JPH0519598B2 - - Google Patents
Info
- Publication number
- JPH0519598B2 JPH0519598B2 JP60099260A JP9926085A JPH0519598B2 JP H0519598 B2 JPH0519598 B2 JP H0519598B2 JP 60099260 A JP60099260 A JP 60099260A JP 9926085 A JP9926085 A JP 9926085A JP H0519598 B2 JPH0519598 B2 JP H0519598B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- clinoptilolite
- raw material
- material gas
- components
- 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.)
- Expired - Lifetime
Links
- 239000002994 raw material Substances 0.000 claims description 31
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 29
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 29
- 239000003463 adsorbent Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 74
- 239000000047 product Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Industrial Gases (AREA)
Description
産業上の利用分野
本発明は、CO2、N2等の非燃焼成分と、H2、
CO、炭化水素成分等の燃焼成分とよりなる原料
ガスから、主として非燃焼成分およびCOを分離
除去して、COを含まない高カロリーの製品ガス
を得る方法に関するものである。
従来の技術
CO2、N2等の非燃焼成分と、H2、CO、炭化水
素等の燃焼成分とよりなる原料ガスから、主とし
て非燃焼成分および有毒なCOを分離除去して、
COを含まない高カロリーの製品ガスを得るには、
原料ガスからCO2、N2等の非燃焼成分および有
毒なCOを効率良く分離除去することが必要であ
る。
従来、CO2、N2またはCO2を含むガスからこれ
らの成分を除去する方法としては、次のような方
法が実用化されている。
(i) CO2の除去
熱炭酸アルカリ法、熱炭酸アルカリとモノエ
タノールアミンの二段処理法、PSA法
(ii) N2の除去
PSA法、深冷分離法
(iii) COの除去
深冷分離法、銅アンモニア法、コソーブ
（COSORB）法、COのメタネーシヨン化
発明が解決しようとする問題点
しかしながら、上記のような各ガス単独の分離
技術は、PSA法を除いては概ね設備費が大であ
る上、電力、蒸気等の熱エネルギーが大きく、し
かもこれらの技術の組合せは一層複雑な設備を要
するため、大容量のガスの処理には適していても
中、小容量のガスの処理には有利とは言えない。
また、中・小容量のガスの処理に適している
PSA法については、各ガス単独の除去は可能で
あるものの、CO2、N2などの非燃焼成分および
有毒なCOを含む原料ガスからこれらの成分を加
温状態で効率良く同時に除去する方法は見当らな
い。
上述の状況に鑑み、本発明は、加温下での
PSA法を採用して、CO2、N2等の非燃焼成分と、
H2、CO、炭化水素等の燃焼成分とよりなる原料
ガスから、主として非燃焼成分およびCOを分離
除去して、COを含まない高カロリーの製品ガス
を得得る工業的に有利な方法を見出すべくなされ
たものである。
問題点を解決するための手段
本発明の高カロリーガスの製造法は、CO2、
N2等の非燃焼成分と、H2、CO、炭化水素等の燃
焼成分とよりなる原料ガスａを、50〜200℃の加
温条件下にクリノプチロライト系吸着剤を充填し
た吸着塔を通過させることにより、主として非燃
焼成分およびCOを分離除去して、COを含まない
高カロリーの製品ガスｂとなすことを特徴とする
ものであり、このような方法を見出すことによ
り、上記問題点を解決するに至つた。
本発明に適用できる原料ガスａとしては、
CO2、N2等の非燃焼成分と、H2、CO、炭化水素
等の燃焼成分とよりなるCOを含む低カロリーガ
スを言い、たとえば、コークス炉から発生するコ
ークス炉ガス、メタン化反応ガス等があげられ
る。ただし、H2、CO、CO2、N2の全ての成分を
含んでいなくてもよい。なお、原料ガスａが
H2Oを含む場合は、これを許容限度以下にまで
