JPH0269303A - Reformer - Google Patents
ReformerInfo
- Publication number
- JPH0269303A JPH0269303A JP21972088A JP21972088A JPH0269303A JP H0269303 A JPH0269303 A JP H0269303A JP 21972088 A JP21972088 A JP 21972088A JP 21972088 A JP21972088 A JP 21972088A JP H0269303 A JPH0269303 A JP H0269303A
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- catalyst
- gas
- main reactor
- catalyst bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000002407 reforming Methods 0.000 claims abstract description 23
- 238000000629 steam reforming Methods 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 57
- 239000002994 raw material Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 231100000572 poisoning Toxicity 0.000 abstract description 7
- 230000000607 poisoning effect Effects 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 239000006200 vaporizer Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- -1 methanol and ethanol Chemical class 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000006057 reforming reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［発明の目的］
［産業上の利用分野］
本発明はメタノール、エタノール等の低級アルコール類
や比較的低級の炭化水素等の原料をガス状で水蒸気改質
して水素を得る改質器に関する。[Detailed Description of the Invention] [Objective of the Invention] [Industrial Application Field] The present invention produces hydrogen by steam reforming raw materials such as lower alcohols such as methanol and ethanol, and relatively lower hydrocarbons in a gaseous state. Regarding a reformer that obtains.
特に塩素イオンを含む原料に適した改質器に関する。一
方常態では液状の原料に適した反応器に関し、更に液状
のアルコールとりわけメタノールに適した改質器に関す
る。In particular, the present invention relates to a reformer suitable for raw materials containing chlorine ions. On the other hand, it relates to a reactor suitable for normally liquid raw materials, and moreover to a reformer suitable for liquid alcohols, especially methanol.
［従来の技術］
従来メタノールに代表される原料を水蒸気改質して水素
を得るには、ＭｅＯＨ十Ｈｚ Ｏ→３Ｈ。[Prior Art] Conventionally, in order to obtain hydrogen by steam reforming a raw material represented by methanol, MeOH 10Hz O→3H is used.
＋ＣＯ２等の改質反応が強い吸熱反応であるので多管式
反応器で反応させるのが通例である。即ちシェル／チュ
ーブ型熱交換器類似の１ｆＩ４造の多管型の反応器の管
内に改質触媒を充填し、この内部にガス状とした原料と
水蒸気とを通過させシェル側から反応熱を適宜の熱源例
えば熱媒油や燃焼ガス等により与えて改質反応をさせる
。Since the reforming reaction of +CO2 and the like is a strongly endothermic reaction, it is customary to carry out the reaction in a multi-tubular reactor. That is, a reforming catalyst is filled in the tubes of a 1fI4 multitubular reactor similar to a shell/tube heat exchanger, and gaseous raw materials and steam are passed through the tube, and the reaction heat is appropriately transferred from the shell side. A reforming reaction is caused by applying heat from a heat source such as heat transfer oil or combustion gas.
この際の改質触媒は例えば原料がメタノールであればＣ
ｕ系の触媒が代表的でＣｕ−Ｚｎ、又はＣｕ−Ｉｎ−Ｃ
ｒ等のＣｕ系触媒が適当な担体に担持されて多管に充填
される。For example, if the raw material is methanol, the reforming catalyst at this time is C
Typical u-based catalysts are Cu-Zn or Cu-In-C.
A Cu-based catalyst such as r is supported on a suitable carrier and packed into a multi-tube.
ところがこの様な触媒は塩素イオンにより被毒されるこ
とがある。被毒は直ちに起こるものではないが、−旦発
生すると改質器にとり致命的であって、運転を中止し触
媒の交換をせねばならない。However, such catalysts may be poisoned by chlorine ions. Although poisoning does not occur immediately, once it occurs, it is fatal to the reformer, and the operation must be stopped and the catalyst replaced.
例えば、多管式改質器にアルミナを担体とするＣｕ−Ｉ
ｎ系触媒を用い、圧力２０ｋｏ／ＣｄＧ、 温に２８０
℃にて約２５ｔ７日のメタノールを水蒸気改質し約３〜
４ｔ／日程度の精製水素を得る際に。For example, Cu-I with alumina as a carrier in a multi-tube reformer.
