JP2018177614A - Hydrogen production system using is process and iodine recovery method - Google Patents
Hydrogen production system using is process and iodine recovery method Download PDFInfo
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011630 iodine Substances 0.000 title claims abstract description 63
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000011084 recovery Methods 0.000 title claims description 22
- 239000007789 gas Substances 0.000 claims abstract description 69
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims abstract description 30
- 230000001172 regenerating effect Effects 0.000 claims abstract description 28
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000007132 Bunsen reaction Methods 0.000 claims abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- 230000008021 deposition Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 229940071870 hydroiodic acid Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DORNNPUYSLRGNT-UHFFFAOYSA-N [I].I Chemical compound [I].I DORNNPUYSLRGNT-UHFFFAOYSA-N 0.000 description 1
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- WXDJHDMIIZKXSK-UHFFFAOYSA-N iodine dioxide Inorganic materials O=I=O WXDJHDMIIZKXSK-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
Description
本発明は、例えば、高温ガス炉から得られる高熱を利用し、ＩＳ（ヨウ素硫黄）プロセスを用いて水を熱分解し、水素を製造するシステムに係り、特に水素製造システムを構成する機器や配管内でのヨウ素の析出を防止した水素製造システム及びそのシステムに適用可能なヨウ素回収方法に関する。 The present invention relates to, for example, a system for producing hydrogen by pyrolyzing water using an IS (iodine sulfur) process using high heat obtained from a high temperature gas furnace, and in particular, equipment and piping that constitute the hydrogen production system The present invention relates to a hydrogen production system in which iodine precipitation is prevented and an iodine recovery method applicable to the system.
ＩＳプロセスは、図１に示されるような高温ガス炉を熱源とする水素製造システムにおいて、効率的な水素製造方法として期待されている。熱化学法であるＩＳプロセスは、ブンゼン反応（硫酸とヨウ化水素の生成反応）、硫酸の熱分解反応、ヨウ化水素の熱分解反応の３化学反応工程により構成され、二酸化炭素を発生することなく、高温ガス炉で発生する高温ガスを利用して、原料である水を分解して水素を製造する。 The IS process is expected as an efficient hydrogen production method in a hydrogen production system using a high temperature gas furnace as a heat source as shown in FIG. The IS process, which is a thermochemical method, is composed of three chemical reaction steps of Bunsen reaction (production reaction of sulfuric acid and hydrogen iodide), thermal decomposition reaction of sulfuric acid, and thermal decomposition reaction of hydrogen iodide to generate carbon dioxide Instead, the high-temperature gas generated in the high-temperature gas furnace is used to decompose water as a raw material to produce hydrogen.
ここで、ブンゼン反応の化学反応式は、図２に模式的に示すように、具体的には以下のように表される。 Here, the chemical reaction formula of the Bunsen reaction is specifically expressed as follows, as schematically shown in FIG.
SO2 + I2+ 2H2O → 2HI + H2SO4 SO 2 + I 2 + 2H 2 O → 2HI + H 2 SO 4
ブンゼン反応工程においては、二酸化硫黄（SO2）ガスをヨウ素(I2)と水（2 H2O）の混合物中に導入することで、共に強酸性を示す、軽液相（硫酸）及び重液相（ポリヨウ化水素酸（HI、I2、H2Oの混合物））に液-液の二相分離する生成溶液が得られる。 In the Bunsen reaction process, sulfur dioxide (SO 2 ) gas is introduced into a mixture of iodine (I 2 ) and water (2 H 2 O) to show both strongly acidic, light liquid phase (sulfuric acid) and heavy A product solution is obtained which is liquid-liquid phase separated (liquid mixture (a mixture of polyhydroiodic acid (HI, I 2 , H 2 O)).
軽液相のH2SO4及び重液相の2HIは、それぞれ別々の系統によって、次の反応をもたらされ、それぞれ酸素及び水素を生成する。 The H 2 SO 4 in the light liquid phase and 2HI in the heavy liquid phase are brought to the next reaction by separate systems to produce oxygen and hydrogen, respectively.
