CN114777412B - A hydrogen liquefaction device with a thermosiphon hydrogen subcooler - Google Patents
A hydrogen liquefaction device with a thermosiphon hydrogen subcooler Download PDFInfo
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- CN114777412B CN114777412B CN202210339493.6A CN202210339493A CN114777412B CN 114777412 B CN114777412 B CN 114777412B CN 202210339493 A CN202210339493 A CN 202210339493A CN 114777412 B CN114777412 B CN 114777412B
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- hydrogen
- heat exchanger
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 309
- 239000001257 hydrogen Substances 0.000 title claims abstract description 309
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 309
- 239000007788 liquid Substances 0.000 claims abstract description 150
- 239000007789 gas Substances 0.000 claims abstract description 117
- 238000003860 storage Methods 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- 238000001816 cooling Methods 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 238000005057 refrigeration Methods 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 22
- 102100029075 Exonuclease 1 Human genes 0.000 description 12
- 101000918264 Homo sapiens Exonuclease 1 Proteins 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 101100450590 Ricinus communis HEX6 gene Proteins 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000013526 supercooled liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 101100230900 Arabidopsis thaliana HEXO1 gene Proteins 0.000 description 3
- 101100230901 Arabidopsis thaliana HEXO2 gene Proteins 0.000 description 3
- 101100412393 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) REG1 gene Proteins 0.000 description 3
- 101100310405 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SLX5 gene Proteins 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- -1 However Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
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- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
- F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
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- F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
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Abstract
Description
技术领域technical field
本发明涉及氢气液化技术领域，具体而言，涉及一种具有热虹吸式氢过冷器的氢气液化装置。The invention relates to the technical field of hydrogen liquefaction, in particular to a hydrogen liquefaction device with a thermosiphon hydrogen subcooler.
背景技术Background technique
随着工业的发展和人们生活水平的提高，对能源的需求与日俱增。由于煤炭、石油等化石能源储量有限，且会污染环境，需要开发高效、洁净的二次能源，需要寻找可再生的绿色能源。氢是自然界存在最普遍的元素，氢的资源丰富，来源多样，作为一种二次能源，它具有燃烧热值高、清洁环保、可储存、可再生等优点。氢能可以同时满足资源、环境和可持续发展的要求，这些独特的优势使其在能源和化工领域具有广泛应用。With the development of industry and the improvement of people's living standards, the demand for energy is increasing day by day. Due to the limited reserves of fossil energy such as coal and petroleum, which will pollute the environment, it is necessary to develop efficient and clean secondary energy and to find renewable green energy. Hydrogen is the most common element in nature. Hydrogen is rich in resources and comes from various sources. As a secondary energy source, it has the advantages of high combustion calorific value, clean and environmentally friendly, storable, and renewable. Hydrogen energy can meet the requirements of resources, environment and sustainable development at the same time. These unique advantages make it widely used in the fields of energy and chemical industry.
氢能在世界范围内备受关注，成为近几年科研热点领域；氢能利用需要解决制取、储运和应用等一系列问题，氢能的储运是氢能应用的关键。氢的原料气经过压缩之后，降温到～-250℃以下使之变为液氢。常压下液氢的密度为气态氢的845倍，液氢的质量密度和体积密度较高。液氢以其体积能量密度高的优点，在远距离运输、储存等方面具有巨大的优势和经济性，在氢能利用中发挥重要的作用；因此氢气液化成为了氢气应用的重要选项。Hydrogen energy has attracted worldwide attention and has become a hot research field in recent years; the utilization of hydrogen energy needs to solve a series of problems such as production, storage, transportation and application, and the storage and transportation of hydrogen energy is the key to the application of hydrogen energy. After the raw material gas of hydrogen is compressed, the temperature is lowered to below -250°C to turn it into liquid hydrogen. The density of liquid hydrogen under normal pressure is 845 times that of gaseous hydrogen, and the mass density and volume density of liquid hydrogen are higher. Due to its high volume energy density, liquid hydrogen has great advantages and economical advantages in long-distance transportation and storage, and plays an important role in the utilization of hydrogen energy; therefore, hydrogen liquefaction has become an important option for hydrogen applications.
氢气通常是正氢和仲氢的平衡混合物，氢气的平衡浓度随温度的不同而有显著变化；当温度降低时，具有高能量基态的正氢自发地向低能态的仲氢转化，直到不能转化，成为该温度下的平衡氢；室温热平衡态下，氢气大约由75％正氢和25％仲氢组成，此称为正常氢；气态氢的正-仲态转化在存在催化剂的情况下才能发生，而液态氢则在没有催化剂的情况下也能自发地发生正仲转化，但是转化速率较慢；氢的正仲转化是一放热反应，在液氢储存过程中，为了避免转化热引起液氢产品的汽化，减少再液化的能耗，对于大型氢液化装置，产品中仲氢含量应超过95％。Hydrogen is usually an equilibrium mixture of orthohydrogen and parahydrogen, and the equilibrium concentration of hydrogen varies significantly with temperature; when the temperature decreases, orthohydrogen with a high-energy ground state spontaneously transforms into a low-energy state of parahydrogen until it cannot be transformed, Become the equilibrium hydrogen at this temperature; in the thermal equilibrium state at room temperature, hydrogen is composed of about 75% orthohydrogen and 25% parahydrogen, which is called normal hydrogen; the normal-paragonal conversion of gaseous hydrogen can only occur in the presence of a catalyst, However, liquid hydrogen can spontaneously undergo normal-to-secondary conversion without a catalyst, but the conversion rate is relatively slow; the normal-to-secondary conversion of hydrogen is an exothermic reaction. The vaporization of the product reduces the energy consumption of reliquefaction. For large-scale hydrogen liquefaction devices, the parahydrogen content in the product should exceed 95%.
但现有技术液氢转换效率低下，且能耗高；因此，现有技术还存在缺陷，有待进一步发展。However, the conversion efficiency of liquid hydrogen in the prior art is low and the energy consumption is high; therefore, there are still defects in the prior art and further development is needed.
