JP2000281308A - Hydrogen generating device and its operation - Google Patents
Hydrogen generating device and its operationInfo
- Publication number
- JP2000281308A JP2000281308A JP11089455A JP8945599A JP2000281308A JP 2000281308 A JP2000281308 A JP 2000281308A JP 11089455 A JP11089455 A JP 11089455A JP 8945599 A JP8945599 A JP 8945599A JP 2000281308 A JP2000281308 A JP 2000281308A
- Authority
- JP
- Japan
- Prior art keywords
- reformer
- gas
- hydrogen
- temperature
- burner
- 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.)
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Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、水素発生装置と
その運転方法、特に運転温度の制御に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen generator and an operation method thereof, and more particularly to control of an operation temperature.
【０００２】[0002]
【従来の技術】雰囲気ガスとして水素を用いる工業用装
置や燃料電池発電プラントなどにおいては、水素発生装
置が必要である。従来、水素発生装置の一つとして、天
然ガス，ＬＮＧ，ＬＰＧ，メタノールなどの原料ガスを
水蒸気とともに触媒層を通過させることにより水素リッ
チな改質ガスを生成する改質器と、前記改質ガスを加圧
するための圧縮機と、加圧された改質ガスから水素を分
離精製する圧力スイング吸着装置（ＰＳＡ）とで構成し
た水素発生装置が採用されている。2. Description of the Related Art A hydrogen generator is required for an industrial apparatus using hydrogen as an atmospheric gas, a fuel cell power plant, and the like. Conventionally, as one of the hydrogen generators, a reformer that generates a hydrogen-rich reformed gas by passing a raw material gas such as natural gas, LNG, LPG, and methanol together with water vapor through a catalyst layer; And a pressure swing adsorption device (PSA) that separates and purifies hydrogen from the pressurized reformed gas.
【０００３】図４は、上記従来の水素発生装置の概略構
成を示すもので、触媒層を有する改質管１ａとバーナ１
ｂとを備えた改質器１と、改質ガスを加圧するための圧
縮機２と、改質ガスから水素を分離精製するＰＳＡ３
と、ＰＳＡにおいて水素を分離除去処理した後のまだ水
素を含む残ガスを前記改質器のバーナ１ｂに供給するた
めの残ガス供給配管６を備える。FIG. 4 shows a schematic structure of the above-mentioned conventional hydrogen generator, in which a reforming tube 1a having a catalyst layer and a burner 1 are shown.
b, a compressor 2 for pressurizing the reformed gas, and a PSA 3 for separating and purifying hydrogen from the reformed gas
And a residual gas supply pipe 6 for supplying a residual gas still containing hydrogen after the hydrogen is separated and removed in the PSA to the burner 1b of the reformer.
【０００４】改質原料ガスは水蒸気とともに、改質原料
ガス導入配管９から改質器１の触媒層に導入され、触媒
による改質反応によって水素リッチなガスに改質され、
圧縮された後ＰＳＡにより精製され、水素濃度が高めら
れる。前記改質反応は吸熱反応のため、外部から熱を供
給する必要があり、そのために、バーナの燃焼排ガスが
加熱媒体として利用される。[0004] The reforming raw material gas is introduced into the catalyst layer of the reformer 1 through the reforming raw material gas introduction pipe 9 together with the steam, and reformed into a hydrogen-rich gas by a reforming reaction by the catalyst.
After being compressed, it is purified by PSA to increase the hydrogen concentration. Since the reforming reaction is an endothermic reaction, it is necessary to supply heat from the outside. Therefore, the combustion exhaust gas of the burner is used as a heating medium.
【０００５】このバーナの燃焼燃料として、主に、前記
したＰＳＡ３において水素を分離除去処理した後のまだ
水素を含む残ガスが用いられ、流量制御弁８を介して残
ガスが、ＰＳＡ３からバーナ１ｂに供給される。残ガス
のみでは、熱量が不十分の場合には、補助燃料をバーナ
用補助燃料配管７から供給して燃焼させる。As the combustion fuel for the burner, a residual gas still containing hydrogen after the hydrogen is separated and removed in the PSA 3 is mainly used. The residual gas is supplied from the PSA 3 via the flow control valve 8 to the burner 1b. Supplied to If the residual gas alone has insufficient heat quantity, auxiliary fuel is supplied from the auxiliary fuel pipe 7 for the burner and burned.
【０００６】ところで、上記改質器はかなり高温で運転
され、例えば天然ガスを改質原料ガスに使用する場合、
触媒反応温度は７００〜８００℃であり、バーナの燃焼
排ガス温度は、１０００℃を上回る。そのため、改質器
の主要部材は、耐熱性材料により製作されているもの
の、反応管の熱疲労による破損の危険性や耐熱寿命の観
点から、改質器の温度（触媒層温度もしくはバーナの燃
焼排ガス温度）が、所定の温度を超えないようにする必
要がある。Incidentally, the above-mentioned reformer is operated at a considerably high temperature. For example, when natural gas is used as a raw material gas,
The catalytic reaction temperature is 700-800 ° C, and the combustion exhaust gas temperature of the burner exceeds 1000 ° C. Therefore, although the main members of the reformer are made of heat-resistant material, the temperature of the reformer (catalyst layer temperature or combustion of burner (Exhaust gas temperature) must not exceed a predetermined temperature.