除去しておく必要がある。H2Oの存在は、クリ
ノプチロライト系吸着剤充填塔において、CO、
CO2のような極性を持つた成分の吸着を妨害する
からである。
クリノプチロライト系吸着剤充填塔における天
然ゼオライトとしては、天然に産出するクリノプ
チロライトを原料とするもの、すなわち、市販の
天然産出クリノプチロライトをそのままあるいは
イオン交換等化学的処理加工後必要に応じ破砕し
たもの、あるいは粉砕して適当な結合剤を加えて
成型、焼結したもの、あるいは単に上記クリノプ
チロライトを熱処理したものなどが用いられ、ま
た、合成法によつて得られたクリノプチロライト
を原料とするものも用いられる。通常のゼオライ
ト吸着剤は低カロリーガスをCOを含まない高カ
ロリーガスとすることができず、本発明の目的に
は適当でない。
クリノプチロライト系吸着剤充填塔の温度は、
50〜200℃の範囲の温度に設定され、50℃未満で
は製品ガスｂ中に有毒なCOが混入するようにな
り、200℃を越えるときは、サイクル時間が短か
くなる上の上熱エネルギーの点からも不利とな
る。特に好ましい温度範囲は、50〜100℃である。
本発明の方法は、さらに詳しくは、次の工程操作
により行われる。
(1) 原料ガスａをクリノプチロライト系吸着剤充
填塔に導入するに先立ち、同塔より導出される
製品ガスｂまたは原料ガスａ自身により同塔を
昇圧する工程、
(2) 原料ガスａを加温下にあるクリノプチロライ
ト系吸着剤充填塔に導入することにより原料ガ
スａ中に含まれるCO、CO2、N2成分を吸着さ
せると共に、これらの成分が除去された製品ガ
スｂを同塔から導出させる工程、
(3) クリノプチロライト系吸着剤充填塔において
吸着されたCO、CO2、N2成分を減圧操作によ
り脱離させてパージガスｃとして除去する工
程。
第１図は、上記工程の流れを示したフローシー
トである。
以下、上記の各工程を詳細に説明する。
工程 １
工程１は、原料ガスａをクリノプチロライト系
吸着剤充填塔に導入するに先立ち、同塔より導出
される製品ガスｂにより同塔を昇圧する工程から
なる。なお、上記製品ガスｂに代えてあるいはこ
のガスｂと共に、原料ガスａ自身を昇圧に用いて
もよい。
このように昇圧することは、CO、CO2、N2の
吸着、およびそれらの成分を炭化水素成分から効
果的に分離するために必要である。
この昇圧工程１における圧力は、１〜50Kg／cm2
Ｇの範囲から選択することができるが、ガス圧縮
のためのエネルギーコストの上昇等の問題を考慮
すると、５〜10Kg／cm2Ｇに設定することが好まし
い。
工程 ２
工程２は、原料ガスａを加温下にあるクリノプ
チロライト系吸着剤充填塔に導入することにより
原料ガスａ中に含まれるCO、CO2、N2成分を吸
着させると共に、これらの成分が除去された製品
ガスｂを同塔から導出させる工程からなる。この
工程は、次の手順で実施する。
前工程１により昇圧された加温状態のクリノプ
チロライト系吸着剤充填塔に原料ガスａを導入し
てCO、CO2、N2成分をクリノプチロライト系吸
着剤に吸着させると同時に、炭化水素成分を濃縮
する。
そして、塔から導出される製品ガスｂ中の最も
沸点の高い炭化水素成分が原料ガスａ中の濃度以
上になつた時点で、原料ガスａの導入を止める。
なお、塔より導出されたCO、CO2、N2成分が
除去された製品ガスｂは、その一部を前述の工程
(1)における塔の昇圧に用いる。
工程 ３
工程３は、クリノプチロライト系吸着剤充填塔
において吸着されたCO、CO2、N2成分を減圧操
作により脱離させてパージガスｃとして除去する
工程からなる。
すなわち、まず塔の圧力を所定圧から大気圧ま
で減圧し、さらに真空減圧する。なお、大気圧ま
で減圧する際、その一部を製品ガスｂとして回収
し、残りをパージガスｃとして除去してもよい。
この工程３における真空度は、０〜760torrの
範囲からCO、CO2、N2の吸着量、脱離量、ある
いは脱離速度に見合うように適宜設定する。
上述のように、工程２において塔から導出され
るガスが製品ガスｂとなり、そのまま燃料とし
て、あるいは代替天然ガス製造に用いる添加剤と
して利用される。
また、工程３において塔から減圧操作により脱
離されるCO、CO2、N2濃縮ガスがパージガスｃ
となり、化学原料等に利用される。
作 用
本発明においては、クリノプチロライト系吸着
剤充填塔における加温下の圧力スイング操作によ
り原料ガスａからCO、CO2、N2成分と製品ガス
ｂとが分離される。
実施例
次に実施例をあげて、本発明をさらに詳細に説
明する。
実施例 １
市販の天然産出クリノプチロライトを吸着剤と
して充填したクリノプチロライト系吸着剤充填塔
に、第１表の原料ガスの欄に示した組成を有する
原料ガスａを導入し、下記の操作条件にてPSA
サイクルを繰り返した。
操作条件
通ガス量 800c.c.／min
充填量 240c.c.
