then feeding the cooled mixture into a raw material hydrogen liquefier 5, performing heat release condensation at a temperature of not higher than 30K to obtain liquid hydrogen, performing adiabatic expansion by using a raw material hydrogen expander 6 to obtain a gas-liquid two-phase common hydrogen mixture with the pressure of 0.11-0.25MPa, the temperature of 20.5-24.0K and the dryness of not more than 0.25, buffering the mixture by using a storage tank 7 to serve as a refrigerant, leading out the refrigerant, sequentially performing heat absorption vaporization by using 5 and 4, and heating the refrigerant to a temperature of not higher than 81K, the waste heat is continuously absorbed by a refrigerant heat collector 13, the temperature is raised to 273-295K, the pressure is increased to 1.8-2.5MPa and the temperature is raised to 513-535K by a refrigerant hydrogen compressor 14, then the heat is released and cooled to not more than 330K by a refrigerant ammonia cooler 15, the heat is released and cooled to not more than 300K by a refrigerant water cooler 16, the heat is continuously released and cooled to not more than 83K by the refrigerant heat collector 13, the heat is released and cooled to not more than 34K by a refrigerant hydrogen cooler 17, and then the mixture of gas-liquid two-phase common hydrogen with the pressure of 0.11-0.25MPa, the temperature of 20.5-24.0K and the dryness of not more than 0.22 is adiabatically expanded by a refrigerant hydrogen expander 27 to be used as an intermediate product to return to the common hydrogen storage tank 7. The method comprises the steps of supplying cold energy to a hydrogen cooler 17 by auxiliary hydrogen (called auxiliary hydrogen for short, the same below) with the outlet pressure of 0.8-1.0 MPa and the temperature of 30-32K of a refrigerant expander 18, wherein the auxiliary hydrogen has the circulation mass flow of 4500kg/h, absorbs heat from the refrigerant hydrogen cooler 17 and is heated to not more than 81K, absorbs heat through an auxiliary hydrogen heat collector 19 and is heated to 273-295K, then the auxiliary hydrogen compressor 20 is used for pressurizing to 12-15MPa, the temperature is reduced to not more than 330K through an auxiliary hydrogen ammonia cooler 21 at the temperature of 513-535K, the temperature is reduced to not more than 300K through an auxiliary hydrogen water cooler 22, the auxiliary hydrogen heat collector 19 releases heat and is cooled to not more than 110K, the temperature is reduced to not more than 82K through an auxiliary hydrogen nitrogen cooler 29, and the auxiliary hydrogen expander 18 forms closed circulation of the auxiliary hydrogen refrigerant. The ammonia expander 25, the refrigerant ammonia condensation storage tank 9, the liquid ammonia pressure pump 23 and the refrigerantThe ammonia cooler 15 forms a cold/heat/dynamic conversion chain of the refrigerant hydrogen, wherein the ammonia expander 25 enables supercritical ammonia heated to the temperature of not more than 535K by the refrigerant ammonia cooler 15 to adiabatically expand from 12 to 169MPa to the pressure of not less than 0.8MPa, enters the refrigerant ammonia condensation storage tank 9 and is cooled and liquefied by a water cooling medium, then the supercritical ammonia is pressurized to 12 to 169MPa by the liquid ammonia pressure pump 23 and enters the cold/heat/dynamic conversion closed circulation chain of the refrigerant hydrogen, the flow of the circulating ammonia working medium is not less than 2.64 times of the mass flow of the raw material hydrogen, and the expansion isentropic work obtained by the unit mass of the ammonia working medium is not less than 450kJ/kg-NH3. An ammonia expansion machine 26, a refrigerant ammonia condensation storage tank 9, a liquid ammonia pressure pump 24 and an auxiliary hydrogen ammonia cooler 21 form an auxiliary hydrogen refrigerant cold/heat/dynamic conversion chain, wherein the ammonia expansion machine 26 enables supercritical ammonia heated to the temperature of not more than 535K by the auxiliary hydrogen ammonia cooler 21 to be adiabatically expanded from 12 to 169mpa to the pressure of not less than 0.8MPa, the supercritical ammonia enters the shared refrigerant ammonia condensation storage tank 9 and is cooled and liquefied by a water cooling medium, then the supercritical ammonia is pressurized to 12 to 16900 MPa by the liquid ammonia pressure pump 24 and enters a cold/heat/dynamic closed circulation chain of the auxiliary hydrogen refrigerant, the flow rate of a circulating ammonia working medium is not less than 4.40 times of the mass flow rate of raw material hydrogen, and the expansion isentropic work of a unit mass ammonia working medium is not less than 450kJ/kg-NH3.