Using n-type catalyst, pressure 20ko/CdG, temperature 280℃
Approximately 25 tons of methanol for 7 days is steam reformed at ℃ for approximately 3~
When obtaining about 4 tons/day of purified hydrogen.
２ ｐｐｌの塩素イオンを含む原料メタノールを用いて
１か月運転を継続すると、被毒の結果水素の生成量が当
初の約４割に激減する９従って事実上これよりもずっと
早く運転を停止して手間と時間のかかる触媒の交換をぜ
ざるを得ない、この程度の規模では運転再開までに４〜
５日間は要してしまつ。If the plant continues to operate for one month using raw methanol containing 2 ppl of chlorine ions, the amount of hydrogen produced will drastically decrease to approximately 40% of the initial amount as a result of poisoning. At this scale, it takes about 4 to 4 hours to restart operation.
It will take 5 days.
塩素イオンの混入は原料メタノールの合成時に由来する
ものではないが、近年０．１〜１０ρｐｉｎ程度の塩素
イオンで汚染された液状の原料例えばメタノールは少く
ない一方、２０〜３０ｔ／日級の大量のメタノールから
かかる塩素イオンをｐｐｎ＋オーダより下まで除去する
工程を水素製造ブラントに併設するのは、規模の点から
もまた適切なプロセス自体が確立されてもおらず、困難
である。The contamination of chlorine ions does not originate during the synthesis of raw material methanol, but in recent years, liquid raw materials, such as methanol, have been contaminated with chlorine ions of about 0.1 to 10 ρpin, and while there is not a small amount of liquid raw materials, such as methanol, in large quantities of 20 to 30 tons/day. It is difficult to add a process for removing such chloride ions from methanol to below ppn+ order to a hydrogen production blunt, both from the standpoint of scale and because no suitable process has been established.
またこのクラスの改質器を２基以上並列させ交互運転す
るのも不経済であり実用できない。Furthermore, it is uneconomical to place two or more reformers of this class in parallel and operate them alternately, which is impractical.
［発明が解決しようとする課題］
本発明は従来の技術が有する上記課題の解決を図り、塩
素イオンで汚染された原料を用いた場合にも、それによ
る触媒被毒に因っては運転を停止する必要のない改質器
を提供する。[Problems to be Solved by the Invention] The present invention aims to solve the above-mentioned problems of the conventional technology, and even when raw materials contaminated with chlorine ions are used, it is possible to stop operation due to catalyst poisoning caused by the chlorine ions. To provide a reformer that does not need to be stopped.
Ｅ発明の構成Ｊ
［課題を解決するための手段］
本発明は、上記問題点を克服すべ〈発明者が鋭意検討を
行って漸く得られた。即ち本発明は。E Structure of the Invention J [Means for Solving the Problems] The present invention was finally achieved after the inventor conducted intensive studies to overcome the above problems. That is, the present invention.
「アルコール又は炭化水素を水蒸気改質する改質器であ
って、改質触媒を使用し外部加熱により改質を行う主反
応器と、これの０９段に配置され改質触媒が充填され断
熱的に改質を行う予備反応器と、予備反応器のバイパス
とからなることを特徴とする改質器」である、以下で詳
細を説明する。"A reformer for steam reforming alcohol or hydrocarbons, which consists of a main reactor that uses a reforming catalyst and performs reforming by external heating, and a main reactor that is placed in the 09th stage of this reactor and is filled with a reforming catalyst and is adiabatic. The reformer is characterized in that it consists of a pre-reactor for carrying out reforming and a bypass of the pre-reactor, and will be described in detail below.