发明内容Contents of the invention
为解决上述问题，本发明的目的在于提供一种具有热虹吸式氢过冷器的氢气液化装置，以解决现有技术液化效率低、能耗高的问题。To solve the above problems, the object of the present invention is to provide a hydrogen liquefaction device with a thermosiphon hydrogen subcooler to solve the problems of low liquefaction efficiency and high energy consumption in the prior art.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
本发明提供的一种具有热虹吸式氢过冷器的氢气液化装置，包括：气体管理模块、制冷模块及与制冷模块连接的液氢储罐，气体管理模块用于调控气体管理模块向制冷模块输出的气压；制冷模块包括第一换热器及热虹吸式氢过冷器，热虹吸式氢过冷器包括氢气液分离器、第八换热器及设置在第八换热器内的第四正仲氢转化器，气体管理模块与第一换热器连接；A hydrogen liquefaction device with a thermosiphon hydrogen subcooler provided by the present invention includes: a gas management module, a refrigeration module, and a liquid hydrogen storage tank connected to the refrigeration module. output air pressure; the refrigeration module includes a first heat exchanger and a thermosiphon hydrogen subcooler, and the thermosiphon hydrogen subcooler includes a hydrogen gas-liquid separator, an eighth heat exchanger, and a first heat exchanger arranged in the eighth heat exchanger Four ortho-parahydrogen converters, the gas management module is connected to the first heat exchanger;
第一换热器与液氢储罐依次连接并形成第一气路，第一换热器、第八换热器及液氢储罐依次连接并形成第二气路，第一换热器的高压侧输入氢气通向第二气路；氢气液分离器的上端与第一气路连接，氢气液分离器的下端与第八换热器的一侧连接，第八换热器的另一侧连接于氢气液分离器的上端；The first heat exchanger is sequentially connected with the liquid hydrogen storage tank to form a first gas path, the first heat exchanger, the eighth heat exchanger and the liquid hydrogen storage tank are sequentially connected to form a second gas path, and the first heat exchanger The hydrogen input on the high-pressure side leads to the second gas path; the upper end of the hydrogen gas-liquid separator is connected to the first gas path, the lower end of the hydrogen gas-liquid separator is connected to one side of the eighth heat exchanger, and the other side of the eighth heat exchanger Connected to the upper end of the hydrogen gas-liquid separator;
氢气液分离器的回流端通过第一换热器与气体管理模块连接并形成第三气路，液氢储罐通过第一换热器与气体管理模块连接并形成第四气路。The return end of the hydrogen gas-liquid separator is connected to the gas management module through the first heat exchanger to form a third gas path, and the liquid hydrogen storage tank is connected to the gas management module through the first heat exchanger to form a fourth gas path.
进一步地，氢气液化装置还包括液氮预冷装置、与第一换热器连接的第二换热器、与第二换热器连接的第九换热器及与第九换热器连接的冷却单元；Further, the hydrogen liquefaction device also includes a liquid nitrogen precooling device, a second heat exchanger connected to the first heat exchanger, a ninth heat exchanger connected to the second heat exchanger, and a cooling unit;
第九换热器内设置有第一正仲氢转化器，第一正仲氢转化器与冷却单元连接，冷却单元与第四正仲氢转化器连接；The ninth heat exchanger is provided with a first ortho-parahydrogen converter, the first ortho-parahydrogen converter is connected to the cooling unit, and the cooling unit is connected to the fourth ortho-parahydrogen converter;
液氮预冷装置分别与第一换热器、第二换热器及第九换热器连接，并对第一换热器、第二换热器及第九换热器进行预冷。The liquid nitrogen precooling device is respectively connected with the first heat exchanger, the second heat exchanger and the ninth heat exchanger, and precools the first heat exchanger, the second heat exchanger and the ninth heat exchanger.
进一步地，氢气液化装置还包括相互并联的第一低温吸附器及第二低温吸附器，第一低温吸附器及第二低温吸附器并联的一端与第二换热器连接，另一端与第一正仲氢转化器连接。Further, the hydrogen liquefaction device also includes a first low-temperature adsorber and a second low-temperature adsorber connected in parallel, one end of the parallel connection of the first low-temperature adsorber and the second low-temperature adsorber is connected to the second heat exchanger, and the other end is connected to the first low-temperature adsorber. Ortho-parahydrogen converter connection.
进一步地，冷却单元包括第三换热器、第四换热器、第五换热器、第六换热器及第七换热器，第三换热器、第四换热器、第五换热器、第六换热器及第七换热器的输出端依次相连并连接于第一气路及第二气路，第三换热器、第四换热器、第五换热器、第六换热器及第七换热器的回流端连接于第三气路；Further, the cooling unit includes a third heat exchanger, a fourth heat exchanger, a fifth heat exchanger, a sixth heat exchanger and a seventh heat exchanger, the third heat exchanger, the fourth heat exchanger, the fifth The output ends of the heat exchanger, the sixth heat exchanger and the seventh heat exchanger are connected in sequence and connected to the first gas path and the second gas path, the third heat exchanger, the fourth heat exchanger, and the fifth heat exchanger . The return ends of the sixth heat exchanger and the seventh heat exchanger are connected to the third gas path;
第三换热器与第一正仲氢转化器连接，第七换热器与液氢储罐连接。The third heat exchanger is connected with the first ortho-parahydrogen converter, and the seventh heat exchanger is connected with the liquid hydrogen storage tank.
进一步地，氢气液化装置还包括设置在第一气路上的第三低温吸附器，第三低温吸附器的一端与第二换热器连接，另一端与第三换热器连接。Further, the hydrogen liquefaction device further includes a third cryogenic adsorber arranged on the first gas path, one end of the third cryogenic adsorber is connected to the second heat exchanger, and the other end is connected to the third heat exchanger.
进一步地，氢气液化装置还包括连接在第二气路上的第二正仲氢转化器及第三正仲氢转化器；Further, the hydrogen liquefaction device also includes a second ortho-parahydrogen converter and a third ortho-parahydrogen converter connected to the second gas path;
第二正仲氢转化器的一端与第四换热器的低压侧连接，第二正仲氢转化器的另一端与第四换热器的高压侧连接；第三正仲氢转化器的一端与第六换热器的低压侧连接，第三正仲氢转化器的另一端与第六换热器的高压侧连接。One end of the second ortho-parahydrogen converter is connected to the low-pressure side of the fourth heat exchanger, and the other end of the second ortho-parahydrogen converter is connected to the high-pressure side of the fourth heat exchanger; one end of the third ortho-parahydrogen converter It is connected to the low-pressure side of the sixth heat exchanger, and the other end of the third ortho-parahydrogen converter is connected to the high-pressure side of the sixth heat exchanger.