The process for preparing refined liquid hydrogen products by continuously processing common hydrogen intermediate products in a long period in a full period as shown in the attached figure 1: liquid ordinary hydrogen (473.33 kg/h) with pressure of 0.11-0.25MPa and temperature of 20.5-24.0K in an ordinary hydrogen storage tank (7) is pressurized to 0.8-0.9 MPa by a primary liquid hydrogen pump (11), and is heated to be not higher than 31K through heat absorption in a cold pipe of a catalytic conversion and liquefaction combination 10, and then is pressurized to be 4.0-6.0 MPa by a secondary liquid hydrogen pump (110) and is returned to the combination 10 under supercritical pressure to be continuously heated to be not higher than 60K, and the liquid ordinary hydrogen is taken as supercritical ordinary cold hydrogen to be output. 460kg/h of common hydrogen gas-liquid two-phase mixture (dryness is 0 to 66%) with pressure of 0.11 to 0.25MPa and temperature of 20.5 to 24.0K in a storage tank 7 is pumped by a hydrogen refining pressurizer 12, the mixture is vaporized by heat absorption in a cold pipe of the combination 10 and heated to be not more than 78K, then the mixture is pressurized to be 0.3 to 0.7MPa and heated to be 128 to 158K by the pressurizer 12, the mixture is cooled to be below 82K by a hydrogen conversion nitrogen cooler 28 and returned to a normal hydrogen conversion secondary state hydrogen catalyst particle layer outside the cold pipe of the combination 10 for conversion and refining, and conversion heat is transferred to 31 to 60K low-temperature supercritical cold hydrogen flowing in the pipe and low-pressure common hydrogen gas-liquid two-phase mixture which is vaporized and absorbs heat below 78K through the wall of the cold pipe. The terminal hydrogen temperature of the conversion refining reaction is 24.5 to 25K, the secondary hydrogen content of the refined hydrogen is more than 98.5 percent, then the refined liquid hydrogen product is obtained by heat release and condensation on the outer surface of the cold pipe through the liquefaction section of the combination 10, and 460kg/h of the refined liquid hydrogen product is stored in a product storage tank 8.
The full-time long-period continuous supercritical common cold hydrogen is taken as a refrigerant and a raw material as shown in the attached figure 2, and the air separation is used for preparing liquid nitrogen and coproducing synthetic ammonia: 473.33kg/H of supercritical common cold hydrogen is taken as a primary refrigerant, the temperature of the primary refrigerant is raised to be not higher than 60K through heat absorption in a cold pipe of the combination 10 of catalytic conversion and liquefaction in the process of refining liquid hydrogen, the primary refrigerant is output at the pressure of 4.0-6.0 MPa, the primary refrigerant is continuously taken as a secondary refrigerant, enters a condenser combination 30 of the air separation tower to absorb heat and raise the temperature to be not lower than 78K, then is subjected to adiabatic expansion and temperature reduction outside the tower to be not lower than 58K after entering the condenser combination again to absorb heat and raise the temperature to be not lower than 78K, and is subjected to adiabatic expansion and temperature reduction outside the tower to be not lower than 58K, the process is repeated for at least 3 times, and the cold energy of 58-78K provided for the condenser combination 30 is not less than 980kJ/kg-H 2 And then the refrigerant is output under the pressure of not less than 0.35MPa and the temperature of not more than 78K and continuously enters the synthesis gas freezing ammonia separation combination 42 as a tertiary refrigerant. The upper tower condensation combination 30 of the air separation tower utilizes the cold energy provided by the secondary refrigerant to obtain pure liquid nitrogen with the pressure not lower than 0.137MPa, the temperature not lower than 80K and the concentration higher than 99.99 percent (v percent) not less than 1136 kg/h and ensures that the upper tower operation reflux ratio of the air separation tower is not less than 1.2. Through connecting the bottom of an upper tower 31 and the top of a lower tower 32 of the air separation tower with an evaporation-condenser, the oxygen-enriched gas with the oxygen concentration not lower than 95.5 percent (v%), the temperature not higher than 93K and the pressure not higher than 0.145MPa is not less than 686kg/h at the bottom of the upper tower, and the oxygen-enriched gas flows through an oxygen-enriched gas recooler 40 after being discharged from the tower to absorb