【０００７】上記に対する対策として、従来は、温度計
５により前記改質器の温度を測定し、前記所定の温度を
超えたことを検知した場合には、前記ＰＳＡ３において
水素を分離除去処理した後のまだ水素を含む残ガスを、
流量制御弁８から放出し、燃焼ガス量を低減して温度を
低下するようにしていた。また、別の方法として、バー
ナの燃焼における空燃比を上昇させて、燃焼温度を下げ
るようにしていた。As a countermeasure against the above, conventionally, the temperature of the reformer is measured by a thermometer 5 and when it is detected that the temperature exceeds the predetermined temperature, the PSA 3 is subjected to a separation and removal treatment of hydrogen. The residual gas, still containing hydrogen,
The temperature is lowered by discharging the gas from the flow control valve 8 and reducing the amount of combustion gas. Further, as another method, the air-fuel ratio in the burner combustion is increased to lower the combustion temperature.
【０００８】[0008]
【発明が解決しようとする課題】上記従来の水素発生装
置、特に改質器の温度制御の方法においては、下記のよ
うな問題があった。The above-mentioned conventional hydrogen generator, particularly the method of controlling the temperature of the reformer, has the following problems.
【０００９】前記のように、改質器の温度が設定値よ
り高くなった場合に、水素精製後の残ガスの余剰分を装
置外に放出することは、エネルギーロスが大きく、経済
上問題があった。As described above, when the temperature of the reformer becomes higher than the set value, discharging the surplus of the residual gas after the hydrogen purification to the outside of the apparatus causes a large energy loss and poses an economic problem. there were.
【００１０】また、上記残ガスは、水素，メタン，一
酸化炭素などの可燃性成分を多く含んでおり、そのまま
系外に放出することは保安上好ましくなく、燃焼器によ
り燃焼させて放出するのが一般的である。この場合、燃
焼器および燃焼制御装置が必要となり、設備コストも増
大する問題があった。The residual gas contains a large amount of combustible components such as hydrogen, methane, and carbon monoxide. It is not preferable to release the residual gas out of the system as it is for security reasons. Is common. In this case, there is a problem that a combustor and a combustion control device are required, and the equipment cost is increased.
【００１１】また、前述のように空燃比を上げる場合
には、火炎温度が低下し、触媒層への伝熱量は若干低下
するものの、燃焼熱量自体は同じ故、改質器の温度低減
効果は、系外放出に比べて小さい。また、バーナ構造お
よび燃焼スペースの制約から、設計値から大きく離れた
空燃比で運転すると、バーナにおける圧力損失が計画範
囲を逸脱し、バーナの運転および図示しない残ガス供給
ブロワなどの関連周辺機器の運転が困難となる。When the air-fuel ratio is increased as described above, the flame temperature decreases and the amount of heat transferred to the catalyst layer slightly decreases, but the amount of heat of combustion itself is the same. , Smaller than out-of-system release. In addition, due to restrictions on the burner structure and combustion space, when operating at an air-fuel ratio far away from the design value, the pressure loss at the burner will deviate from the planned range, and the operation of the burner and related peripheral equipment such as a residual gas supply blower not shown Driving becomes difficult.
【００１２】この発明は、上記のような問題点を解決す
るためになされたもので、本発明の課題は、水素精製後
の残ガスを無駄に放出することなく適正な改質器の温度
制御が可能であって、かつ、設備コスト及び運転コスト
が低い水素発生装置とその運転方法を提供することにあ
る。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to appropriately control the temperature of a reformer without wastefully discharging the residual gas after hydrogen purification. It is an object of the present invention to provide a hydrogen generator and a method of operating the hydrogen generator, which are capable of reducing equipment costs and operating costs.
【００１３】[0013]
【課題を解決するための手段】前述の課題を解決するた
め、この発明の水素発生装置の運転方法においては、改
質器の温度（前記触媒層温度もしくはバーナの燃焼排ガ
ス温度）が改質器の耐熱性の観点から定めた所定の設定
値を超えた場合に、圧縮機の吐出圧力とＰＳＡの吸着圧
力を上昇させ、ＰＳＡにおける水素収率を向上させるこ
とによって、ＰＳＡからバーナに供給する残ガスの発熱
量を低減させ、前記改質器の温度を設定値以下に低下さ
せることとする（請求項１）。In order to solve the above-mentioned problems, in the operation method of the hydrogen generator according to the present invention, the temperature of the reformer (the temperature of the catalyst layer or the temperature of the combustion exhaust gas of the burner) is changed. When the pressure exceeds a predetermined set value determined from the viewpoint of heat resistance, the discharge pressure of the compressor and the adsorption pressure of the PSA are increased to improve the hydrogen yield in the PSA, so that the residual pressure supplied from the PSA to the burner is increased. The calorific value of the gas is reduced, and the temperature of the reformer is reduced to a set value or less (claim 1).
【００１４】あるいは、改質器の温度が改質器の耐熱性
の観点から定めた所定の設定値を超えた場合に、残ガス
の一部を前記触媒層に再循環し、ＰＳＡにおける水素収
率を向上させることによって、バーナに供給する前記残
ガスの発熱量を低減させ、改質器の温度を設定値以下に
低下させることとする（請求項３）。Alternatively, when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of the heat resistance of the reformer, a part of the residual gas is recirculated to the catalyst layer, and the hydrogen recovery in the PSA is performed. By improving the rate, the calorific value of the residual gas supplied to the burner is reduced, and the temperature of the reformer is reduced to a set value or less (claim 3).
【００１５】前述のＰＳＡにおける水素収率を向上させ
ることによる発熱量の低減作用について、以下に詳述す
る。The effect of reducing the calorific value by improving the hydrogen yield in the PSA will be described in detail below.