进一步地，氢气液化装置还包括第一氢气透平膨胀机机组及第二氢气透平膨胀机机组，第一氢气透平膨胀机机组的一端连接在第三换热器及第四换热器之间的第一气路上，第一氢气透平膨胀机机组的另一端连接于第五换热器的高压侧；Further, the hydrogen liquefaction device also includes a first hydrogen turboexpander unit and a second hydrogen turboexpander unit, one end of the first hydrogen turboexpander unit is connected between the third heat exchanger and the fourth heat exchanger The other end of the first hydrogen turboexpander unit is connected to the high-pressure side of the fifth heat exchanger on the first gas path between them;
第二氢气透平膨胀机机组的一端连接于第五换热器的低压侧，第二氢气透平膨胀机机组的另一端连接于第六换热器的低压侧并依次连接第五换热器、第四换热器、第三换热器、第一换热器至气体管理模块。One end of the second hydrogen turboexpander unit is connected to the low-pressure side of the fifth heat exchanger, and the other end of the second hydrogen turboexpander unit is connected to the low-pressure side of the sixth heat exchanger and connected to the fifth heat exchanger in turn , the fourth heat exchanger, the third heat exchanger, the first heat exchanger to the gas management module.
进一步地，氢气液分离器的上端与第一气路连接之间设置有第八节流阀，第一气路上设置有第九节流阀且位于第八节流阀与液氢储罐之间，第二气路上设置有第十节流阀且位于冷却单元与第八换热器之间。Further, an eighth throttle valve is provided between the upper end of the hydrogen gas-liquid separator and the connection of the first gas circuit, and a ninth throttle valve is provided on the first gas circuit and is located between the eighth throttle valve and the liquid hydrogen storage tank , the second gas path is provided with a tenth throttle valve and is located between the cooling unit and the eighth heat exchanger.
进一步地，气体管理模块包括串联的中压氢气压缩机组和高压氢气压缩机组，中压氢气压缩机组远离高压氢气压缩机组的一端与第一换热器的回流端连接，高压氢气压缩机组远离中压氢气压缩机组的一端与第一换热器的输入端连接；Further, the gas management module includes a medium-pressure hydrogen compressor unit and a high-pressure hydrogen compressor unit connected in series, the end of the medium-pressure hydrogen compressor unit away from the high-pressure hydrogen compressor unit is connected to the return end of the first heat exchanger, and the high-pressure hydrogen compressor unit is far away from the medium-pressure hydrogen compressor unit. One end of the hydrogen compressor unit is connected to the input end of the first heat exchanger;
中压氢气压缩机组与高压氢气压缩机组之间通过第一换热器与第三换热器连接。The medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit are connected through the first heat exchanger and the third heat exchanger.
进一步地，氢气液化装置还包括气体缓冲罐，气体缓冲罐一端与第一换热器连接，另一端通过第十三调节阀与第二气路连接。Further, the hydrogen liquefaction device further includes a gas buffer tank, one end of the gas buffer tank is connected to the first heat exchanger, and the other end is connected to the second gas path through the thirteenth regulating valve.
本发明提出了一种具有热虹吸式氢过冷器的氢气液化装置，采用了热虹吸式氢过冷器，原料气路(第二气路)输入的气液两相氢被过冷成为过冷液氢，并同时进行正仲氢转化，生成仲氢含量合格的产品氢进入液氢储罐形成液氢产品；本发明采用热虹吸式氢过冷器，充分利用了液氢的潜热和显热，液化效率高，安全性好，能耗低。The present invention proposes a hydrogen liquefaction device with a thermosiphon hydrogen subcooler. The thermosiphon hydrogen subcooler is used, and the gas-liquid two-phase hydrogen input from the raw material gas path (second gas path) is supercooled into supercooled hydrogen. Cool the liquid hydrogen, and carry out the conversion of ortho-parahydrogen at the same time to generate the product hydrogen with qualified para-hydrogen content and enter the liquid hydrogen storage tank to form the liquid hydrogen product; the invention adopts the thermosiphon type hydrogen supercooler, which makes full use of the latent heat and sensible heat of liquid hydrogen Heat, high liquefaction efficiency, good safety, low energy consumption.
附图说明Description of drawings
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：The accompanying drawings described here are used to provide a further understanding of the present invention and constitute a part of the application. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations to the present invention. In the attached picture:
图1是本发明具有热虹吸式氢过冷器的氢气液化装置的结构图。Fig. 1 is a structural diagram of a hydrogen liquefaction device with a thermosiphon hydrogen subcooler of the present invention.
其中附图标记为：HEX1-第一换热器、HEX2-第二换热器、HEX3-第三换热器、HEX4-第四换热器、HEX5-第五换热器、HEX6-第六换热器、HEX7-第七换热器、HEX-OP4-第八换热器、HEX-OP1-第九换热器；The reference signs are: HEX1-first heat exchanger, HEX2-second heat exchanger, HEX3-third heat exchanger, HEX4-fourth heat exchanger, HEX5-fifth heat exchanger, HEX6-sixth Heat exchanger, HEX7-seventh heat exchanger, HEX-OP4-eighth heat exchanger, HEX-OP1-ninth heat exchanger;
OP1-第一正仲氢转化器、OP2-第二正仲氢转化器、OP3-第三正仲氢转化器、OP4-第四正仲氢转化器、A1-第一低温吸附器、A2-第二低温吸附器、A3-第三低温吸附器；OP1-first ortho-parahydrogen converter, OP2-second ortho-parahydrogen converter, OP3-third ortho-parahydrogen converter, OP4-fourth ortho-parahydrogen converter, A1-first cryogenic adsorber, A2- The second cryogenic adsorber, A3-the third cryogenic adsorber;
Cold Box-冷箱、D4200-液氢储罐、D4100-氢气液分离器、D3100-氮气液分离器、Buffer Tank-氢气缓冲罐；Cold Box-cold box, D4200-liquid hydrogen storage tank, D4100-hydrogen gas-liquid separator, D3100-nitrogen gas-liquid separator, Buffer Tank-hydrogen buffer tank;
CV04-加载阀、CV03-卸载阀、CV02-低压旁通阀、CV01-中压旁通阀、CV08-第八节流阀、CV09-第九节流阀、CV10-第十节流阀、CV12-第十二调节阀、CV13-第十三调节阀。CV04-loading valve, CV03-unloading valve, CV02-low pressure bypass valve, CV01-medium pressure bypass valve, CV08-eighth throttle valve, CV09-ninth throttle valve, CV10-tenth throttle valve, CV12 - Twelfth regulating valve, CV13 - Thirteenth regulating valve.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the solutions of the present invention, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only It is an embodiment of a part of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.