the heat of the air in the tower, so that the temperature is raised to be not lower than 290K and the system is output; pure liquid nitrogen with pressure not lower than 0.50MPa, temperature not lower than 94K and concentration higher than 99.99% (v%) is obtained at the lower tower top and is not less than 1089 kg/h; the liquid nitrogen generated at the top of the upper tower is stored in a liquid nitrogen storage tank 35, the liquid nitrogen generated at the top of the lower tower is decompressed by a liquid nitrogen expansion valve 34 and then is also stored in the liquid nitrogen storage tank 35, and the top of the storage tank and the top of the upper air separation tower are provided with gas phase balance pipes to ensure the pressure balance of the two. Pressurizing the liquid nitrogen in the storage tank 35 to a supercritical state with the operating pressure of 0.3 to 0.5MPa higher than that of the ammonia synthesis tower 45 and the temperature of no more than 90K by a liquid nitrogen booster pump 36The cold nitrogen is firstly used as refrigerant nitrogen to cool the air entering the tower to the temperature not higher than 105K through the cold nitrogen recooler 41, the temperature of the supercritical cold nitrogen is increased back to the temperature not higher than 200K, and the cold nitrogen is continuously used as the refrigerant nitrogen to enter the synthesis gas freezing ammonia separation combination 42. Raw air 2260Nm 3 The pressure of the air compressor 37 is increased to 0.5 to 0.8MPa, the temperature is increased to 180 to 220 ℃, the heat is released and cooled to be not lower than 60 ℃ through the compression heat recoverer 38, and then the temperature is reduced to be not higher than 27 ℃ through the air dehydration/purification combination 39, the total impurity content is not more than 0.2 multiplied by 10 -4 And v%, continuously cooling to 260K or below through an oxygen-enriched gas recooler 40, cooling to 105K or below through a cold nitrogen recooler 41, entering an air separation lower tower 32 for rectification separation, obtaining a pure liquid nitrogen product from the lower tower top, collecting oxygen-enriched liquid air at the bottom of the lower tower, cooling and reducing the pressure through a liquid-air expansion valve 33 to a boiling point, feeding the oxygen-enriched liquid air into an air upper tower for further rectification separation, obtaining a pure liquid nitrogen product from the upper tower top, and outputting oxygen-enriched gas from the upper tower bottom as described above.
The process for coproducing synthetic ammonia is shown in the attached figure 2: the refrigerant is taken as a tertiary refrigerant, the refrigerant is input into a synthesis gas ammonia freezing separation combination 42 from an air separation condenser combination 30, the hydrogen cooling pressure is not lower than 0.35MPa, the temperature is not higher than 78K, the refrigerant absorbs heat in the ammonia freezing separation combination 42, the refrigerant is gradually heated to 27 ℃ to carry out adiabatic expansion until the temperature is not higher than-51 ℃ and the pressure is not lower than 0.125MPa, the generated cold energy is provided for the ammonia freezing separation combination 42 so that the hydrogen cooling temperature is raised to be higher than 27 ℃ again, the refrigerant is taken as a synthesis ammonia raw material and enters a hydrogen pressurizing unit 43, is subjected to multistage compression, transfers heat to a compression heat recoverer 38 step by step until the pressure reaches 4.0-5.0 MPa and the temperature reaches 60-65 ℃, is pressurized to 10-20MPa through a hydrogen pressurizing single unit 44, is heated to 180-240 ℃, and is merged with synthesis circulation gas and enters an ammonia synthesis tower 45. The supercritical cold nitrogen passes through an air separation cold nitrogen recooler 41, the temperature of the supercritical cold nitrogen is not higher than 200K, the supercritical cold nitrogen is continuously used as refrigerant nitrogen to enter a synthesis gas freezing ammonia separation combination 42, the refrigerant nitrogen and the synthesis circulating gas which is returned to be lower than-60 ℃ after the refrigerant nitrogen and ammonia separator 50 are carried out for three times, the ammonia-containing synthesis gas which is cooled to be lower than 30 ℃ through a synthesis gas water cooler 49 is cooled to be lower than-60 ℃, the ammonia-containing synthesis gas enters a gas-liquid ammonia separator 50 to complete ammonia separation, and the gas phase equilibrium ammonia-containing concentration of the returned synthesis