H2SO4 → H2O + SO2 + 0.5O2
2HI → H2 + I2
H 2 SO 4 → H 2 O + SO 2 + 0.5 O 2
2HI → H 2 + I 2
ＩＳプロセスは、水以外のヨウ素、二酸化硫黄の反応物質がプロセス内で繰り返し使用する閉サイクルであるため、環境に優しく、非常に効率的に水素を生成できるプロセスとして注目されている。 The IS process is attracting attention as a process that can generate hydrogen very environmentally-friendly and very efficiently because it is a closed cycle in which iodine and sulfur dioxide reactants other than water are repeatedly used in the process.
そのような水素製造システムの一例を、図３を参照して説明する。まず、図の中央に示されたブンゼン反応器に水（2H2O）とヨウ素(I2)ガスが供給され、そこに二酸化硫黄（SO2）ガスが導入され、ブンゼン反応を起こさせる。その結果得られるH2SO4と2HIは、二相分離器に送られ、ここでヨウ化水素（HI）を主成分とする重液と硫酸（H2SO4）を主成分とする軽液に分離させられ、それぞれ別の系統に送られる。 An example of such a hydrogen production system is described with reference to FIG. First, water (2H 2 O) and iodine (I 2 ) gas are supplied to the Bunsen reactor shown at the center of the figure, and sulfur dioxide (SO 2 ) gas is introduced therein to cause the Bunsen reaction. The resulting H 2 SO 4 and 2 HI are sent to a two-phase separator, where heavy liquid containing hydrogen iodide (HI) as the main component and light liquid containing sulfuric acid (H 2 SO 4 ) as the main component Separated and sent to different lines.
ヨウ化水素（HI）は精製・濃縮された後、ヨウ化水素（HI）蒸留塔で気体として分離される。その後、再生熱交換器を通してヨウ化水素（HI）分解器に送られ、水素（H2）、ヨウ素（I2）などから成る混合ガスに熱分解させられる。これらの混合ガスは、再度再生熱交換器を通された後、HI-I2回収分離器に送られ、最終的に水素分離塔を介して水素（H2）として取り出される。 Hydrogen iodide (HI) is purified and concentrated and then separated as a gas in a hydrogen iodide (HI) distillation column. Thereafter, it is sent to a hydrogen iodide (HI) decomposer through a regenerative heat exchanger, and thermally decomposed into a mixed gas composed of hydrogen (H 2 ), iodine (I 2 ) and the like. These mixed gases are again passed through the regenerative heat exchanger, and then sent to the HI-I 2 recovery separator, and finally taken out as hydrogen (H 2 ) through the hydrogen separation column.
一方、硫酸（H2SO4）は、精製された後、硫酸分解反応工程の硫酸濃縮塔にて濃縮され、硫酸分解器に送られる。硫酸分解器において、硫酸蒸発によって気相化され、三酸化硫黄（SO3）などを含む混合気体とされ、触媒にて二酸化硫黄（SO2）等に分解させられた後、SO2ガス分離器を介して前述のブンゼン反応器に送られる。 On the other hand, sulfuric acid (H 2 SO 4 ) is purified and then concentrated in the sulfuric acid concentration column of the sulfuric acid decomposition reaction step and sent to a sulfuric acid decomposer. In a sulfuric acid decomposer, it is vaporized by sulfuric acid evaporation, made into a mixed gas containing sulfur trioxide (SO 3 ) and the like, and after being decomposed into sulfur dioxide (SO 2 ) and the like by a catalyst, a SO 2 gas separator Through to the aforementioned Bunsen reactor.
上述の従来技術では、大きく分けて以下のような課題がある。
（１）ヨウ素を含む高温の混合ガスは、まず、HI分解器の後段にある再生熱交換器で冷却されるが、熱交換器内部を流通する混合ガスの温度は能動的に制御することができず、再生熱交換器の内部でヨウ素が析出しやすい。
（２-１）水素を発生させるHI分解反応工程（図３の紙面左端）では、水素以外にヨウ素やヨウ化水素を含む混合ガスが生成され、目的物の水素を分離する過程で行われる冷却時に、ヨウ素がHI-I2回収分離器内に析出し易い。
（２-２）ヨウ素を含む混合ガスを冷却して水素ガスを分離する際，ヨウ素が析出し，配管を閉塞させる可能性がある。
The above-described prior art is roughly divided into the following problems.