【００１６】まず、請求項１に関わり、ＰＳＡの吸着圧
力を変化させた場合の水素収率（ＰＳＡに投入された水
素の内、製品水素として分離される割合）の一例を下表
に示す。下表は、吸着圧力を６．５kg/cm2Ｇで設計した
ＰＳＡについて、その吸着圧力を上昇させた場合の各水
素収率を求めたものである。 ＰＳＡ水素収率が７１％，７４％の場合の、バーナに戻
るガスの発熱量を比較すると、水素の含有量が低下する
ために、７４％の場合は８．３％小さくなる。First, the following table shows an example of the hydrogen yield (the ratio of the hydrogen supplied to the PSA that is separated as product hydrogen) when the adsorption pressure of PSA is changed. The following table shows the hydrogen yields of PSA designed at an adsorption pressure of 6.5 kg / cm 2 G when the adsorption pressure was increased. When comparing the calorific value of the gas returning to the burner when the PSA hydrogen yield is 71% and 74%, the content of hydrogen is reduced, and when the PSA hydrogen yield is 74%, the gas is reduced by 8.3%.
【００１７】なお、ＰＳＡの吸着圧力を高くするために
は、圧縮機の動力が増加し、その分の費用が余分に発生
することになるが、試算によれば、６．５から９kg/cm2
Ｇに増加させた場合の動力増加費用は、水素収率が向上
することによって増加する水素の価格の２〜３割であ
り、十分にコストメリットがある。In order to increase the PSA adsorption pressure, the power of the compressor is increased and an extra cost is incurred. However, according to a trial calculation, it is 6.5 to 9 kg / cm. Two
The power increase cost when the power is increased to G is 20 to 30% of the price of hydrogen which is increased by the improvement in the hydrogen yield, and there is a sufficient cost merit.
【００１８】次に、請求項３に関わり、残ガスの一部を
前記触媒層に再循環し、ＰＳＡにおける水素収率を向上
させる場合について試算した結果について述べる。Next, the results of a trial calculation regarding a case where the residual gas is partly recirculated to the catalyst layer to improve the hydrogen yield in PSA will be described.
【００１９】例えば、ＰＳＡで水素を回収精製した後の
残ガスの５％，１０％を触媒層に再循環した場合、ＰＳ
Ａ水素収率７１％の場合を比較のベースとすると、製品
水素の回収量はそれぞれ１．７％，３．４％増加する。
これは、ＰＳＡ水素収率に換算して、それぞれ７２．２
％，７３．４％に相当する。For example, when 5% or 10% of the residual gas after the recovery and purification of hydrogen by PSA is recycled to the catalyst layer, PS
If the case of A hydrogen yield of 71% is used as a comparison base, the recovered amount of product hydrogen increases by 1.7% and 3.4%, respectively.
This translates into 72.2 PSA hydrogen yields each.
%, 73.4%.
【００２０】以上のとおり、この発明の前記いずれの方
法においても、ＰＳＡにおける水素収率を向上させるこ
とによって、バーナに供給する前記残ガスの発熱量を低
減させ、改質器の温度を設定値以下に低下させる制御が
可能である。As described above, in any of the above methods of the present invention, by improving the hydrogen yield in the PSA, the calorific value of the residual gas supplied to the burner is reduced, and the temperature of the reformer is set to a set value. The following control is possible.
【００２１】この発明の方法を実施するための装置とし
ては、例えば、請求項２または４の発明に係る装置が好
適であり、その他、この発明の技術思想の範囲内で、種
々の変形が可能である。請求項２の発明によれば、天然
ガス，ＬＮＧ，ＬＰＧ，メタノールなどの炭化水素改質
原料ガスを，水蒸気とともに触媒層を通過させることに
より水素リッチな改質ガスを生成するための改質管と、
燃焼排ガスを改質原料の加熱媒体として利用するための
バーナとを備えた改質器と、前記改質ガスまたは原料ガ
スを加圧するための圧縮機と、加圧された改質ガスから
水素を分離精製する圧力スイング吸着装置（ＰＳＡ）
と、このＰＳＡにおいて水素を分離除去処理した後の残
ガスを前記改質器のバーナに供給して燃焼させるように
構成した水素発生装置において、前記圧縮機の吐出側の
圧力を測定する圧力計と、この圧力を制御する手段とし
て圧縮機の吐出側から吸い込み側に接続されたバイパス
配管経路に設けた制御弁と、前記改質器の温度（前記触
媒層温度もしくはバーナの燃焼排ガス温度）を測定する
温度計と、前記改質器の温度が改質器の耐熱性の観点か
ら定めた所定の設定値を超えた場合に，前記圧縮機の吐
出圧力とＰＳＡの吸着圧力を上昇させ，前記改質器の温
度を設定値以下に低下させるるような制御装置とを備え
たものとする。As a device for carrying out the method of the present invention, for example, a device according to the second or fourth aspect of the present invention is suitable, and various modifications are possible within the scope of the technical idea of the present invention. It is. According to the invention of claim 2, a reforming pipe for generating a hydrogen-rich reformed gas by passing a hydrocarbon reforming raw material gas such as natural gas, LNG, LPG, and methanol together with steam through a catalyst layer. When,
A reformer provided with a burner for using the combustion exhaust gas as a heating medium for the reforming raw material, a compressor for pressurizing the reformed gas or the raw material gas, and hydrogen from the pressurized reformed gas. Pressure swing adsorption device (PSA) for separation and purification
And a pressure gauge for measuring a pressure on a discharge side of the compressor in a hydrogen generator configured to supply residual gas after hydrogen is separated and removed in the PSA to a burner of the reformer for combustion. A control valve provided as a means for controlling this pressure in a bypass pipe path connected from the discharge side to the suction side of the compressor, and the temperature of the reformer (the catalyst layer temperature or the combustion exhaust gas temperature of the burner). When the temperature of the thermometer to be measured and the temperature of the reformer exceed a predetermined set value determined from the viewpoint of heat resistance of the reformer, the discharge pressure of the compressor and the adsorption pressure of PSA are increased, And a control device for lowering the temperature of the reformer below a set value.