circulating gas is lower than 0.34% (v%). The supercritical cold nitrogen absorbs heat from the synthesis gas ammonia freezing separation combination 42 and is heated to more than 295K, then absorbs heat through the synthesis cycle gas cooling heat exchange combination 47 and is heated to 200-230 ℃, and the synthesis cycle gas heated to 200-230 ℃ through the combination is converged and enters the synthesis tower 45. The raw materials of hydrogen and nitrogen added into the synthesis tower are converged with synthesis circulating gas with the molar flow ratio being 1.2 to 1.8 times larger than the sum of the molar flow ratio, then the synthesis circulating gas enters the synthesis tower 45 at the temperature of 200 to 230 ℃ and the ammonia concentration being not higher than 0.16 percent (v%) under the pressure of 10 to 20MPa, ammonia synthesis reaction is completed in a temperature zone of 400 to 500 ℃ in a catalyst particle layer with a built-in heat exchange tube, the ammonia concentration of the synthesis gas out of the synthesis tower reaches 16 to 18 percent (v%), the temperature is 480 to 500 ℃, and the processes of synthesis gas reaction heat recovery and cooling, freezing, condensation and ammonia separation are carried out according to the following sequence: the synthesis gas discharged from the tower is firstly released and cooled to 230 to 250 ℃ through a reaction heat recoverer 46, then released and cooled to be not lower than 65 ℃ (higher than the dew point temperature of gas phase ammonia) through a circulating air cooling heat exchange combination 47, then released and cooled to be not lower than 45 ℃ through a synthesis gas ammonia cooler 48 so as to gradually condense ammonia with saturation content higher than the gas phase, then released and cooled to be not lower than 20 ℃ through a synthesis gas water cooler 49 so as to condense more ammonia, finally cooled to be not higher than-60 ℃ through a synthesis gas ammonia freezing separation combination 42, and then enters a gas-liquid separator 50 to complete an ammonia separation process, liquid ammonia separated at the temperature is stored in a high-pressure liquid ammonia storage tank 52, the gas phase (hydrogen and nitrogen) is used as synthesis circulating gas, the saturation ammonia concentration is not higher than 0.34% (v%), the circulating reflux is reheated to 20 to 25 ℃ through the synthesis gas ammonia freezing combination 42, is boosted through a circulating air cooling heat exchange combination 47, is further reheated to be 200 to 230 ℃ through a circulating air cooling heat exchange combination 47, and then enters a booster 45. The process of recovering the heat generated by the process system and converting the heat into power output through the supercritical ammonia working medium thermal-dynamic circulation is as follows: a high-pressure liquid ammonia storage tank 52 is used as a liquid supply tank for supercritical ammonia working medium circulation, the operating pressure in the tank is 10-20MPa (the same as that of a gas-liquid separator 50 of an ammonia synthesis loop), the working medium temperature is lower than 35 ℃, the working medium flows through a synthesis gas ammonia cooler 48 under the action of the pressure in the tank to absorb heat and raise the temperature to be not lower than 55 ℃, the working medium continuously flows through a compression heat recoverer 38 to absorb heat and raise the temperature to be not lower than 125 ℃, then flows through a reaction heat recoverer 46 to absorb heat and raise the temperature to be not lower than 280 ℃, is subjected to adiabatic expansion through an ammonia working medium expander 53 to reach a pressure of not lower than 1.0MPa, a temperature of not lower than 26 ℃, and an isentropic work of not less than 500 kJ/kg-ammonia working medium is output, then is condensed into liquid ammonia through an ammonia working medium condenser 54, is stored in a medium-pressure liquid ammonia storage tank 55, is boosted by a liquid ammonia booster pump 56, and is sent into the high-pressure liquid ammonia tank 52 for buffering, enters the supercritical ammonia working medium thermal-dynamic circulation, and the circulation mass flow of not less than 2.55 times of the ammonia output. 2680kg/h of liquid synthetic ammonia product obtained by reaction and separation participates in the thermal-dynamic circulation of supercritical ammonia working medium, and then is output through a medium-pressure liquid ammonia storage tank 55.
The invention is not limited to the above-described embodiments, the technical solutions of which have been described in the summary of the invention.