本発明の予備反応器は１台がバイパスラインと共に設け
られ、バイパスラインの活用により予備反応器の触媒交
換時に主反応器の運転を停止せず済むようにする。なお
バイパスラインは同様の予備反応器を含んでもよい、こ
の場合予備反応器が並列して設けられたことになる
予備反応器の容量はこれに充填される触媒にもよるが、
最も一般的な両反応器で同じ触媒を用いる場合１通学生
反応器の触媒容量の１０〜１００％、好ましくは３０〜
８０％、特に好ましくは４０〜５０％程度とするとよい
、容量が過少では主反応器の触媒被毒防止が不充分とな
り、過多では改質反応に寄与しない触媒が多くなって予
備反応器の容器、触媒に関する機器費が高くなり不経済
である。One pre-reactor of the present invention is provided with a bypass line, and by utilizing the bypass line, it is not necessary to stop the operation of the main reactor when replacing the catalyst in the pre-reactor. Note that the bypass line may include a similar pre-reactor, in which case the pre-reactors will be provided in parallel, although the capacity of the pre-reactor will depend on the catalyst filled in it.
Most commonly, when the same catalyst is used in both reactors, 10 to 100% of the catalyst capacity of the student reactor, preferably 30 to
It is recommended to set the capacity to 80%, particularly preferably around 40 to 50%. If the capacity is too small, prevention of catalyst poisoning in the main reactor will be insufficient, and if it is too large, there will be too much catalyst that does not contribute to the reforming reaction and the container of the preliminary reactor will be , the cost of equipment related to the catalyst increases and is uneconomical.
予備反応器を断熱型としたのは、断熱型ならば多管式と
異り円筒型等の単純な形状の空間にガスの入口、出口、
及び触媒の交換口を設ければよく構造か簡単でかつ触媒
交換が容易の為である。The reason why the pre-reactor is an adiabatic type is that unlike a multi-tube type, an adiabatic type has a gas inlet, outlet, etc. in a simple space such as a cylinder.
This is because the structure is simple and the catalyst can be easily replaced by providing a catalyst replacement port.
予備反応器に充填される改質触媒は主反応器と同じでも
よく、また異ってもよい、被毒を予備反応器内にとどめ
て主反応器に至らせない為のものであるが、同時に、原
料の水蒸気改質能力を持ち主反応器の容量を低減させる
。The reforming catalyst charged in the preliminary reactor may be the same as or different from that in the main reactor, and is intended to keep poisoning within the preliminary reactor and not to reach the main reactor. At the same time, it has the ability to steam reform the raw material and reduces the capacity of the main reactor.
予備反応器の触媒はまた塩素イオンを積極的に捕える為
に、カルシウム、マグネシウム等のアルカリ土類金属の
酸化物等のアルカリ性物質を、担体の成分として又は担
持された成分として、改質能力を害さないまた吸湿等か
らの変形・崩れ等により交換の妨げとならない範囲で、
有してもよい。The catalyst in the pre-reactor also has the ability to actively capture chloride ions by adding an alkaline substance such as an oxide of an alkaline earth metal such as calcium or magnesium as a component of the carrier or as a supported component. As long as it does not cause any damage or prevent replacement due to deformation or collapse due to moisture absorption, etc.
May have.
［作用］
本発明の改質器では塩素イオン由来の改質触媒の被毒、
劣化が、触媒交換か容易な予備反応器で食い止められる
。また予備反応器の触媒交換時はバイパスラインの利用
により主反応器の運転を停止する必要がない。[Function] The reformer of the present invention prevents poisoning of the reforming catalyst derived from chlorine ions,
Degradation can be stopped with catalyst replacement or a simple pre-reactor. Furthermore, when replacing the catalyst in the preliminary reactor, there is no need to stop the operation of the main reactor by using the bypass line.
［図面による例の説明〕
第１図に１本発明の改質器を含む機器構成が概念的に示
される。原料メタノール１−はポンプ３により定量的に
弁５．ライン７経由供給され、ライン７で後記するリサ
イクル液と混合してから予熱器９で予熱され、混合物が
蒸発器１１で気化され。[Explanation of Examples with Drawings] FIG. 1 conceptually shows an equipment configuration including a reformer of the present invention. The raw material methanol 1- is quantitatively supplied by the pump 3 to the valve 5. It is supplied via line 7, mixed with a recycle liquid to be described later in line 7, preheated in preheater 9, and the mixture is vaporized in evaporator 11.