【００２２】また、請求項４の発明によれば、前記残ガ
スを改質器のバーナに供給する経路に設けた三方向流量
制御弁と、前記残ガスの一部を前記三方向流量制御弁か
ら前記触媒層に還流するための還流バイパス配管と、前
記改質器の温度（前記触媒層温度もしくはバーナの燃焼
排ガス温度）を測定する温度計と、前記改質器の温度が
改質器の耐熱性の観点から定めた所定の設定値を超えた
場合に，前記残ガスの一部を触媒層に再循環させ，前記
改質器の温度を設定値以下に低下させるるような制御装
置とを備えたものとする。Further, according to the invention of claim 4, a three-way flow control valve provided in a path for supplying the residual gas to the burner of the reformer, and a part of the residual gas is supplied to the three-way flow control valve. A reflux bypass pipe for returning to the catalyst layer from the thermometer; a thermometer for measuring the temperature of the reformer (the temperature of the catalyst layer or the temperature of the combustion exhaust gas of the burner); A control device for recirculating a part of the residual gas to the catalyst layer when the temperature exceeds a predetermined set value determined from the viewpoint of heat resistance, thereby lowering the temperature of the reformer to a set value or less. Shall be provided.
【００２３】[0023]
【発明の実施の形態】図面に基づき、本発明の実施の形
態について以下にのべる。Embodiments of the present invention will be described below with reference to the drawings.
【００２４】図１，２および３は、この発明のそれぞれ
異なる実施例を示す概略構成図である。図１，２および
３において、図４の従来装置と同一部材については同一
の符合を付して説明を省略する。FIGS. 1, 2 and 3 are schematic structural views showing different embodiments of the present invention. 1, 2, and 3, the same members as those of the conventional device of FIG. 4 are denoted by the same reference numerals, and description thereof is omitted.
【００２５】図１は、請求項１，２の発明に関わる実施
例である。この実施例の水素発生装置は、触媒層を有す
る改質管１ａと、バーナ１ｂとを備えた改質器１と、改
質ガスを加圧するための圧縮機２と、加圧された改質ガ
スから水素を分離精製する圧力スイング吸着装置（ＰＳ
Ａ）３と、前記圧縮機の吐出側の圧力を測定する圧力計
１６と、この圧力を制御する手段として圧縮機の吐出側
から吸い込み側に接続されたバイパス配管経路に設けた
制御弁１７と、触媒層温度を測定する温度計５と、前記
改質器の温度が改質器の耐熱性の観点から定めた所定の
設定値を超えた場合に，前記圧縮機の吐出圧力を上昇さ
せ，前記改質器の温度を設定値以下に低下させるるよう
な制御装置１４とを備える。また、図１には図示してい
ないが、圧縮機２の吐出圧力上昇に合わせてＰＳＡ３の
吸着圧力を上昇させるような調節弁をＰＳＡ３は備えて
いる。FIG. 1 shows an embodiment according to the first and second aspects of the present invention. The hydrogen generator of this embodiment includes a reformer 1 having a reforming pipe 1a having a catalyst layer, a burner 1b, a compressor 2 for pressurizing reformed gas, and a pressurized reformer. Pressure swing adsorption device (PS) for separating and purifying hydrogen from gas
A) 3, a pressure gauge 16 for measuring the pressure on the discharge side of the compressor, and a control valve 17 provided as a means for controlling the pressure in a bypass pipe route connected from the discharge side to the suction side of the compressor. A thermometer 5 for measuring the temperature of the catalyst layer, and when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of heat resistance of the reformer, the discharge pressure of the compressor is increased, A controller 14 for lowering the temperature of the reformer to a set value or less. Although not shown in FIG. 1, the PSA 3 includes a control valve that increases the adsorption pressure of the PSA 3 in accordance with the increase in the discharge pressure of the compressor 2.
【００２６】天然ガス，メタノールのような改質原料ガ
スは、改質管１ａにおいて、水蒸気改質反応によって、
水素，二酸化炭素，一酸化炭素を主成分とする改質ガス
に変換される。改質原料を効率よく水素に変換するため
に、図示しない一酸化炭素変成器により、一酸化炭素と
水蒸気を反応させて水素と二酸化炭素に変成することが
一般に行われている。このようにして製造された改質ガ
スの成分は、概ね、水素濃度７０％余り、二酸化炭素濃
度約２０％で、残りは、水蒸気，メタンと若干の一酸化
炭素である。A reforming raw material gas such as natural gas or methanol is subjected to a steam reforming reaction in the reforming pipe 1a.
It is converted into a reformed gas containing hydrogen, carbon dioxide and carbon monoxide as main components. In order to efficiently convert the reforming raw material into hydrogen, it is common practice to convert carbon monoxide and water vapor into hydrogen and carbon dioxide by using a carbon monoxide converter not shown. The components of the reformed gas produced in this manner generally have a hydrogen concentration of about 70% or more and a carbon dioxide concentration of about 20%, and the balance is water vapor, methane, and some carbon monoxide.