(1) The high-temperature mixed gas containing iodine is first cooled by the regenerative heat exchanger downstream of the HI decomposer, but the temperature of the mixed gas flowing inside the heat exchanger can be actively controlled It is not possible to easily precipitate iodine inside the regenerative heat exchanger.
(2-1) In the HI decomposition reaction step (left end of the sheet of FIG. 3) for generating hydrogen, a mixed gas containing iodine and hydrogen iodide in addition to hydrogen is generated, and the cooling is performed in the process of separating the target hydrogen Sometimes, iodine is likely to precipitate in the HI-I 2 recovery separator.
(2-2) When the mixed gas containing iodine is cooled to separate hydrogen gas, iodine may be deposited to clog the piping.
従って、本発明の目的は、ＩＳプロセスを用いて水素を製造するシステムのHI分解反応工程において、処理中に各機器や配管内でヨウ素が析出することを防止できる水素製造システムを提供することにある。 Therefore, an object of the present invention is to provide a hydrogen production system capable of preventing iodine from being precipitated in each apparatus and piping during processing in the HI decomposition reaction step of the system for producing hydrogen using IS process is there.
上記目的を達成するため本発明に係る水素製造システムにおいては、大きく分けて次のような解決手段を講じている。 In order to achieve the above object, in the hydrogen production system according to the present invention, the following solutions are roughly classified.
（１）予備加熱器による再生熱交換器内での混合ガスの低温化防止
再生熱交換器内部で混合ガスがヨウ素析出温度（120℃）より低温にならないよう、これと熱交換する低温側プロセス流体の温度を能動的に制御するようにした。再生熱交換器を流れるプロセス流体は水素製造量によって流量が変化し、再生熱交換器の交換熱量が変動するため、低温側プロセス流体を昇温する予備加熱器を導入し、いかなる条件でもヨウ素を析出させないように、熱交換する混合ガスを固体ヨウ素が析出しない温度以上に間接的に制御するようにした。
(1) Prevention of temperature reduction of mixed gas in the regenerative heat exchanger by the preheater Low temperature side process of exchanging heat with the mixed gas so that the temperature of the mixed gas does not become lower than iodine precipitation temperature (120 ° C) inside the regenerative heat exchanger The temperature of the fluid was actively controlled. The process fluid flowing through the regenerative heat exchanger changes its flow rate depending on the amount of hydrogen production, and the heat exchange amount of the regenerative heat exchanger fluctuates. Therefore, introduce a preheater that raises the temperature of the low-temperature process fluid and In order not to precipitate, the mixed gas to be heat-exchanged was indirectly controlled to a temperature at which solid iodine does not precipitate or more.
（２）高温混合ガスと水とを直接接触させて溶液化
ヨウ素を含む混合ガスに水を注入することによりヨウ素を溶解する溶媒（ヨウ化水素酸）を生成させ、これにヨウ素を溶解させることで冷却過程でも常時流体とする。ヨウ素は水には溶解しにくいため、充填塔を用いて、塔上部から少量の水を流下させつつ，高温に維持したままの混合ガスを上昇させて、直接接触させる。充填塔の上部では水がヨウ素濃度の薄くなった混合ガスと接触し、混合ガス中に含まれる未分解HIガスを吸収することにより溶媒となるヨウ化水素酸を生成し，塔下部にてヨウ素濃度の濃い混合ガスと溶媒が接触しヨウ素を溶解させる。
(2) Solution by bringing the high temperature mixed gas and water into direct contact to form a solution Pouring water into the mixed gas containing iodine to form a solvent (hydroiodic acid) that dissolves iodine, and dissolving iodine in this In the cooling process, the fluid is always used. Since iodine is difficult to dissolve in water, a small amount of water is allowed to flow down from the top of the column while the mixed gas kept at a high temperature is raised and brought into direct contact using a packed column. At the upper part of the packed column, water comes in contact with the mixed gas with a reduced iodine concentration, and absorbs the uncracked HI gas contained in the mixed gas to form hydroiodic acid as a solvent, and iodine in the lower part of the column The mixed gas of high concentration comes in contact with the solvent to dissolve iodine.