（必要に応じ予熱器１５で更に）予備改質に必要な熱を
与えられ、弁１つを経て予備反応器２１内に送入され、
予備反応器内で予備改質触媒床２１１により所望の程度
の５〜３０％程度まで予備改質されてから、弁２３を含
むライン２４経由多管式主反応器２５の多数のチューブ
２５１内の主改質触媒床を、シェル２５３側から反応熱
を供給されつつ通過し、この間に所望の程度改質される
。The heat necessary for preliminary reforming is given (further by a preheater 15 if necessary), and the mixture is fed into the preliminary reactor 21 through one valve.
After being pre-reformed to a desired degree of about 5 to 30% by the pre-reforming catalyst bed 211 in the pre-reactor, it is then pre-reformed to a desired degree of about 5-30% and then to the tubes 251 of the multi-tubular main reactor 25 via the line 24 including the valve 23. It passes through the main reforming catalyst bed while being supplied with reaction heat from the shell 253 side, and is reformed to a desired degree during this time.
１３．１７．２７は何れも加熱用熱媒を示す。13, 17, and 27 all indicate heating medium.
主改質器からライン２６に流出した改質済みガスは予熱
器９で前記ライン７からの流れを予熱してから、冷却器
２９で充分冷やされ気液混合物となり洗滌塔３１に下部
から流入し、コンデンセート液は底部に落ち、ガスはシ
ャワーヘッド３５からスプレーされる水で向流的に洗わ
れる。The reformed gas flowing out from the main reformer into the line 26 is preheated in the preheater 9 as it flows from the line 7, and then sufficiently cooled in the cooler 29 to form a gas-liquid mixture, which flows into the scrubbing tower 31 from the bottom. , the condensate liquid falls to the bottom and the gas is washed countercurrently with water sprayed from the shower head 35.
このスプレーされた水はまず充填床３３で改質済みガス
と接触し次いでその下方で液滴として落下しガスと向流
してからコンデンセートと共にリサイクル液となりライ
ン６２．ポンプ６３．弁６４経由送られ、ライン７で原
料メタノールと合流して前記の経路をたどる。This sprayed water first comes into contact with the reformed gas in the packed bed 33, then falls below it as droplets, flows countercurrently with the gas, and becomes a recycled liquid along with the condensate in the line 62. Pump 63. It is sent via the valve 64, joins with the raw material methanol in the line 7, and follows the above-mentioned route.
スプレーされる水は副原料の水蒸気となる水３７で、ポ
ンプ３９．弁４１．ライン４３経由定量的に供給される
。The water to be sprayed is water 37 which becomes steam as an auxiliary raw material, and is pumped by a pump 39. Valve 41. It is supplied quantitatively via line 43.
予備反応器２１．バイパス２２とライン２４゜主反応器
２５が本発明の改質器を構成する。 洗滌塔３１で洗わ
れたガスはミストセパレータ４５でミストを去ってから
ノックアウトドラム４７にて気液分離され、廃液４９が
下方に排出される一方、上方からミストセパレータ４５
．ライン５０経由弁５１を経てＰＳＡ等の精製装置１Ｆ
５３で処理され、製品水素５５として取出される。なお
精製装置５３からの副生ガス５７．弁５９経山放出され
ることもある放出ガス６１等は、これらの組成と必要に
応じ適当な用途に燃料として利用され。Pre-reactor 21. Bypass 22 and line 24° main reactor 25 constitute the reformer of the present invention. The gas washed in the washing tower 31 leaves the mist in the mist separator 45 and is separated into gas and liquid in the knockout drum 47, and the waste liquid 49 is discharged downward, while the mist separator 45
．． Via line 50 Via valve 51 1F of purification equipment such as PSA
53 and extracted as product hydrogen 55. Note that the by-product gas 57 from the purification device 53. The discharged gas 61, which may be discharged through the valve 59, is used as fuel for appropriate purposes depending on the composition and necessity.