【００２７】このような改質ガスを圧縮機２へ供給し
て、改質ガスを６．５〜９kg/cm2Ｇ程度に加圧する。図
１は、改質器１を略大気圧で運転し、ＰＳＡ３に投入す
る改質ガスを圧縮機２で加圧する方式の実施例を示す
が、図２に示すように、改質原料ガスを加圧して高圧の
水蒸気とともに改質器１に供給し、改質器１を加圧状態
で運転することもできる。The reformed gas is supplied to the compressor 2 to pressurize the reformed gas to about 6.5 to 9 kg / cm 2 G. FIG. 1 shows an embodiment of a system in which the reformer 1 is operated at substantially atmospheric pressure and the reformed gas to be injected into the PSA 3 is pressurized by the compressor 2, but as shown in FIG. The reformer 1 can be operated in a pressurized state by pressurizing and supplying the reformer 1 together with high-pressure steam.
【００２８】図１に戻って説明を続けると、圧縮機２で
加圧された改質ガスはＰＳＡ３に供給される。ＰＳＡ
は、複数の容器に活性炭やゼオライト等の吸着剤を充填
し、圧力を変動させることにより特定のガスを吸着分離
する装置である。ＰＳＡ３で分離精製された水素は系外
に取り出されて利用される。Returning to FIG. 1, the reformed gas pressurized by the compressor 2 is supplied to the PSA 3. PSA
Is an apparatus for filling a plurality of containers with an adsorbent such as activated carbon or zeolite, and adsorbing and separating a specific gas by changing the pressure. The hydrogen separated and purified by PSA3 is taken out of the system and used.
【００２９】ＰＳＡにおいては、その運転条件、性能に
よって違いはあるが、投入された水素に対して、概略６
５〜７５％が分離精製されて利用される。残余の水素お
よび他の成分は下流に排出される。下流に放出されるこ
の残ガスは、水素，メタン，一酸化炭素などの可燃成分
を多量に含んでいる。一方改質器１における水蒸気改質
反応は吸熱反応であり、その熱源として前記残ガスを使
用し、このガスをバーナ１ｂで燃焼させることにより、
この燃焼ガスから熱を供給する。バーナ１ｂで燃焼させ
るためには、図示しない燃焼用空気の供給装置が必要で
ある。In PSA, although there are differences depending on the operating conditions and performance, about 6% of
5 to 75% is used after being separated and purified. Residual hydrogen and other components are discharged downstream. This residual gas discharged downstream contains a large amount of combustible components such as hydrogen, methane, and carbon monoxide. On the other hand, the steam reforming reaction in the reformer 1 is an endothermic reaction, and the residual gas is used as a heat source, and this gas is burned by the burner 1b.
Heat is supplied from this combustion gas. In order to burn with the burner 1b, a combustion air supply device (not shown) is required.
【００３０】上記のような装置において、温度計５の測
定値が設定値より高い場合には、圧縮機２の吐出圧力を
測定する圧力計１６の測定値に基づき、圧縮機２の吐出
圧力を上昇させるように制御装置１４は、制御弁１７を
調整する。逆に、温度計５の測定値が設定値より低い場
合は、圧力計１６の測定値が低くなるように制御装置１
４は、制御弁１７を調整する。このようにして、改質器
の温度が、改質器の耐熱性の観点から定めた所定の設定
値を超えた場合に、圧縮機２の吐出圧力を上昇させ、Ｐ
ＳＡ３における水素収率を向上させることによって、バ
ーナ１ｂに供給する残ガスの発熱量を低減させ、前記改
質器の温度を設定値以下に低下させることができる。In the above apparatus, when the measured value of the thermometer 5 is higher than the set value, the discharge pressure of the compressor 2 is determined based on the measured value of the pressure gauge 16 for measuring the discharge pressure of the compressor 2. The controller 14 adjusts the control valve 17 so as to raise it. Conversely, when the measured value of the thermometer 5 is lower than the set value, the control device 1
4 adjusts the control valve 17. In this way, when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of the heat resistance of the reformer, the discharge pressure of the compressor 2 is increased, and P
By improving the hydrogen yield in SA3, the calorific value of the residual gas supplied to the burner 1b can be reduced, and the temperature of the reformer can be reduced to a set value or less.
【００３１】図３は、請求項２，４の発明に関わるこの
発明の異なる実施例を示す。この実施例では、温度計５
の測定値が設定値より高い場合は、ＰＳＡ３の水素精製
後の残ガスをバーナ１ｂに戻す経路に三方向流量制御弁
１８を設け、温度計５と連携する制御装置２４により、
燃焼に必要なガス量に対して過剰分は、改質器の上流側
に戻し、再び触媒層を有する触媒管１ａに還流する制御
を行う。なお、この実施例においては、温度計５の計測
端を、バーナの燃焼排ガス部に設けている。FIG. 3 shows a different embodiment of the present invention according to the second and fourth aspects of the present invention. In this embodiment, the thermometer 5
If the measured value is higher than the set value, a three-way flow control valve 18 is provided on a path for returning the residual gas after hydrogen purification of the PSA 3 to the burner 1b, and the control device 24 cooperating with the thermometer 5
An excess amount of the gas required for the combustion is returned to the upstream side of the reformer, and is controlled to return to the catalyst tube 1a having the catalyst layer again. In this embodiment, the measuring end of the thermometer 5 is provided in the combustion exhaust gas portion of the burner.