Claims (6)
1. A method for dividing common cryogenic hydrogen into two parts to process refined liquid hydrogen and output supercritical hydrogen refrigerant is characterized in that common hydrogen with the pressure of 0.12 to 0.25MPa and the temperature of 5 to 35 ℃ is firstly processed into a gas-liquid two-phase common hydrogen mixture with the pressure of 0.11 to 0.25MPa, the temperature of 20.5 to 24.0K and the dryness of not more than 0.15 by cryogenic cooling, and then the mixture is divided into two parts: pressurizing a part of liquid common hydrogen to 0.8 to 0.9MPa by a primary liquid hydrogen pump to serve as a primary hydrogen refrigerant, carrying out heat absorption and temperature rise in a cold pipe of a hydrogen refining combination until the temperature is not higher than 31K, then pressurizing to a supercritical pressure of 4.0 to 6.0MPa by a secondary liquid hydrogen pump, returning to the combination, continuously carrying out heat absorption and temperature rise until the temperature is not higher than 60K, and outputting as a supercritical secondary hydrogen refrigerant; the dryness of the other part of gas-liquid two-phase common hydrogen mixture is 0 to 0.95, the other part of gas-liquid two-phase common hydrogen mixture is pumped by a hydrogen refining pressurizer, is subjected to endothermic vaporization in a cold tube combining hydrogen refining catalytic conversion and liquefaction, is heated to be not more than 78K, is then pressurized to be 0.3 to 0.7MPa, is heated to be 128 to 158K, is cooled to be lower than 82K by a hydrogen conversion nitrogen cooler, returns to a combined catalyst particle layer for a conversion refining process of normal hydrogen to secondary hydrogen, and the conversion heat is transferred to a primary hydrogen refrigerant flowing in the tube at the temperature of 31 to 60K and a common hydrogen gas-liquid two-phase mixture subjected to vaporization heating and endothermic heating at the temperature of less than 78K through cooling tubes distributed on the catalyst particle layer; the reaction end temperature of refined hydrogen is 24.5 to 29K, the composition of parahydrogen is 97.2 to 99.2 percent, and the refined hydrogen is stored in a refined liquid hydrogen product storage tank with the pressure not higher than 0.7MPa and the temperature not higher than 29K after being condensed by heat release of a liquefaction segment cooling pipe of a hydrogen refining combination; the mass flow ratio of the output supercritical secondary hydrogen refrigerant to the refined liquid hydrogen product is not less than 1.0;
the ordinary hydrogen is hydrogen prepared by an ordinary industrial process, and is not converted into parahydrogen by ortho-hydrogen, the composition of the parahydrogen is not higher than 30 percent, and the composition of the ortho-hydrogen is not lower than 70 percent;
the temperature difference of the heat transfer process ends of heat release and heat absorption through the cold pipe is not less than 2 ℃.
2. A method for producing liquid nitrogen and outputting supercritical nitrogen refrigerant by air separation coupled with a liquid hydrogen refining process is characterized in that supercritical secondary hydrogen refrigerant with the output temperature of not higher than 60K in the liquid hydrogen refining process is utilized to absorb heat through a liquid nitrogen condenser at the top of an upper tower of an air separation rectifying tower in a combined manner, so that pure nitrogen with the pressure of not lower than 0.137MPa, the temperature of not lower than 80K and the concentration of more than 99.99 v% is released and condensed into a pure liquid nitrogen product; the secondary hydrogen refrigerant absorbs heat and is heated to be not less than 78K, then is subjected to adiabatic expansion and is cooled to be not less than 58K, and then returns to the liquid nitrogen condenser for combined heat absorption, and the operation is repeated for at least 3 times until the pressure of the secondary hydrogen refrigerant is reduced to be not less than 0.35MPa and the temperature is not higher than 78K, and the secondary hydrogen refrigerant is output as a tertiary hydrogen refrigerant for subsequent use; the cold energy of a 58-78K temperature zone provided by each kg of secondary hydrogen refrigerant for the liquid nitrogen condenser combination is not less than 980kJ, so that the pure liquid nitrogen product obtained from the upper tower top is not less than 2.4kg under the condition that the reflux ratio of the rectifying tower is not less than 1.2, and the pure liquid nitrogen with the pressure not less than 0.50MPa, the temperature not less than 94K and the concentration more than 99.99 percent obtained from the lower tower top is not less than 2.3kg; pure liquid nitrogen products prepared by the upper tower and the lower tower are stored in the same liquid nitrogen storage tank, the top of the liquid nitrogen product is lower than the bottom of the upper tower of the air separation rectifying tower, and the gas phase pressure of the liquid nitrogen product is balanced with the gas phase pressure of the top of the upper tower of the air separation rectifying tower;
and pressurizing the liquid nitrogen in the storage tank into supercritical cold nitrogen with the temperature not more than 90K by using a liquid nitrogen pressurizing pump, cooling the air entering the air separation tower to the temperature not higher than 105K by using the supercritical cold nitrogen as a primary nitrogen refrigerant, raising the temperature of the primary nitrogen refrigerant to not higher than 200K, and outputting the cooled air as a secondary nitrogen refrigerant for subsequent use.