又はフレアスタックで燃焼廃棄される等される。Or it is burned and disposed of in a flare stack.
なお放出ガスは蓄積する不要成分のパージにもなる。Note that the released gas also serves as a purge of accumulated unnecessary components.
予備改質触媒床２１１の取替時には、弁１９１を開き弁
１９．２３を閉じてバイパス２２経由原料混合物ガスを
主反応器２５に流してこの反応器での反応を続けたまま
触媒床２１１を交換することができる。交換は一定期間
毎にしてもよいしまたメタノールの不純物組成等が変動
する場合等には、予備反応器２１の触媒床内の温度分布
、予備反応器出口温度、又は流出ガス組成等の変化で触
媒の劣化を知ってから行ってもよい。When replacing the preliminary reforming catalyst bed 211, the valve 191 is opened, the valve 19.23 is closed, and the raw material mixture gas is passed through the bypass 22 to the main reactor 25, and the catalyst bed 211 is replaced while the reaction in this reactor continues. Can be exchanged. Replacement may be carried out at regular intervals, or if the impurity composition of methanol changes, etc., it may be replaced due to changes in the temperature distribution in the catalyst bed of the pre-reactor 21, the temperature at the outlet of the pre-reactor, or the composition of the outflow gas. You can do this after knowing that the catalyst has deteriorated.
［実施例〕
塩素イオン０．３Ｄｐｒｍを含む純度９８．５％のメタ
ノール１は７４０ 、３Ｎ／／ｈｒ相当量で、件数とし
て２ＯＮｄ／ｈｒ相当量の水分を伴い上記の装置系に送
入され、一方温度３０℃の純水３７は６３７、３ＮＩｌ
／ｈｒ相当量で送入され、 １＊述のライン６２からの
リサイクル液に含まれてメタノールとライン７で混合す
る。[Example] Methanol 1 with a purity of 98.5% containing 0.3 Dprm of chloride ions was sent to the above equipment system in an amount equivalent to 740.3 N/hr, accompanied by an amount of water equivalent to 2 ONd/hr, On the other hand, pure water 37 at a temperature of 30°C is 637,3NIl
/hr, is included in the recycled liquid from line 62 mentioned in 1*, and is mixed with methanol in line 7.
この混合液は予熱器９で加熱され温度１５０℃となって
蒸発器１１に入る。蒸発器を出たガスは１９５℃となる
が、これを予熱器１５で３００℃に昇温してから予備反
応器２１に送り込む、予備反応を終えた２５０℃のガス
はライン２４から主反応器２５に入って改質され、温度
２５０℃の改質済みガスは冷却器２９で４０℃に冷却さ
れてガスとコンデンセートに分かれてから洗浄塔３１に
流入してガスが洗浄される。This liquid mixture is heated in the preheater 9 to a temperature of 150° C. and enters the evaporator 11. The gas exiting the evaporator has a temperature of 195°C, but it is heated to 300°C in the preheater 15 and then sent to the pre-reactor 21. After the pre-reaction, the gas at 250°C is sent from the line 24 to the main reactor. The reformed gas at a temperature of 250° C. is cooled to 40° C. in a cooler 29 and separated into gas and condensate, and then flows into a cleaning tower 31 where the gas is cleaned.
コンデンセートと洗気に用いた供給水との混合物である
リサイクル液はライン６２からリサイクルされ洗′ａ後
のガスはライン４６からノックアウトドラム４７に入る
。The recycle liquid, which is a mixture of condensate and the feed water used for washing, is recycled from line 62, and the gas after washing'a enters knockout drum 47 from line 46.
ノックアウトドラムから排出される廃液４９と別れた粗
製ガスはライン５０から精製装置５３に入り精製されて
純度９９．９９９％の水素５５約１７００ Ｎａｆ／ｈ
ｒが得られる。副生ガス５７は熱媒１７．１３．２７等
の加熱用補助燃料として利用される。The crude gas separated from the waste liquid 49 discharged from the knockout drum enters the purification device 53 through the line 50 and is purified to produce hydrogen 55 with a purity of 99.999% at approximately 1700 Naf/h.
r is obtained. The by-product gas 57 is used as an auxiliary fuel for heating the heat medium 17, 13, 27, etc.