具体的には、本発明の一つの観点に係る水素製造システムでは、再生熱交換器内でのヨウ素の析出を防止するため、次のような手段を設けている。すなわち、ブンゼン反応後に得られるヨウ化水素（HI）を気化させた後、再生熱交換器を通してヨウ化水素（HI）分解器に送り込み、水素（H2）やヨウ素（I2）などから成る混合ガスに熱分解した後、再度前記再生熱交換器を介してHI-I2回収分離器に送り、最終的に水素を分離回収するＩＳプロセスを用いた水素製造システムにおいて、前記再生熱交換器の前段に予備加熱器を設け、前記再生熱交換器内部で前記混合ガスがヨウ素析出温度より低温にならないよう、これと熱交換する低温側プロセス流体の温度を能動的に制御するようにしている。 Specifically, in the hydrogen production system according to one aspect of the present invention, the following means are provided in order to prevent the precipitation of iodine in the regenerative heat exchanger. That is, after hydrogen iodide (HI) obtained after the Bunsen reaction is vaporized, it is sent to a hydrogen iodide (HI) decomposer through a regenerative heat exchanger to mix hydrogen (H 2 ), iodine (I 2 ), etc. After being pyrolyzed into gas, the regenerated heat exchanger is sent to the HI-I 2 recovery separator again through the regenerative heat exchanger, and finally the hydrogen is separated and recovered in the hydrogen production system using the IS process. A preheater is provided at the front stage, and the temperature of the low temperature side process fluid that exchanges heat with the inside of the regenerative heat exchanger is controlled actively so that the mixed gas does not become lower than the iodine precipitation temperature.
さらに、本発明の別な観点での水素製造システムでは、下流に設けられたHI-I2回収分離器でのヨウ素の析出を防止するため、次の手段を設けている。すなわち、前記の新規な水素製造装置において、さらにHI-I2回収分離器の最上部に水注入手段を設け、ヨウ素を含む前記混合ガスに水を注入することによりヨウ素を溶解する溶媒を生成させ、これにヨウ素を溶解させることで冷却過程でも常時流体とするようにしている。 Furthermore, in the hydrogen production system according to another aspect of the present invention, the following means are provided in order to prevent the precipitation of iodine in the HI-I 2 recovery separator provided downstream. That is, in the novel hydrogen production apparatus described above, water injection means is further provided at the top of the HI-I 2 recovery separator, and water is injected into the mixed gas containing iodine to generate a solvent that dissolves iodine. By dissolving iodine in this, it is always made to be a fluid even in the cooling process.
さらに具体的には、上述の水素製造システムでは、前記HI-I2回収分離器を、塔下部付近から塔上部付近までラシヒリングが充填された充填塔で構成し、前記充填塔の塔上部から水を流下させつつ，高温に維持したままの前記混合ガスを上昇させ、前記水と前記混合ガスを直接接触させ、前記充填塔の塔上部では水がヨウ素濃度の薄くなった混合ガス中に含まれる未分解HIガスを吸収することにより溶媒となるヨウ化水素酸を生成し，塔下部にて溶媒とヨウ素濃度の濃い前記混合ガスを接触させてヨウ素を溶解させている。 More specifically, in the above-mentioned hydrogen production system, the HI-I 2 recovery separator comprises a packed column packed with Raschig rings from near the bottom of the column to near the top of the column, and water from the top of the column The mixed gas as it is maintained at a high temperature is raised while flowing down, and the water and the mixed gas are brought into direct contact, and water is contained in the mixed gas having a reduced iodine concentration at the top of the packed column By absorbing the undecomposed HI gas, hydroiodic acid as a solvent is generated, and the solvent is made to contact the mixed gas having a high concentration of iodine at the bottom of the column to dissolve iodine.