3. A process and system for co-production of synthetic ammonia coupled with a process of refining liquid hydrogen and outputting a supercritical hydrogen refrigerant and a process of separating air to prepare liquid nitrogen and outputting a supercritical nitrogen refrigerant are characterized in that the supercritical secondary hydrogen refrigerant output in the process of refining liquid hydrogen uses the cold energy in the process of preparing liquid nitrogen by air separation, then the output tertiary hydrogen refrigerant with the pressure not lower than 0.35MPa and the temperature not higher than 78K is continuously used as the refrigerant of the synthesis gas freezing combination of a synthetic ammonia process system, the supercritical secondary nitrogen refrigerant with the temperature not higher than 200K is also transmitted to the combination in the process of preparing liquid nitrogen by air separation, and the supercritical secondary hydrogen refrigerant with the temperature not higher than-60 ℃ and the circulating gas refrigerant with the temperature not higher than-60 ℃ are together transmitted, the ammonia-containing synthesis gas cooled to the temperature not higher than 30 ℃ by the freezing combination is cooled to the temperature lower than-60 ℃ for gas-liquid ammonia separation, and the ammonia concentration of the circulating gas flowing back is less than 0.34v%; the tertiary hydrogen refrigerant absorbs heat in the refrigeration combination and is heated to be not higher than 27 ℃, the temperature of the tertiary hydrogen refrigerant is reduced to be not higher than-51 ℃ and not lower than 0.125MPa through adiabatic expansion, the generated cold energy is returned to the refrigeration combination, the temperature of the quaternary hydrogen refrigerant is raised to be more than 27 ℃ again, the quaternary hydrogen refrigerant is compressed by a hydrogen pressurizing unit and the compression heat is recovered, the pressure reaches 4.0 to 5.0MPa and the temperature reaches 60 to 65 ℃, the quaternary hydrogen refrigerant is pressurized to 10 to 20MPa through a hydrogen pressurizing single machine and is heated to 180 to 240 ℃, the quaternary hydrogen serving as an ammonia synthesis raw material is merged with the secondary nitrogen refrigerant serving as the nitrogen of the ammonia synthesis raw material after reheating and the recycle gas, and the mixture enters a synthesis tower to carry out ammonia synthesis catalytic reaction; the process of reheating the secondary nitrogen refrigerant comprises the steps of carrying out heat absorption and temperature rise to more than 295K together with the circulating gas through a frozen ammonia separation combination, and then carrying out heat absorption and temperature rise to 200-230 ℃ together through a circulating gas cold-heat exchange combination; the molar flow ratio of hydrogen to nitrogen which is used as synthesis ammonia feed gas and enters a synthesis tower is 3.0, the ammonia concentration is not higher than 0.16 v% after the synthesis ammonia feed gas is merged with synthesis circulating gas, the ammonia synthesis reaction at a temperature ranging from 400 ℃ to 500 ℃ is completed through a synthesis tower catalyst layer under the pressure ranging from 10 MPa to 200 MPa, and the ammonia concentration of the synthesis gas which is discharged from the synthesis tower reaches 16% to 18 v%, and the temperature ranges from 480 ℃ to 500 ℃; the synthesis gas discharged from the tower is firstly cooled to 230 to 250 ℃ through the heat release of a reaction heat recoverer, then cooled to not less than 65 ℃ through the heat release of a circulating air cooling heat exchange combination, then cooled to not less than 45 ℃ through the heat release of a synthesis gas ammonia cooler, cooled to not less than 30 ℃ through a water cooler, cooled to not more than-60 ℃ through a synthesis gas ammonia freezing separation combination, and then enters a gas-liquid separator to complete the ammonia separation process, the separated liquid ammonia at the temperature is stored in a high-pressure liquid ammonia storage tank, the separated gas phase is used as circulating gas reflux, reheated to 20 to 25 ℃ through the ammonia freezing separation combination, pressurized by a circulating booster, further reheated to 200 to 230 ℃ through a circulating air cooling heat exchange combination, merged with the nitrogen and the hydrogen of the synthesis ammonia raw material, and enters a synthesis tower and a synthesis process system to circulate;
the temperature difference between the heat absorption and heat release or freezing process heat exchange fluid ends is not less than 2 ℃.