容量的０．６５１１１”の予備改質触媒床２１１１合計
容量約容量的イの主改質触媒床２５１として充填された
触媒は粒状でＣｕｂ、２ｎＯ，アルミナが夫々２０．５
０．３０重量％の組成を持つ。The catalyst packed as the main reforming catalyst bed 251 with a total capacity of approximately 0.65111" in volume is granular and contains 20.5" each of Cub, 2nO, and alumina.
It has a composition of 0.30% by weight.
上記した以外の物質収支に関する組成、量は表１に示す
、なお反応圧力は２０ ｋａ／ｃ１１／Ｇである。The compositions and amounts regarding material balance other than those mentioned above are shown in Table 1, and the reaction pressure was 20 ka/c11/G.
上記運転を３か月継続後に主反応器を運転したまま予備
改質触媒床２１１を交換することを１年間続け、この間
主反応器の触媒の格別の劣化は認められいが、１年後に
は定期点検修理時に主改質触媒床も交換して運転を再開
する。予備改質触媒床の交換後再利用開始には、弁１９
１を開いてから約８時間、工数としては約４０人・時間
を要する。After continuing the above operation for three months, we continued to replace the preliminary reforming catalyst bed 211 with the main reactor operating for one year. During this period, no particular deterioration of the catalyst in the main reactor was observed, but after one year, During periodic inspection and repair, the main reforming catalyst bed will also be replaced and operation will resume. To start reuse after replacing the pre-reforming catalyst bed, valve 19
It takes about 8 hours after opening 1, and it takes about 40 people and hours.
これに対し比較例として、予備改質触媒床を利用せずバ
イパスライン２２から直接、原料混合ガスを（メタノー
ル１．純水３７と共に）予備改質触媒床の能力に相当す
る分だけ減らして運転すると、３１日目には製品水素カ
スの生成量か運転開始時よりも３０％落ちるので、運転
を停止し主反応触媒床を交換して運転を再開する。運転
停止期間は５日に及び、工数は約２５人・日である。On the other hand, as a comparative example, an operation was performed in which the raw material mixed gas (along with methanol 1 and pure water 37) was reduced by an amount corresponding to the capacity of the preliminary reforming catalyst bed directly from the bypass line 22 without using the preliminary reforming catalyst bed. Then, on the 31st day, the amount of product hydrogen sludge produced decreased by 30% compared to when the operation started, so the operation was stopped, the main reaction catalyst bed was replaced, and the operation was restarted. The period of outage was 5 days, and the number of man-hours was approximately 25 man-days.
上記例の改質反応の圧力は２０ｋｇ／ｃｍＧだが。The pressure of the reforming reaction in the above example is 20 kg/cmG.
本発明では効率と設備の経済性からこの圧力が７〜３０
ｋｇ／ｃｍＧであるのが好ましく、１０〜２０ｋ（１／
ＣｄＧが特に好ましい。In the present invention, this pressure is 7 to 30
kg/cmG is preferable, and 10 to 20k (1/cmG) is preferable.
CdG is particularly preferred.
［発明の効果］
以上から明らかな様に１本発明により次の主要な効果が
得られる。即ち、予備反応器の触媒交換を主反応器の運
転を継続したまま実施し、主反応器の触媒交換は、熱等
の他の原因由来の劣化によるものたけと出来、触媒交換
の為の運転停止が通常の定期点検程度の為の停止頻度以
下に減らし得る。[Effects of the Invention] As is clear from the above, the present invention provides the following main effects. In other words, the catalyst in the preliminary reactor is replaced while the main reactor continues to operate, and the main reactor's catalyst is replaced only due to deterioration caused by other causes such as heat. The frequency of outages can be reduced to below that required for regular periodic inspections.