【００３２】上記により、改質器の温度（前記触媒層温
度もしくはバーナの燃焼排ガス温度）が改質器の耐熱性
の観点から定めた所定の設定値を超えた場合に、残ガス
の一部を前記触媒層に再循環し、ＰＳＡ３における水素
収率を向上させることによってバーナ１ｂに供給する前
記残ガスの発熱量を低減させ、改質器の温度を設定値以
下に低下させることができる。As described above, when the temperature of the reformer (the temperature of the catalyst layer or the temperature of the combustion exhaust gas of the burner) exceeds a predetermined value determined from the viewpoint of the heat resistance of the reformer, a part of the residual gas is removed. Is recirculated to the catalyst layer to improve the hydrogen yield in the PSA 3, thereby reducing the calorific value of the residual gas supplied to the burner 1b and lowering the temperature of the reformer below a set value.
【００３３】[0033]
【発明の効果】上記のように、本発明によれば、改質器
の温度（前記触媒層温度もしくはバーナの燃焼排ガス温
度）が改質器の耐熱性の観点から定めた所定の設定値を
超えた場合に、圧縮機の吐出圧力とＰＳＡの吸着圧力を
上昇させ、ＰＳＡにおける水素収率を向上させることに
よって、ＰＳＡからバーナに供給する残ガスの発熱量を
低減させ、前記改質器の温度を設定値以下に低下させる
こととする、あるいは、改質器の温度が改質器の耐熱性
の観点から定めた所定の設定値を超えた場合に、残ガス
の一部を前記触媒層に再循環し、ＰＳＡにおける水素収
率を向上させることによって、バーナに供給する前記残
ガスの発熱量を低減させ、改質器の温度を設定値以下に
低下させることとしたので、水素精製後の残ガスを無駄
に放出することなく、適正な改質器の温度制御が可能と
なる。また、配管，圧力計などの一部の周辺機器の追加
のみで製品水素の製造量を増加させることができる。総
じて、設備コスト及び運転コストが低い水素発生装置と
その運転方法を提供することができる。As described above, according to the present invention, the temperature of the reformer (the temperature of the catalyst layer or the temperature of the combustion exhaust gas of the burner) is set to a predetermined value determined from the viewpoint of the heat resistance of the reformer. If it exceeds, the discharge pressure of the compressor and the adsorption pressure of the PSA are increased to increase the hydrogen yield in the PSA, thereby reducing the calorific value of the residual gas supplied from the PSA to the burner. When the temperature is to be reduced to a set value or less, or when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of the heat resistance of the reformer, part of the residual gas is converted to the catalyst layer. By reducing the calorific value of the residual gas supplied to the burner and reducing the temperature of the reformer to a set value or less by improving the hydrogen yield in the PSA, Do not waste the remaining gas , It is possible to control the temperature of the proper reformer. Further, the production amount of product hydrogen can be increased only by adding some peripheral devices such as a pipe and a pressure gauge. In general, it is possible to provide a hydrogen generator and a method of operating the hydrogen generator, which have low equipment costs and low operation costs.
【図１】この発明の第１の実施例を示す水素発生装置の
概略構成図である。FIG. 1 is a schematic configuration diagram of a hydrogen generator showing a first embodiment of the present invention.
【図２】この発明の第２の実施例を示す水素発生装置の
概略構成図である。FIG. 2 is a schematic configuration diagram of a hydrogen generator showing a second embodiment of the present invention.
【図３】この発明の第３の実施例を示す水素発生装置の
概略構成図である。FIG. 3 is a schematic configuration diagram of a hydrogen generator showing a third embodiment of the present invention.
【図４】従来例の水素発生装置の概略構成図である。FIG. 4 is a schematic configuration diagram of a conventional hydrogen generator.
１：改質器、１ａ：改質管、１ｂ：バーナ、２：圧縮
機、３：圧力スイング吸着装置（ＰＳＡ）、４，１４，
２４：制御装置、５：温度計、１６：圧力計、１７：制
御弁、１８：三方向流量制御弁。1: reformer, 1a: reforming tube, 1b: burner, 2: compressor, 3: pressure swing adsorption device (PSA), 4, 14,
24: control device, 5: thermometer, 16: pressure gauge, 17: control valve, 18: three-way flow control valve.
フロントページの続き (72)発明者 高見 晋 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 (72)発明者 永瀬 真一 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 Ｆターム(参考） 4G040 EA02 EA03 EA06 EB12 EB33 EB43 EB44 EB45 Continuation of the front page (72) Inventor Susumu Takami 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Osaka Gas Co., Ltd. (72) Inventor Shinichi Nagase 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka No. Osaka Gas Co., Ltd. F-term (reference) 4G040 EA02 EA03 EA06 EB12 EB33 EB43 EB44 EB45
Claims (4)
などの炭化水素改質原料ガスを，水蒸気とともに触媒層
を通過させることにより水素リッチな改質ガスを生成す
るための改質管と、燃焼排ガスを改質原料の加熱媒体と
して利用するためのバーナとを備えた改質器と、前記改
質ガスまたは改質原料ガスを加圧するための圧縮機と、
加圧された改質ガスから水素を分離精製する圧力スイン
グ吸着装置（ＰＳＡ）と、このＰＳＡにおいて水素を分
離除去処理した後の残ガスを前記改質器のバーナに供給
して燃焼させるように構成した水素発生装置の運転方法
において、前記改質器の温度（前記触媒層温度もしくは
バーナの燃焼排ガス温度）が改質器の耐熱性の観点から
定めた所定の設定値を超えた場合に、前記圧縮機の吐出
圧力とＰＳＡの吸着圧力を上昇させ、前記ＰＳＡにおけ
る水素収率を向上させることによって前記バーナに供給
する前記残ガスの発熱量を低減させ、前記改質器の温度
を設定値以下に低下させることを特徴とする水素発生装
置の運転方法。1. A reforming pipe for generating a hydrogen-rich reformed gas by passing a hydrocarbon reforming raw material gas such as natural gas, LNG, LPG, and methanol together with steam through a catalyst layer, and a combustion exhaust gas. A reformer provided with a burner for utilizing the heating medium for the reforming raw material, and a compressor for pressurizing the reformed gas or the reforming raw material gas,
A pressure swing adsorption apparatus (PSA) for separating and purifying hydrogen from pressurized reformed gas, and a residual gas after separating and removing hydrogen in the PSA is supplied to a burner of the reformer for combustion. In the operating method of the configured hydrogen generator, when the temperature of the reformer (the catalyst layer temperature or the combustion exhaust gas temperature of the burner) exceeds a predetermined set value determined from the viewpoint of the heat resistance of the reformer, By raising the discharge pressure of the compressor and the adsorption pressure of PSA, and improving the hydrogen yield in the PSA, the calorific value of the residual gas supplied to the burner is reduced, and the temperature of the reformer is set to a set value. A method for operating a hydrogen generator, wherein the method is reduced as follows.