4. The method according to claim 1, wherein the cryogenic common hydrogen is divided into two parts to process refined liquid hydrogen and output supercritical hydrogen refrigerant, the method is characterized in that the raw material hydrogen is pressurized to 0.4 to 0.8MPa, the compression waste heat is recovered, the nitrogen cooling medium is used for circulating cooling to no more than 83K after water cooling and adsorption purification, the temperature is further reduced to no more than 31K through the hydrogen cooler, the raw material hydrogen liquefier enters the raw material hydrogen expander, the liquid hydrogen is condensed through heat release at no more than 30K, the gas-liquid two-phase hydrogen mixture with the pressure of 0.11 to 0.25MPa, the temperature of 20.5 to 24.0K and the dryness of no more than 0.15 enters the intermediate product storage tank for homogenization and buffer transition and is led out as the refrigerant hydrogen, absorbing heat and vaporizing by a hydrogen liquefier and a hydrogen cooler in sequence, heating to no more than 81K, continuously heating to 273-295K by a refrigerant heat collector, pressurizing to 1.8-2.5MPa, heating to 513-535K, then releasing heat and cooling to no more than 330K by a refrigerant ammonia cooler, releasing heat and cooling to no more than 300K by a refrigerant water cooler, continuously heating and cooling to no more than 83K by the refrigerant heat collector in sequence, releasing heat and cooling to no more than 34K by the refrigerant hydrogen cooler, finally performing adiabatic expansion by a refrigerant hydrogen expander to obtain a gas-liquid two-phase common hydrogen mixture with the pressure of 0.11-0.25MPa, the temperature of 20.5-24.0K and the dryness of no more than 0.15, and returning to a common hydrogen product storage tank, wherein the normal hydrogen and the secondary hydrogen consist of: the orthohydrogen is higher than 70 percent, and the parahydrogen is lower than 30 percent;
the cold quantity required by the hydrogen cooler of the refrigerant is provided by a hydrogen-assisted refrigerant with the outlet pressure of 0.8 to 1.0MPa and the temperature of 30 to 32K, the mass flow of the circulation of the hydrogen-assisted refrigerant is not less than 1.60 times of the mass flow of the raw material hydrogen, the heat is absorbed from the hydrogen cooler of the refrigerant and is heated to be not more than 81K, the heat is absorbed by a hydrogen-assisted heat collector and is heated to 273 to 295K, then the pressure is increased to 12 to 15MPa, the heat is released by a hydrogen-assisted ammonia cooler and is cooled to be not more than 330K at the temperature of 513 to 535K, the heat is released by the hydrogen-assisted water cooler and is cooled to be not more than 300K, the heat is released by the hydrogen-assisted heat collector and is cooled to be not more than 110K, the heat is cooled to be not more than 82K by a hydrogen-assisted nitrogen cooler, and the cold refrigerant enters the hydrogen-assisted expander to form a hydrogen-assisted closed circulation;
an ammonia expansion machine, a refrigerant ammonia condensation storage tank, a liquid ammonia pressure pump and a refrigerant ammonia cooler form a cold/heat/kinetic conversion chain of refrigerant hydrogen, wherein the ammonia expansion machine enables supercritical ammonia which is heated to the temperature of not more than 535K by the refrigerant ammonia cooler to adiabatically expand from 12 to 169pa until the pressure is not lower than 0.8MPa, the supercritical ammonia enters the refrigerant ammonia condensation storage tank and is cooled and liquefied by a water cooling medium, then the supercritical ammonia is pressurized to 12 to 169pa by the liquid ammonia pressure pump and enters the cold/heat/kinetic conversion chain of the refrigerant hydrogen for closed circulation, and the mass flow of the circulating ammonia is not less than 2.64 times of the mass flow of the raw material hydrogen;
the cold/heat/dynamic conversion chain of the hydrogen-assisted refrigerant is composed of a shared refrigerant ammonia condensation storage tank, an ammonia expansion machine, a liquid ammonia pressure pump and a hydrogen-assisted ammonia cooler, wherein the ammonia expansion machine enables supercritical ammonia which is heated to the temperature of not more than 535K by the hydrogen-assisted ammonia cooler to adiabatically expand from 12 to 169pa to not less than 0.8MPa, the supercritical ammonia enters the shared refrigerant ammonia condensation storage tank to be cooled and liquefied, then the supercritical ammonia is pressurized to 12 to 169pa by the liquid ammonia pressure pump and enters the cold/heat/dynamic conversion chain of the hydrogen-assisted refrigerant to be in closed circulation, and the mass flow of the circulating ammonia is not less than 4.40 times of the mass flow of the raw material hydrogen.