氢气液化装置在开车预冷阶段和稳定运行阶段具有不同的工艺要求；需要考虑如下几个问题：1、外接液氢储罐大热容，对于5TPD(5吨/天)和10TPD(10吨/天)氢气液化装置外接的液氢储罐容量大，热容大，需要考虑开车预冷阶段的液氢储罐预冷问题；2、稳定运行阶段，进入液氢储罐的须是仲氢含量合格的产品氢，产品氢中液相分数越高越好，最好是全液相，这样液氢储罐可以减少回气管线，降低液氢储罐罐体安全阀的压力；3、氢气液化装置进入稳定运行阶段后，循环气路进行封闭制冷循环，原料气路氢气原料气全部液化并经正仲氢转化后成为仲氢含量合格的产品氢进入液氢储罐。The hydrogen liquefaction device has different process requirements in the start-up pre-cooling stage and the stable operation stage; the following issues need to be considered: 1. The large heat capacity of the external liquid hydrogen storage tank, for 5TPD (5 tons/day) and 10TPD (10 tons/day) Day) The liquid hydrogen storage tank externally connected to the hydrogen liquefaction device has a large capacity and a large heat capacity, so it is necessary to consider the pre-cooling problem of the liquid hydrogen storage tank in the pre-cooling stage of the start-up; Qualified product hydrogen, the higher the liquid phase fraction in the product hydrogen, the better, preferably full liquid phase, so that the liquid hydrogen storage tank can reduce the return gas pipeline and reduce the pressure of the safety valve of the liquid hydrogen storage tank; 3. Hydrogen liquefaction After the device enters the stable operation stage, the circulating gas path conducts a closed refrigeration cycle, and the hydrogen raw material gas in the raw gas path is completely liquefied and converted into ortho-parahydrogen to become product hydrogen with qualified parahydrogen content and enter the liquid hydrogen storage tank.
为了解决如上问题，本发明提出了一种具有热虹吸式氢过冷器的氢气液化装置，在氢液化器开车预冷阶段，循环氢节流后得到含液氢的两相氢进入液氢储罐，对液氢储罐进行预冷降温；待液氢储罐降温到合适温度，比如50K后，氢气液化装置进入稳定生产阶段；本发明采用了热虹吸式氢过冷器，在稳定生产阶段，原料气路生成的气液两相氢被过冷成为过冷液氢，并同时进行正仲氢转化，生成仲氢含量合格的产品氢进入液氢储罐形成液氢产品；本发明综合考虑了氢液化器开车预冷阶段和稳定生产阶段的不同工艺要求，采用了热虹吸式氢过冷器，充分利用了液氢的潜热和显热；稳定运行阶段循环气路和原料气路不再连通，避免影响液氢产品的纯度；稳定运行阶段，液氢储罐的回气不再进入循环气路，避免造成循环气路中气体过多，增加氢液化器的整体调控复杂程度，也有利于保持氢液化器中循环气路和原料气路的热平衡；本氢气液化装置液化效率高，安全性好，能耗低。In order to solve the above problems, the present invention proposes a hydrogen liquefaction device with a thermosiphon hydrogen subcooler. In the pre-cooling stage of the hydrogen liquefier, the two-phase hydrogen containing liquid hydrogen is obtained after throttling the circulating hydrogen and enters the liquid hydrogen storage. tank, to pre-cool the liquid hydrogen storage tank; after the liquid hydrogen storage tank cools down to a suitable temperature, such as 50K, the hydrogen liquefaction device enters the stable production stage; , the gas-liquid two-phase hydrogen generated by the raw material gas path is supercooled into supercooled liquid hydrogen, and at the same time, it is transformed into ortho-parahydrogen to generate product hydrogen with qualified parahydrogen content and enter the liquid hydrogen storage tank to form a liquid hydrogen product; the present invention comprehensively considers The different process requirements of the start-up precooling stage and the stable production stage of the hydrogen liquefier are met, and a thermosiphon hydrogen subcooler is adopted to make full use of the latent and sensible heat of liquid hydrogen; the circulating gas path and the raw material gas path are no longer Connected to avoid affecting the purity of the liquid hydrogen product; in the stable operation stage, the return gas of the liquid hydrogen storage tank will no longer enter the circulation gas circuit, so as to avoid excessive gas in the circulation gas circuit and increase the overall regulation complexity of the hydrogen liquefier, and also It is beneficial to maintain the heat balance of the circulation gas path and the raw material gas path in the hydrogen liquefier; the hydrogen liquefaction device has high liquefaction efficiency, good safety and low energy consumption.
如图1所示，本发明实施例的一种具有热虹吸式氢过冷器的氢气液化装置，包括：中压氢气压缩机组CL，高压氢气压缩机组CH，氢气缓冲罐，冷箱Cold Box，液氮预冷装置，第一氢气透平膨胀机机组，第二氢气透平膨胀机机组，原料气路低温吸附器组，循环气路低温吸附器，换热器组，正仲氢转化器组，热虹吸式氢过冷器，常温调节阀，低温调节阀和节流阀，以及液氢储罐D4200。As shown in Figure 1, a hydrogen liquefaction device with a thermosiphon hydrogen subcooler according to an embodiment of the present invention includes: a medium-pressure hydrogen compressor unit CL, a high-pressure hydrogen compressor unit CH, a hydrogen buffer tank, a cold box Cold Box, Liquid nitrogen pre-cooling device, the first hydrogen turboexpander unit, the second hydrogen turboexpander unit, feed gas path cryogenic adsorber group, circulating gas path cryogenic adsorber group, heat exchanger group, ortho-parahydrogen converter group , Thermosiphon hydrogen subcooler, normal temperature regulating valve, low temperature regulating valve and throttle valve, and liquid hydrogen storage tank D4200.