（21mmφ×690mmＨ）
圧 力 ７Kg ／cm2Ｇ
塔内温度 80℃
PSAサイクル
昇 圧 60torr→７Kg／cm2Ｇ
（製品ガスｂ使用）
吸 着 7min
大気圧減圧 ７Kg／cm2Ｇ→０Kg／cm2Ｇ
真空減圧 ０Kg／cm2Ｇ→60torr
サイクル実施30回目のときのクリノプチロライ
ト系吸着剤充填塔から導出される製品ガスｂの組
成を第１表の製品ガスの欄に示す。
比較例 １
比較のため、塔内温度を20℃としかつ吸着時間
を16分としたほかは実施例１と全く同一の条件で
PSAサイクルを２回繰り返したときの結果を第
１表に併せて示す。
比較例 ２
また比較のため、上記と同一の原料ガスａを市
販のゼオライト吸着剤MS−5Aを吸着剤として充
填した塔に導入し、実施例１と全く同一の条件で
PSAサイクルを５回繰り返したときの結果を第
１表に併せて示す。
Industrial Application Field The present invention is applicable to non-combustible components such as CO 2 and N 2 and H 2 ,
This invention relates to a method for obtaining a high-calorie product gas that does not contain CO by separating and removing mainly non-combustible components and CO from a raw material gas consisting of combustion components such as CO and hydrocarbon components. Conventional technology Mainly non-combustible components and toxic CO are separated and removed from a raw material gas consisting of non-combustible components such as CO 2 and N 2 and combustible components such as H 2 , CO and hydrocarbons.
To obtain a high-calorie product gas that does not contain CO,
It is necessary to efficiently separate and remove non-combustible components such as CO 2 and N 2 and toxic CO from raw material gas. Conventionally, the following methods have been put into practical use as methods for removing these components from gases containing CO 2 , N 2 or CO 2 . (i) Removal of CO 2 Hot alkaline carbonate method, two-stage treatment method of hot alkali carbonate and monoethanolamine, PSA method (ii) Removal of N 2 PSA method, cryogenic separation method (iii) Removal of CO Cryogenic separation Problems to be solved by the CO methanation method, copper ammonia method, COSORB method, and the invention for CO methanation Moreover, the thermal energy of electricity, steam, etc. is large, and the combination of these technologies requires more complex equipment, so although it is suitable for processing large volumes of gas, it is not suitable for processing small to medium volumes of gas. I can't say it's advantageous. It is also suitable for processing medium and small volumes of gas.