などの炭化水素改質原料ガスを，水蒸気とともに触媒層
を通過させることにより水素リッチな改質ガスを生成す
るための改質管と、燃焼排ガスを改質原料の加熱媒体と
して利用するためのバーナとを備えた改質器と、前記改
質ガスまたは原料ガスを加圧するための圧縮機と、加圧
された改質ガスから水素を分離精製する圧力スイング吸
着装置（ＰＳＡ）と、このＰＳＡにおいて水素を分離除
去処理した後の残ガスを前記改質器のバーナに供給して
燃焼させるように構成した水素発生装置において、前記
圧縮機の吐出側の圧力を測定する圧力計と、この圧力を
制御する手段として圧縮機の吐出側から吸い込み側に接
続されたバイパス配管経路に設けた制御弁と、前記改質
器の温度（前記触媒層温度もしくはバーナの燃焼排ガス
温度）を測定する温度計と、前記改質器の温度が改質器
の耐熱性の観点から定めた所定の設定値を超えた場合
に，前記圧縮機の吐出圧力とＰＳＡの吸着圧力を上昇さ
せ，前記改質器の温度を設定値以下に低下させるるよう
な制御装置とを備えたことを特徴とする水素発生装置。2. A reforming pipe for generating a hydrogen-rich reformed gas by passing a hydrocarbon reforming raw material gas such as natural gas, LNG, LPG, and methanol together with steam through a catalyst layer, and a combustion exhaust gas. A reformer equipped with a burner for utilizing the heat as a heating medium for the reforming raw material, a compressor for pressurizing the reformed gas or the raw material gas, and separating and purifying hydrogen from the pressurized reformed gas A pressure swing adsorption device (PSA), and a hydrogen generator configured to supply residual gas after separation and removal of hydrogen in the PSA to a burner of the reformer for combustion, and discharge the discharge of the compressor. A pressure gauge for measuring the pressure on the pressure side, a control valve provided as a means for controlling the pressure in a bypass pipe route connected from the discharge side to the suction side of the compressor, and a temperature of the reformer (the catalyst A thermometer for measuring a bed temperature or a combustion exhaust gas temperature of a burner, and a discharge pressure of the compressor when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of heat resistance of the reformer. And a control device for increasing the PSA adsorption pressure and lowering the temperature of the reformer below a set value.
などの炭化水素改質原料ガスを，水蒸気とともに触媒層
を通過させることにより水素リッチな改質ガスを生成す
るための改質管と、燃焼排ガスを改質原料の加熱媒体と
して利用するためのバーナとを備えた改質器と、前記改
質ガスまたは改質原料ガスを加圧するための圧縮機と、
加圧された改質ガスから水素を分離精製する圧力スイン
グ吸着装置（ＰＳＡ）と、このＰＳＡにおいて水素を分
離除去処理した後の残ガスを前記改質器のバーナに供給
して燃焼させるように構成した水素発生装置の運転方法
において、前記改質器の温度（前記触媒層温度もしくは
バーナの燃焼排ガス温度）が改質器の耐熱性の観点から
定めた所定の設定値を超えた場合に、前記残ガスの一部
を前記触媒層に再循環し、前記ＰＳＡにおける水素収率
を向上させることによって前記バーナに供給する前記残
ガスの発熱量を低減させ、前記改質器の温度を設定値以
下に低下させることを特徴とする水素発生装置の運転方
法。3. A reforming pipe for generating a hydrogen-rich reformed gas by passing a hydrocarbon reforming raw material gas such as natural gas, LNG, LPG, and methanol together with steam through a catalyst layer, and a combustion exhaust gas. A reformer provided with a burner for utilizing the heating medium for the reforming raw material, and a compressor for pressurizing the reformed gas or the reforming raw material gas,
A pressure swing adsorption apparatus (PSA) for separating and purifying hydrogen from pressurized reformed gas, and a residual gas after separating and removing hydrogen in the PSA is supplied to a burner of the reformer for combustion. In the operating method of the configured hydrogen generator, when the temperature of the reformer (the catalyst layer temperature or the combustion exhaust gas temperature of the burner) exceeds a predetermined set value determined from the viewpoint of the heat resistance of the reformer, A part of the residual gas is recirculated to the catalyst layer, the amount of heat generated by the residual gas supplied to the burner is reduced by improving the hydrogen yield in the PSA, and the temperature of the reformer is set to a set value. A method for operating a hydrogen generator, wherein the method is reduced as follows.