液氮预冷装置，第一氢气透平膨胀机机组，第二氢气透平膨胀机机组，原料气路低温吸附器组，循环气路低温吸附器，换热器组，正仲氢转化器组，热虹吸式氢过冷器，低温调节阀和节流阀均安装于冷箱内；其中，正仲氢转化器组包括第一正仲氢转化器OP1、第二正仲氢转化器OP2、第三正仲氢转化器OP3、第四正仲氢转化器OP4；低温吸附器组包括第一低温吸附器A1和第二低温吸附器A2。Liquid nitrogen pre-cooling device, the first hydrogen turboexpander unit, the second hydrogen turboexpander unit, feed gas path cryogenic adsorber group, circulating gas path cryogenic adsorber group, heat exchanger group, ortho-parahydrogen converter group , a thermosyphon hydrogen subcooler, a low temperature regulating valve and a throttle valve are all installed in the cold box; wherein, the ortho-parahydrogen converter group includes the first ortho-parahydrogen converter OP1, the second ortho-parahydrogen converter OP2, The third ortho-parahydrogen converter OP3, the fourth ortho-parahydrogen converter OP4; the low-temperature adsorber group includes a first low-temperature adsorber A1 and a second low-temperature adsorber A2.
中压氢气压缩机组，高压氢气压缩机组都是无油活塞压缩机，组成氢气压缩机站；氢气缓冲罐Buffer Tank、加载阀CV04、卸载阀CV03、低压旁通阀CV02、中压旁通阀CV01组成氢液化器的气体管理模块；气体管理模块用来调节控制中压氢气压缩机组和高压氢气压缩机组进出口压力。The medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit are all oil-free piston compressors, forming a hydrogen compressor station; hydrogen buffer tank, loading valve CV04, unloading valve CV03, low-pressure bypass valve CV02, and medium-pressure bypass valve CV01 The gas management module that forms the hydrogen liquefier; the gas management module is used to adjust and control the inlet and outlet pressure of the medium-pressure hydrogen compressor unit and the high-pressure hydrogen compressor unit.
液氮预冷装置包括液氮入口管线、液氮入口管线调节阀CV06、氮气液分离器D3100、液氮管路、氮气液分离器出口管路、气氮排气管路及气氮回气管路等；液氮预冷装置用来预冷第一换热器，第二换热器以及第九换热器HEX-OP1；液氮预冷装置采用了热虹吸式液氮热交换器，充分利用了液氮的潜热和显热，预冷效率高。The liquid nitrogen pre-cooling device includes liquid nitrogen inlet pipeline, liquid nitrogen inlet pipeline regulating valve CV06, nitrogen gas-liquid separator D3100, liquid nitrogen pipeline, nitrogen gas-liquid separator outlet pipeline, gas nitrogen exhaust pipeline and gas nitrogen return pipeline etc.; the liquid nitrogen precooling device is used to precool the first heat exchanger, the second heat exchanger and the ninth heat exchanger HEX-OP1; the liquid nitrogen precooling device adopts a thermosiphon liquid nitrogen heat exchanger, making full use of The latent heat and sensible heat of liquid nitrogen are eliminated, and the precooling efficiency is high.
第一氢气透平膨胀机组由两个氢气透平E11和E12串联组成；第二氢气透平膨胀机组由两个氢气透平E21和E22串联组成；原料气路(第一气路)第一低温吸附器A1和第二低温吸附器A2并联，切换使用，一个工作，另一个可同时再生；循环路低温吸附器(第三低温吸附器)A3可在线手动再生，换热器组包括第一换热器HEX1、第二换热器HEX2、液氮正仲氢转化换热器(第九换热器)HEX-OP1、第三换热器HEX3、第四换热器HEX4、第五换热器HEX5、第六换热器HEX6、第七换热器HEX7及液氢正仲氢转化换热器(第八换热器)HEX-OP4。The first hydrogen turboexpander unit consists of two hydrogen turbines E11 and E12 connected in series; the second hydrogen turboexpander unit consists of two hydrogen turbines E21 and E22 connected in series; The adsorber A1 and the second low-temperature adsorber A2 are connected in parallel and switched to use, one works and the other can be regenerated at the same time; the low-temperature adsorber (the third low-temperature adsorber) A3 of the circulation path can be manually regenerated online, and the heat exchanger group includes the first exchange Heater HEX1, second heat exchanger HEX2, liquid nitrogen ortho-parahydrogen conversion heat exchanger (ninth heat exchanger) HEX-OP1, third heat exchanger HEX3, fourth heat exchanger HEX4, fifth heat exchanger HEX5, the sixth heat exchanger HEX6, the seventh heat exchanger HEX7 and the liquid hydrogen ortho-parahydrogen conversion heat exchanger (eighth heat exchanger) HEX-OP4.
第一换热器HEX1与液氢储罐D4200依次连接并形成第一气路，第一换热器HEX1、第八换热器HEX-OP4及液氢储罐D4200依次连接并形成第二气路，第一换热器HEX1的高压侧输入氢气通向第二气路；氢气液分离器D4100的上端与第一气路连接，氢气液分离器D4100的下端与第八换热器的一侧连接，第八换热器HEX-OP4的另一侧连接于氢气液分离器D4100的上端；氢气液分离器D4100的回流端通过第一换热器HEX1与气体管理模块连接并形成第三气路，液氢储罐D4200通过第一换热器HEX1与气体管理模块连接并形成第四气路。The first heat exchanger HEX1 is sequentially connected with the liquid hydrogen storage tank D4200 to form the first gas path, and the first heat exchanger HEX1, the eighth heat exchanger HEX-OP4 and the liquid hydrogen storage tank D4200 are sequentially connected to form the second gas path , the high-pressure side of the first heat exchanger HEX1 inputs hydrogen to the second gas path; the upper end of the hydrogen gas-liquid separator D4100 is connected to the first gas path, and the lower end of the hydrogen gas-liquid separator D4100 is connected to one side of the eighth heat exchanger , the other side of the eighth heat exchanger HEX-OP4 is connected to the upper end of the hydrogen gas-liquid separator D4100; the return end of the hydrogen gas-liquid separator D4100 is connected to the gas management module through the first heat exchanger HEX1 to form a third gas path, The liquid hydrogen storage tank D4200 is connected to the gas management module through the first heat exchanger HEX1 and forms the fourth gas path.