表１（数値はｎ／／ｈｒ机１Ｌ
水素 ２１２４．７
ＣＯ□ ６５１
メタノール １３０．６ ８７０．９ １３３．
６メタン ０．３
水 １２８６．４１３０６．４６５５．１２１２４
．７
３ １３０．６
０．３
６４９、１Table 1 (Numbers are n//hr machine 1L Hydrogen 2124.7 CO□ 651 Methanol 130.6 870.9 133.
6 Methane 0.3 Water 1286.41306.4655.12124
．． 7 3 130.6 0.3 649, 1
第１図は本発明の改質器を用いたプロセスの１例を示す
図である。FIG. 1 is a diagram showing an example of a process using the reformer of the present invention.
Claims (1)
あって、改質触媒を使用し外部加熱により改質を行う主
反応器と、これの前段に配置され改質触媒が充填され断
熱的に改質を行う予備反応器と、予備反応器のバイパス
とからなることを特徴とする改質器。1) A reformer for steam reforming alcohol or hydrocarbons, which includes a main reactor that uses a reforming catalyst and performs reforming by external heating, and a main reactor that is placed in front of this and filled with the reforming catalyst and is adiabatic. A reformer comprising a preliminary reactor for performing reforming and a bypass of the preliminary reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63219720A JP2632557B2 (en) | 1988-09-02 | 1988-09-02 | Reformer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63219720A JP2632557B2 (en) | 1988-09-02 | 1988-09-02 | Reformer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0269303A true JPH0269303A (en) | 1990-03-08 |
| JP2632557B2 JP2632557B2 (en) | 1997-07-23 |
Family
ID=16739914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63219720A Expired - Lifetime JP2632557B2 (en) | 1988-09-02 | 1988-09-02 | Reformer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2632557B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187501A (en) * | 1990-11-21 | 1992-07-06 | Mitsubishi Heavy Ind Ltd | Reforming of methanol |
| JP2002326801A (en) * | 2001-04-27 | 2002-11-12 | Ishikawajima Harima Heavy Ind Co Ltd | Reforming method and reformer |
| JP2008529943A (en) * | 2005-02-10 | 2008-08-07 | エレクトロファック アクチェンゲゼルシャフト | Hydrogen production |
| JP2009500274A (en) * | 2005-06-30 | 2009-01-08 | ゼネラル・エレクトリック・カンパニイ | Apparatus and method for hydrogen production |
| JP2020100534A (en) * | 2018-12-21 | 2020-07-02 | 東京瓦斯株式会社 | Hydrogen production apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428401A (en) * | 1977-08-03 | 1979-03-03 | Orenstein & Koppel Ag | Rapid exchanging device for attachment of earthhmoving machine |
| JPS61122102A (en) * | 1984-11-20 | 1986-06-10 | Jgc Corp | Steam reforming of hydrocarbon |
-
1988
- 1988-09-02 JP JP63219720A patent/JP2632557B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428401A (en) * | 1977-08-03 | 1979-03-03 | Orenstein & Koppel Ag | Rapid exchanging device for attachment of earthhmoving machine |
| JPS61122102A (en) * | 1984-11-20 | 1986-06-10 | Jgc Corp | Steam reforming of hydrocarbon |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187501A (en) * | 1990-11-21 | 1992-07-06 | Mitsubishi Heavy Ind Ltd | Reforming of methanol |
| JP2002326801A (en) * | 2001-04-27 | 2002-11-12 | Ishikawajima Harima Heavy Ind Co Ltd | Reforming method and reformer |
| JP2008529943A (en) * | 2005-02-10 | 2008-08-07 | エレクトロファック アクチェンゲゼルシャフト | Hydrogen production |
| JP2009500274A (en) * | 2005-06-30 | 2009-01-08 | ゼネラル・エレクトリック・カンパニイ | Apparatus and method for hydrogen production |
| JP2020100534A (en) * | 2018-12-21 | 2020-07-02 | 東京瓦斯株式会社 | Hydrogen production apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2632557B2 (en) | 1997-07-23 |
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