などの炭化水素改質原料ガスを，水蒸気とともに触媒層
を通過させることにより水素リッチな改質ガスを生成す
るための改質管と、燃焼排ガスを改質原料の加熱媒体と
して利用するためのバーナとを備えた改質器と、前記改
質ガスまたは原料ガスを加圧するための圧縮機と、加圧
された改質ガスから水素を分離精製する圧力スイング吸
着装置（ＰＳＡ）と、このＰＳＡにおいて水素を分離除
去処理した後の残ガスを前記改質器のバーナに供給して
燃焼させるように構成した水素発生装置において、前記
残ガスを改質器のバーナに供給する経路に設けた三方向
流量制御弁と、前記残ガスの一部を前記三方向流量制御
弁から前記触媒層に還流するための還流バイパス配管
と、前記改質器の温度（前記触媒層温度もしくはバーナ
の燃焼排ガス温度）を測定する温度計と、前記改質器の
温度が改質器の耐熱性の観点から定めた所定の設定値を
超えた場合に，前記残ガスの一部を触媒層に再循環さ
せ，前記改質器の温度を設定値以下に低下させるるよう
な制御装置とを備えたことを特徴とする水素発生装置。4. A reforming pipe for generating a hydrogen-rich reformed gas by passing a hydrocarbon reforming raw material gas such as natural gas, LNG, LPG, and methanol together with steam through a catalyst layer, and a combustion exhaust gas. A reformer equipped with a burner for utilizing the heat as a heating medium for the reforming raw material, a compressor for pressurizing the reformed gas or the raw material gas, and separating and purifying hydrogen from the pressurized reformed gas A pressure swing adsorption device (PSA), and a hydrogen generator configured to supply the residual gas after the hydrogen is separated and removed in the PSA to a burner of the reformer to burn the residual gas. A three-way flow control valve provided in a path for supplying to the burner of the reformer; a reflux bypass pipe for returning a part of the residual gas from the three-way flow control valve to the catalyst layer; temperature A thermometer for measuring (the temperature of the catalyst layer or the temperature of the combustion exhaust gas of the burner); and, when the temperature of the reformer exceeds a predetermined set value determined from the viewpoint of heat resistance of the reformer, the residual gas And a control device for recirculating a part of the gas to the catalyst layer to lower the temperature of the reformer below a set value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08945599A JP4116731B2 (en) | 1999-03-30 | 1999-03-30 | Hydrogen generator and operation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08945599A JP4116731B2 (en) | 1999-03-30 | 1999-03-30 | Hydrogen generator and operation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000281308A true JP2000281308A (en) | 2000-10-10 |
| JP4116731B2 JP4116731B2 (en) | 2008-07-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP08945599A Expired - Lifetime JP4116731B2 (en) | 1999-03-30 | 1999-03-30 | Hydrogen generator and operation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269593A (en) * | 2006-03-31 | 2007-10-18 | Osaka Gas Co Ltd | Hydrogen manufacturing plant |
| JP2008524107A (en) * | 2004-12-17 | 2008-07-10 | テキサコ ディベラップメント コーポレイション | Apparatus and method for hydrogen production |
| JP2008524106A (en) * | 2004-12-17 | 2008-07-10 | テキサコ ディベラップメント コーポレイション | Apparatus and method for producing hydrogen |
| JP2008526657A (en) * | 2004-12-17 | 2008-07-24 | テキサコ ディベラップメント コーポレイション | Apparatus and method for controlling speed of compressor motor of hydrogen production apparatus |
| CN100420507C (en) * | 2003-07-24 | 2008-09-24 | 乔治洛德方法研究和开发液化空气有限公司 | Adsorption method for producing hydrogen and device for carrying out said method |
| CN110621614A (en) * | 2017-05-04 | 2019-12-27 | 林德股份公司 | Improved use of residual gas from pressure swing adsorption units |
| CN112209342A (en) * | 2020-10-10 | 2021-01-12 | 辽宁华融富瑞新能源科技股份有限公司 | Reforming furnace for producing hydrogen by reforming natural gas |
-
1999
- 1999-03-30 JP JP08945599A patent/JP4116731B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420507C (en) * | 2003-07-24 | 2008-09-24 | 乔治洛德方法研究和开发液化空气有限公司 | Adsorption method for producing hydrogen and device for carrying out said method |
| JP2008524107A (en) * | 2004-12-17 | 2008-07-10 | テキサコ ディベラップメント コーポレイション | Apparatus and method for hydrogen production |
| JP2008524106A (en) * | 2004-12-17 | 2008-07-10 | テキサコ ディベラップメント コーポレイション | Apparatus and method for producing hydrogen |
| JP2008526657A (en) * | 2004-12-17 | 2008-07-24 | テキサコ ディベラップメント コーポレイション | Apparatus and method for controlling speed of compressor motor of hydrogen production apparatus |
| JP2007269593A (en) * | 2006-03-31 | 2007-10-18 | Osaka Gas Co Ltd | Hydrogen manufacturing plant |
| CN110621614A (en) * | 2017-05-04 | 2019-12-27 | 林德股份公司 | Improved use of residual gas from pressure swing adsorption units |
| CN112209342A (en) * | 2020-10-10 | 2021-01-12 | 辽宁华融富瑞新能源科技股份有限公司 | Reforming furnace for producing hydrogen by reforming natural gas |
| CN112209342B (en) * | 2020-10-10 | 2022-06-28 | 辽宁华融富瑞新能源科技股份有限公司 | Reforming furnace for reforming natural gas to produce hydrogen |
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| Publication number | Publication date |
|---|---|
| JP4116731B2 (en) | 2008-07-09 |
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