换热器包括输出端及回流端，输出端为气体流向液氢储罐方向一端的气路，即第一气路和第二气路；回流端为气体回流至第一换热器方向一端的气路，即第三气路和第四气路；换热器具有高压侧及低压侧，以图1方向为准，换热器的右侧为低压侧。The heat exchanger includes an output end and a return end. The output end is the gas path where the gas flows to the direction of the liquid hydrogen storage tank, that is, the first gas path and the second gas path; the return end is the gas path that flows back to the end of the first heat exchanger. Gas paths, namely the third gas path and the fourth gas path; the heat exchanger has a high-pressure side and a low-pressure side, refer to the direction in Figure 1, and the right side of the heat exchanger is the low-pressure side.
节流阀包括第八节流阀CV08、第九节流阀CV09和第十节流阀CV10，第十二调节阀CV12是开车调试阶段的快速降温管路阀门；第一正仲氢转化器OP1是内嵌在HEX-OP1中的液氮温度级正仲氢转化器，等温转化；第二正仲氢转化器OP2和第三正仲氢转化器OP3是绝热转化，第四正仲氢转化器OP4是内嵌在第八换热器HEX-OP4中的液氢温度级正仲氢转化器，等温转化。The throttle valves include the eighth throttle valve CV08, the ninth throttle valve CV09 and the tenth throttle valve CV10, the twelfth regulating valve CV12 is a rapid cooling pipeline valve in the commissioning stage; the first positive-parahydrogen converter OP1 It is a liquid nitrogen temperature-level ortho-parahydrogen converter embedded in HEX-OP1, isothermal reforming; the second ortho-parahydrogen converter OP2 and the third ortho-parahydrogen converter OP3 are adiabatic reforming, the fourth ortho-parahydrogen converter OP4 is a liquid hydrogen temperature-level ortho-parahydrogen converter embedded in the eighth heat exchanger HEX-OP4, with isothermal conversion.
氢气液分离器D4100，液氢正仲氢转化换热器HEX-OP4，注液管线7，液氢管线1，回气管线2，回气管线3构成了热虹吸式回路；本发明氢气液分离器D4100的液位高度高于液氢正仲氢转化换热器HEX-OP4的顶部，以保证换热器HEX-OP4的通道完全浸泡在液氢里边，这种设计利用了氢的密度差，充分利用了液氢的潜热和显热。Hydrogen-gas-liquid separator D4100, liquid hydrogen ortho-parahydrogen conversion heat exchanger HEX-OP4, liquid injection pipeline 7, liquid hydrogen pipeline 1, return gas pipeline 2, and return gas pipeline 3 constitute a thermosiphon loop; hydrogen gas-liquid separation in the present invention The liquid level of the device D4100 is higher than the top of the liquid hydrogen ortho-parahydrogen conversion heat exchanger HEX-OP4 to ensure that the channel of the heat exchanger HEX-OP4 is completely immersed in the liquid hydrogen. This design takes advantage of the density difference of hydrogen, The latent heat and sensible heat of liquid hydrogen are fully utilized.
在开车预冷阶段，循环气路的氢气经过管道6进入第九节流阀CV09，生成气液两相的流体，其中液氢用于预冷液氢储罐D4200，气相氢则经过管道10回气，经过第十二调节阀CV12回到第一换热器HEX1低压入口侧，快速降温；待液氢储罐D4200降温到合适温度，比如50K后，慢慢关闭第九节流阀CV09，同时慢慢开启第八节流阀CV08，D4100开始积液，待D4100液位达到一定高度，第十节流阀CV10开始节流，氢气液化装置进入稳定生产阶段。In the pre-cooling stage of start-up, the hydrogen in the circulating gas path enters the ninth throttle valve CV09 through the
用于预冷液氢储罐D4200的循环气液氢因为仲氢含量不合格，这部分液氢要被抛弃掉；在循环气液氢预冷液氢储罐D4200过程中，气体缓冲罐Buffer Tank中的氢气会减少，此时通过第十三调节阀CV13自原料气路向氢气缓冲罐Buffer Tank补气。The circulating gas-liquid hydrogen used for pre-cooling the liquid hydrogen storage tank D4200 is discarded because the parahydrogen content is unqualified; during the process of circulating gas-liquid hydrogen pre-cooling the liquid hydrogen storage tank D4200, the gas buffer tank The hydrogen in the tank will decrease, and at this time, the thirteenth regulating valve CV13 will supply gas from the raw material gas path to the hydrogen buffer tank Buffer Tank.
氢气液分离器D4100是氢气过冷器，氢气液分离器D4100底部液氢管道1内的过冷液氢用于冷却自原料气路来的气液两相流体，过冷液氢之后成为饱和氢气通过管道2进入氢气液分离器D4100；氢气液分离器D4100内饱和氢气通过管道3回气到第七换热器HEX7低压侧入口。The hydrogen gas-liquid separator D4100 is a hydrogen subcooler. The supercooled liquid hydrogen in the liquid hydrogen pipeline 1 at the bottom of the hydrogen gas-liquid separator D4100 is used to cool the gas-liquid two-phase fluid from the raw material gas path. After the supercooled liquid hydrogen becomes saturated hydrogen Enter the hydrogen gas-liquid separator D4100 through the pipeline 2; the saturated hydrogen in the hydrogen gas-liquid separator D4100 returns to the low-pressure side inlet of the seventh heat exchanger HEX7 through the pipeline 3.
原料氢气经过第十节流阀CV10节流成为气液两相的流体，经过第八换热器HEX-OP4，被氢气液分离器D4100底部液氢管道1来的过冷液氢过冷成为过冷液氢，并同时经过第四正仲氢转化器OP4进行等温正仲氢转化，成为仲氢含量合格的产品氢进入液氢储罐D4200。The raw material hydrogen is throttled by the tenth throttle valve CV10 to become a gas-liquid two-phase fluid. After passing through the eighth heat exchanger HEX-OP4, it is supercooled by the supercooled liquid hydrogen from the liquid hydrogen pipeline 1 at the bottom of the hydrogen-gas-liquid separator D4100 to become a supercooled fluid. Cool liquid hydrogen, and at the same time pass through the fourth ortho-parahydrogen converter OP4 for isothermal ortho-parahydrogen conversion, and become product hydrogen with qualified parahydrogen content and enter the liquid hydrogen storage tank D4200.