5. The process and system for co-producing synthetic ammonia coupled with the process of refining liquid hydrogen and outputting supercritical hydrogen refrigerant and the process of separating air to prepare liquid nitrogen and outputting supercritical nitrogen refrigerant according to claim 3, characterized in that the heat generated by the process system is converted into power output by a supercritical ammonia working medium thermal-dynamic circulation ring: the method comprises the steps of taking a high-pressure liquid ammonia storage tank as a liquid supply tank of a supercritical ammonia working medium circulation loop, enabling the operating pressure in the tank to be 10-20MPa, enabling the working medium temperature to be lower than 35 ℃, enabling the working medium to flow under the action of the pressure in the tank to pass through a synthesis gas ammonia cooler to absorb heat and raise the temperature to be not lower than 55 ℃, enabling the working medium to continuously flow through a compression heat recovery device to absorb heat and raise the temperature to be not lower than 125 ℃, enabling the working medium to flow through a reaction heat recovery device to absorb heat and raise the temperature to be not lower than 280 ℃, enabling the working medium to expand in an adiabatic mode through an ammonia working medium expansion machine to enable the pressure to be not lower than 1.0MPa, enabling the temperature to be not lower than 26 ℃, generating an isentropic work to be not lower than 500 kJ/kg-ammonia working medium, condensing the working medium ammonia to be liquid ammonia to be stored in a medium-pressure liquid ammonia storage tank, enabling the liquid ammonia to be pressurized to be in a supercritical state, enabling the high-pressure ammonia tank to be buffered, enabling the liquid ammonia to enter the supercritical working medium heat-dynamic circulation loop, and enabling the mass flow to be not lower than 2.55 times of ammonia production; and after the liquid ammonia product separated from the ammonia synthesis process system is circulated through a supercritical ammonia working medium thermal-dynamic circulation loop, the liquid ammonia product is output from the medium-pressure liquid ammonia storage tank.
6. The method for processing refined liquid hydrogen and outputting a supercritical hydrogen refrigerant by dividing cryogenic common hydrogen into two parts according to claim 1 and the process and the system for co-producing synthetic ammonia by coupling the process for processing refined liquid hydrogen and outputting the supercritical hydrogen refrigerant and the process for separating air to produce liquid nitrogen and outputting the supercritical nitrogen refrigerant according to claim 3, wherein the processes for processing refined liquid hydrogen and outputting the supercritical hydrogen refrigerant and air separating to produce liquid nitrogen and outputting the supercritical nitrogen refrigerant and the coupling and co-producing synthetic ammonia are long-period continuous operation processes, and the process for deep cold processing common hydrogen at a pressure of 0.12 to 0.25MPa, a temperature of 5 to 35 ℃ into a gas-liquid two-phase common hydrogen intermediate product at a pressure of 0.11 to 0.25MPa, a temperature of 20.5 to 24.0K and a dryness of not more than 0.15 is a periodic intermittent process, and the production time is not less than 8 hours in each 24 hours; the amount of the gas-liquid two-phase common hydrogen intermediate product is taken per hour in the long-period continuous operation process, the product of the production capacity and the production time of the intermediate product per hour is taken as a base number, and the fluctuation is not more than 20% on average according to 24 hours.
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