本発明によれば、ＩＳプロセスを用いた水素製造システムにおいて、通常ヨウ素の析出が起こり易い機器に、析出を能動的に防止する手段を備えているので、各種機器の性能を長期にわたって保持することができる。 According to the present invention, in a hydrogen production system using an IS process, a device in which precipitation of iodine usually tends to occur is provided with means for actively preventing precipitation, so that performance of various devices is maintained over a long period of time. Can.
以下、図３及び図４を参照して、本発明について詳細に説明する。図４において、HI蒸留塔で分離・気化されたヨウ化水素ガスは、予備加熱器10に送られ、その後再生熱交換器20に送られる。再生熱交換器20で熱交換されたヨウ化水素ガスは、HI分解器30に送られ、ここでH2,I2,HIから成る混合ガスとされ、再度再生熱交換器20に送られる。
Hereinafter, the present invention will be described in detail with reference to FIGS. 3 and 4. In FIG. 4, hydrogen iodide gas separated and vaporized in the HI distillation column is sent to the preheater 10 and then sent to the
従来構成では、HI蒸留塔からのヨウ化水素ガスを予備加熱器10によって十分昇温させていないため、前記混合ガスが再度再生熱交換器20を通る際に、図４に示されているようにヨウ素が熱交換壁に析出してしまう恐れがあった。図４ではこの状態をわかり易く示すために、あえて従来技術において析出したヨウ素も図示している。しかし、本発明では予備加熱器10においてヨウ化水素ガスをヨウ素析出温度（120℃）よりも十分高い温度に加熱して、ヨウ化水素ガスの再生熱交換器20への入口温度を十分高め、HI分解器30からの前記混合ガスが再生熱交換器20を再度通過する際にヨウ素析出温度以下に降下しないようにしているので、本発明では、ここに図示したようなヨウ素の析出は起こらない。
In the conventional configuration, since the hydrogen iodide gas from the HI distillation column is not sufficiently heated by the preheater 10, as shown in FIG. 4 when the mixed gas passes through the
なお、特に図示されていないが、HI-I2回収分離器40に与えられる混合ガスの温度がヨウ素析出温度以下に降下しないように、再生熱交換器２０の出口部に温度検出器を設け、その検出温度に応じて予備加熱器10の加熱温度をフィードバック制御することがより望ましい。
Although not particularly shown, a temperature detector is provided at the outlet of the
再生熱交換器20を再通過した前記混合ガスは加熱された後、HI-I2回収分離器40に送られる。図４に示されているように、本発明では、HI-I2回収分離器40は図4に示されるように塔下部付近から塔上部付近までラシヒリングが充填された充填塔で構成されている。充填塔の塔上部には外部から充填塔の上部に水を引き込むための水注入管（図示せず）が設けられている。
The mixed gas repassed through the
充填塔40の塔上部から水を少しずつ流下させつつ、高温に維持したままの前記混合ガスを上昇させ、前記水と前記混合ガスを直接接触させる。ラシヒリング41は、ガラス製の短い筒であって、気液の接触効率を上げるため、隙間なく充填されている。前記充填塔の塔上部では水がヨウ素濃度の薄い混合ガス中に含まれる未分解HIガスを吸収することにより溶媒となるヨウ化水素酸を生成し、塔下部にて溶媒とヨウ素濃度の濃い前記混合ガスを接触させてヨウ素を溶解させている。 While the water is allowed to gradually flow down from the top of the packed column 40, the mixed gas kept at a high temperature is raised to bring the water and the mixed gas into direct contact with each other. The Raschig ring 41 is a short glass cylinder, and is filled without gaps in order to increase the gas-liquid contact efficiency. In the upper part of the packed column, the water absorbs the undecomposed HI gas contained in the mixed gas with a low iodine concentration to generate hydroiodic acid as a solvent, and the lower part of the column is rich in the solvent and iodine concentration. The mixed gas is brought into contact to dissolve iodine.