本申请氢气液化装置的工作过程如下：The working process of the hydrogen liquefaction device of this application is as follows:
循环氢路：Circulating hydrogen circuit:
(1)活塞高压氢气压缩机组CH排出的高压氢气进入冷箱。(1) The high-pressure hydrogen discharged from the piston high-pressure hydrogen compressor unit CH enters the cold box.
(2)进入冷箱Cold Box的高压氢气经过第一换热器HEX1和第二换热器HEX2被返流冷氢气及预冷用的LN冷却到一定温度后进入第三换热器HEX3降至更低温度，之后分成两股流，其中大部分进入两组透平串联(第一氢气透平膨胀机组及第二氢气透平膨胀机组)，中间降温的膨胀回路进行绝热膨胀制冷，变成低温中压的氢气回到第六换热器HEX6低压侧入口，并依次逆流依次通过第五换热器至第一换热器(HEX5～HEX1)，回收冷量后出冷箱ColdBox，再回到高压氢气压缩机组CH吸气端进行再次循环。(2) The high-pressure hydrogen gas entering the Cold Box passes through the first heat exchanger HEX1 and the second heat exchanger HEX2, is cooled to a certain temperature by the backflow cold hydrogen gas and the LN used for pre-cooling, and then enters the third heat exchanger HEX3 to drop to a certain temperature. Lower temperature, and then divided into two streams, most of which enter two sets of turbines in series (the first hydrogen turboexpander unit and the second hydrogen turboexpander unit), and the middle cooling expansion circuit performs adiabatic expansion refrigeration to become a low temperature The medium-pressure hydrogen returns to the inlet of the sixth heat exchanger HEX6 on the low-pressure side, and passes through the fifth heat exchanger to the first heat exchanger (HEX5~HEX1) sequentially in countercurrent. The CH suction end of the high-pressure hydrogen compressor unit is recirculated.
(3)分流的另一部分高压氢气继续通过第四换热器至第七换热器(HEX4～HEX7)被回流的低温低压氢气冷却；在开车预冷阶段，循环氢经过第九节流阀CV09节流后得到含液氢的两相氢进入液氢储罐D4200，对液氢储罐D4200进行预冷降温；液氢储罐D4200降温到合适温度，比如50K后，慢慢关闭节流阀CV09，同时慢慢开启第八节流阀CV08，氢气液分离器D4100开始积液，待氢气液分离器D4100液位达到一定高度，第十节流阀CV10开始节流，氢液化器进入稳定生产阶段；循环氢经过第八节流阀CV08节流后得到含液氢的两相氢进入氢气液分离器D4100；氢气液分离器D4100和第八换热器HEX-OP4形成热虹吸式回路，充分利用氢的密度差，对原料气路生成的液氢进行再次冷却，使之生成过冷液氢，并同时对过冷液氢进行OP转化，生成仲氢含量合格的产品氢进入液氢储罐D4200形成液氢产品；本申请氢气液分离器D4100液位高度必须高于第八换热器HEX-OP4顶部，以保证第八换热器HEX-OP4的通道完全浸泡在液氢里边。(3) The other part of the split high-pressure hydrogen continues to pass through the fourth heat exchanger to the seventh heat exchanger (HEX4～HEX7) and is cooled by the low-temperature and low-pressure hydrogen that flows back; in the pre-cooling stage of starting up, the circulating hydrogen passes through the ninth throttle valve CV09 After throttling, the two-phase hydrogen containing liquid hydrogen enters the liquid hydrogen storage tank D4200, and pre-cools the liquid hydrogen storage tank D4200; after the liquid hydrogen storage tank D4200 cools down to an appropriate temperature, such as 50K, slowly close the throttle valve CV09 , and at the same time slowly open the eighth throttle valve CV08, the hydrogen gas-liquid separator D4100 begins to accumulate liquid, when the liquid level of the hydrogen gas-liquid separator D4100 reaches a certain height, the tenth throttle valve CV10 starts to throttle, and the hydrogen liquefier enters the stable production stage The circulating hydrogen is throttled by the eighth throttle valve CV08 to obtain two-phase hydrogen containing liquid hydrogen and enters the hydrogen gas-liquid separator D4100; the hydrogen gas-liquid separator D4100 and the eighth heat exchanger HEX-OP4 form a thermosyphon loop, making full use of The density of hydrogen is different, and the liquid hydrogen generated by the raw material gas path is cooled again to produce supercooled liquid hydrogen, and at the same time, the OP conversion is performed on the supercooled liquid hydrogen to generate product hydrogen with qualified parahydrogen content and enter the liquid hydrogen storage tank D4200 Form liquid hydrogen products; the liquid level of the hydrogen gas-liquid separator D4100 in this application must be higher than the top of the eighth heat exchanger HEX-OP4 to ensure that the channel of the eighth heat exchanger HEX-OP4 is completely immersed in liquid hydrogen.
(4)氢气液分离器D4100中产生的饱和氢蒸汽通过回气管道3返流经过第七换热器HEX7对节流前的高压氢气进行冷却，并依次逆流通过第六换热器至第一换热器(HEX6～HEX1)，回收冷量后出冷箱，再回到中压压缩机CL吸气端，通过中压压缩机CL压缩到中压压力，并与透平回气的中压氢气进行混合。(4) The saturated hydrogen vapor generated in the hydrogen gas-liquid separator D4100 flows back through the return gas pipeline 3 and passes through the seventh heat exchanger HEX7 to cool the high-pressure hydrogen before throttling, and then passes through the sixth heat exchanger to the first The heat exchanger (HEX6～HEX1) recovers the cooling capacity and exits the cold box, then returns to the suction end of the medium-pressure compressor CL, and is compressed to the medium-pressure pressure by the medium-pressure compressor CL, and is connected with the medium-pressure return air of the turbine. hydrogen for mixing.
(5)开车预冷阶段，液氢储罐D4200中的回气自第十二调节阀CV12返回到HEX1低压侧入口，进行快速降温预冷。(5) During the start-up pre-cooling stage, the return air in the liquid hydrogen storage tank D4200 returns from the twelfth regulating valve CV12 to the inlet of the low-pressure side of HEX1 for rapid cooling and pre-cooling.
(6)用于预冷液氢储罐D4200的循环气液氢因为仲氢含量不合格，这部分液氢要被抛弃掉；在循环气液氢预冷液氢储罐D4200过程中，气体缓冲罐Buffer Tank中的氢气会减少，此时通过第十三调节阀CV13自原料气路向气体缓冲罐Buffer Tank补气。(6) The circulating gas-liquid hydrogen used for pre-cooling the liquid hydrogen storage tank D4200 must be discarded because the parahydrogen content is unqualified; The hydrogen in the Buffer Tank will decrease, and at this time, the thirteenth regulating valve CV13 will supply gas from the raw material gas path to the buffer tank.
原料气的冷却及液化过程如下：The cooling and liquefaction process of raw gas is as follows:
(1)原料氢气(正常氢)经过第一换热器HEX1和第二换热器HEX2被返流冷氢气及预冷用的LN冷却到一定温度后进入液氮浸泡的第一正仲氢转化器OP1内进行等温正仲氢转化，同时将反应热通过液氮排出。(1) The raw material hydrogen (normal hydrogen) passes through the first heat exchanger HEX1 and the second heat exchanger HEX2, is cooled to a certain temperature by the backflow cold hydrogen gas and the LN used for pre-cooling, and then enters the first ortho-parahydrogen conversion soaked in liquid nitrogen The isothermal ortho-parahydrogen conversion is carried out in the device OP1, and the reaction heat is discharged through liquid nitrogen at the same time.
(2)被液氮冷却后的氢气仲氢比例有所上升，随后进入第三换热器HEX3和第四换热器HEX4被返流冷氢气进一步冷却，并进入第二正仲氢转化器OP2，由于没有相应的低温液体进行等温放热，此时的正仲氢转化是绝热转化，在仲氢比例升高的同时，低温液体的温度也会提高，因此将第二正仲氢转化器OP2出口处的氢气重新引入第四换热器HEX4热端入口，并在第四换热器HEX4内通过回流气体将反应热带走。(2) The para-hydrogen ratio of hydrogen cooled by liquid nitrogen has increased, and then enters the third heat exchanger HEX3 and the fourth heat exchanger HEX4 to be further cooled by backflow cold hydrogen, and enters the second ortho-parahydrogen converter OP2 , since there is no corresponding low-temperature liquid for isothermal heat release, the ortho-parahydrogen conversion at this time is an adiabatic conversion. When the para-hydrogen ratio increases, the temperature of the low-temperature liquid will also increase, so the second ortho-parahydrogen converter OP2 The hydrogen at the outlet is reintroduced into the hot end inlet of the fourth heat exchanger HEX4, and the heat of reaction is taken away by the reflux gas in the fourth heat exchanger HEX4.
(3)从第四换热器HEX4出来的低温氢气进入第五换热器HEX5和第六换热器HEX6，同时被返流冷氢气进一步冷却，进入第三正仲氢转化器OP3，氢气在第三正仲氢转化器OP3内发生正仲氢绝热转化，将第三正仲氢转化器OP3出口处的氢气重新引入第六换热器HEX6热端入口，并在第六换热器HEX6内通过回流气体将反应热带走。(3) The low-temperature hydrogen from the fourth heat exchanger HEX4 enters the fifth heat exchanger HEX5 and the sixth heat exchanger HEX6, and is further cooled by the backflow cold hydrogen at the same time, and enters the third ortho-parahydrogen converter OP3. Ortho-parahydrogen adiabatic conversion occurs in the third ortho-parahydrogen converter OP3, and the hydrogen at the outlet of the third ortho-parahydrogen converter OP3 is reintroduced into the hot end inlet of the sixth heat exchanger HEX6, and is transferred in the sixth heat exchanger HEX6 The heat of reaction is removed by the refluxing gas.
(4)从第六换热器HEX6出来的低温氢气进入第七换热器HEX7进一步被回流气体冷却，此时温度已经达到节流前的最佳温度。由于节流后的两相氢的仲氢浓度达不到95％，此时需要在第十节流阀CV10后增加一个第四正仲氢转化器OP4；第四正仲氢转化器OP4安装在第八换热器HEX-OP4中，被液氢浸泡，第四正仲氢转化器OP4是一个等温型的正仲氢转化器。(4) The low-temperature hydrogen from the sixth heat exchanger HEX6 enters the seventh heat exchanger HEX7 and is further cooled by the reflux gas, and the temperature has reached the optimal temperature before throttling. Since the parahydrogen concentration of the two-phase hydrogen after throttling cannot reach 95%, a fourth ortho-parahydrogen converter OP4 needs to be added after the tenth throttle valve CV10; the fourth ortho-parahydrogen converter OP4 is installed in The eighth heat exchanger HEX-OP4 is immersed in liquid hydrogen, and the fourth ortho-parahydrogen converter OP4 is an isothermal ortho-parahydrogen converter.
(5)经过第四正仲氢转化器OP4后，仲氢的浓度超过95％，且被第八换热器HEX-OP4完全冷却，形成具有一定过冷度的液氢，进入液氢储罐D4200内，形成液氢产品。(5) After passing through the fourth ortho-parahydrogen converter OP4, the concentration of parahydrogen exceeds 95%, and is completely cooled by the eighth heat exchanger HEX-OP4 to form liquid hydrogen with a certain degree of supercooling, which enters the liquid hydrogen storage tank In D4200, a liquid hydrogen product is formed.
(6)稳定运行阶段循环气路和原料气路不再连通，避免影响液氢产品的纯度；稳定运行阶段，液氢储罐D4200的回气不再进入循环气路，避免造成循环气路中气体过多，增加氢液化器的整体调控复杂程度，也有利于保持氢液化器中循环气路和原料气路的热平衡。(6) During the stable operation stage, the circulation gas path and the raw material gas path are no longer connected to avoid affecting the purity of the liquid hydrogen product; during the stable operation stage, the return gas of the liquid hydrogen storage tank D4200 will no longer enter the cycle gas path, so as to avoid causing damage in the cycle gas path. Too much gas increases the complexity of the overall regulation of the hydrogen liquefier, and is also conducive to maintaining the heat balance of the circulating gas path and the raw material gas path in the hydrogen liquefier.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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