本発明では、HI-I2回収分離器40を充填塔として、充填塔40の塔上部から水を供給し、ヨウ素溶解用の溶媒（ヨウ化水素酸）を作成し、溶媒によってヨウ素を吸収させているので、溶液中からヨウ素が析出することがない。 In the present invention, water is supplied from the top of the packed column 40 with the HI-I 2 recovery separator 40 as a packed column, a solvent for dissolving iodine (hydroiodic acid) is prepared, and the solvent absorbs iodine. Therefore, iodine does not precipitate out of the solution.
以上の実施例では、ヨウ素の析出沈着を防止した水素製造システムの構成について説明したが、上述のHI-I2回収分離器40は、一つの汎用性のあるヨウ素回収器として捉えることもできる。すなわち、上述のヨウ素回収器は、「塔下部付近から塔上部付近までラシヒリングが充填された充填塔から構成され、前記充填塔の塔上部から水を流下させつつ，前記充填塔の塔下部からヨウ化水素ガスを供給し、前記充填塔内を上昇させ、前記水と前記ヨウ化水素ガスを直接接触させ、前記充填塔の塔上部では水がヨウ化水素ガスを吸収することにより溶媒となるヨウ化水素酸を生成し，塔下部にて前記溶媒とヨウ化水素ガスを接触させてヨウ素を溶解させる構成を持つ単独の機器」としても捉えることができる。 In the above embodiments, the configuration of the hydrogen production system in which precipitation deposition of iodine is prevented has been described, but the above-described HI-I 2 recovery separator 40 can also be regarded as one versatile iodine recovery unit. That is, the above-mentioned iodine recovery unit is composed of a packed column filled with Raschig rings from the lower part of the column to the upper part of the column, and water is allowed to flow down from the upper part of the packed column The hydrogen chloride gas is supplied, the inside of the packed tower is raised, the water and the hydrogen iodide gas are brought into direct contact, and the water in the upper part of the packed tower becomes a solvent by absorbing the hydrogen iodide gas. It can be considered as a single device having a configuration in which hydrobromic acid is generated and the solvent and hydrogen iodide gas are brought into contact in the lower part of the column to dissolve iodine.
また、以上の実施例では、HI-I2回収分離器40として充填塔を例に説明したが、本発明のヨウ素回収方法の原理は、充填塔に限らず、他の気液接触器であっても同様に適用可能である。 Also, in the above embodiments, a packed column was described as an example of the HI-I 2 recovery separator 40, but the principle of the iodine collection method of the present invention is not limited to the packed column, but other gas-liquid contactors. The same is applicable.
10…予備加熱器
20…再生熱交換器
30…HI分解器
40…HI-I2回収分離器(充填塔)
10 ... Preheater
20 ... Regeneration heat exchanger
30 ... HI decomposer
40 ... HI-I 2 recovery separator (packing tower)
Claims (5)
前記再生熱交換器の前段に予備加熱器を設け、前記再生熱交換器内部で前記混合ガスがヨウ素析出温度より低温にならないよう、これと熱交換する低温側プロセス流体の温度を能動的に制御するようにしたことを特徴とする水素製造システム。 After hydrogen iodide (HI) obtained after the Bunsen reaction is vaporized, it is sent to a hydrogen iodide (HI) decomposer through a regenerative heat exchanger to form a mixed gas consisting of hydrogen (H 2 ), iodine (I 2 ), etc. In the hydrogen production system using the IS process, after thermal decomposition, it is again sent to the HI-I 2 recovery separator via the regenerative heat exchanger, and hydrogen is finally separated and recovered,
A preheater is provided at the front stage of the regenerative heat exchanger, and the temperature of the low-temperature process fluid in heat exchange with the mixed gas is actively controlled so that the mixed gas does not become lower than the iodine deposition temperature inside the regenerative heat exchanger. The hydrogen production system characterized by having done.
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