Regarding the PSA method, although it is possible to remove each gas individually, there is no way to efficiently remove non-combustible components such as CO 2 and N 2 and toxic CO from the raw material gas simultaneously under heating conditions. I can't find it. In view of the above-mentioned situation, the present invention provides
By adopting the PSA method, non-combustible components such as CO 2 and N 2 and
To find an industrially advantageous method for obtaining a high-calorie product gas that does not contain CO by separating and removing mainly non-combustible components and CO from a raw material gas consisting of combustion components such as H 2 , CO, and hydrocarbons. This is something that has been done as much as possible. Means for Solving the Problems The method for producing high calorie gas of the present invention uses CO 2 , CO 2 ,
A raw material gas a consisting of non-combustible components such as N 2 and combustible components such as H 2 , CO, and hydrocarbons is heated to 50 to 200°C in an adsorption tower filled with clinoptilolite adsorbent. This method is characterized by separating and removing mainly non-combustible components and CO to produce a high-calorie product gas b that does not contain CO. By discovering such a method, the above problems can be solved. I was able to resolve the issue. As the raw material gas a that can be applied to the present invention,
A low-calorie gas containing CO, which consists of non-combustible components such as CO 2 and N 2 and combustible components such as H 2 , CO, and hydrocarbons. For example, coke oven gas generated from coke ovens, methanation reaction gas, etc. etc. can be mentioned. However, it does not have to contain all the components of H 2 , CO, CO 2 and N 2 . Note that the raw material gas a is
If it contains H 2 O, it must be removed to below permissible limits. The presence of H 2 O means that CO,
This is because it interferes with the adsorption of polar components such as CO 2 . The natural zeolite used in the clinoptilolite-based adsorbent packed tower is one made from naturally occurring clinoptilolite, that is, commercially available naturally occurring clinoptilolite as it is or after chemical processing such as ion exchange. If necessary, clinoptilolite is crushed, or crushed and molded and sintered with the addition of an appropriate binder, or simply heat-treated from the above clinoptilolite.Also, it can be obtained by synthetic methods. Those made from clinoptilolite are also used. Ordinary zeolite adsorbents cannot convert low-calorie gas into high-calorie gas that does not contain CO, and are not suitable for the purpose of the present invention. The temperature of the clinoptilolite adsorbent packed column is
The temperature is set in the range of 50 to 200°C. If it is less than 50°C, toxic CO will be mixed into the product gas b, and if it exceeds 200°C, the cycle time will be shortened and the thermal energy will be used. It is also disadvantageous from this point of view. A particularly preferred temperature range is 50-100°C.
More specifically, the method of the present invention is carried out by the following process operations. (1) Prior to introducing raw material gas a into the clinoptilolite-based adsorbent-packed column, a step of pressurizing the column with product gas b or raw material gas a itself derived from the column; (2) raw material gas a is introduced into a heated clinoptilolite-based adsorbent packed column to adsorb CO, CO 2 and N 2 components contained in raw material gas a, and produce product gas b from which these components have been removed. (3) A step of desorbing CO, CO 2 and N 2 components adsorbed in the clinoptilolite-based adsorbent packed column by depressurization operation and removing them as purge gas c. FIG. 1 is a flow sheet showing the flow of the above steps. Each of the above steps will be explained in detail below. Step 1 Step 1 consists of a step in which, prior to introducing raw material gas a into a clinoptilolite-based adsorbent-packed column, the pressure of the column is increased by product gas b derived from the column. Note that, instead of or together with the product gas b, the raw material gas a itself may be used for pressurization. This pressure increase is necessary for the adsorption of CO, CO 2 , N 2 and the effective separation of these components from the hydrocarbon components. The pressure in this pressure increasing step 1 is 1 to 50Kg/cm 2
Although it can be selected from the range of 5 to 10 kg/cm 2 G, considering problems such as increase in energy cost for gas compression, it is preferable to set it to 5 to 10 kg/cm 2 G. Step 2 In Step 2, CO, CO 2 and N 2 components contained in the raw material gas a are adsorbed by introducing the raw material gas a into a column packed with clinoptilolite adsorbent under heating. The product gas b from which the components have been removed is discharged from the same column. This process is carried out in the following steps. The raw material gas a is introduced into the heated clinoptilolite-based adsorbent packed column whose pressure has been increased in the previous step 1, and at the same time, CO, CO 2 and N 2 components are adsorbed on the clinoptilolite-based adsorbent. Concentrate hydrocarbon components. Then, when the concentration of the hydrocarbon component with the highest boiling point in product gas b derived from the tower reaches a concentration equal to or higher than that in raw material gas a, the introduction of raw material gas a is stopped. In addition, a part of the product gas b from which the CO, CO 2 and N 2 components have been removed is passed through the above-mentioned process.
Used for increasing the pressure of the column in (1). Step 3 Step 3 consists of a step in which the CO, CO 2 and N 2 components adsorbed in the clinoptilolite-based adsorbent packed column are desorbed by a reduced pressure operation and removed as purge gas c. That is, first, the pressure in the tower is reduced from a predetermined pressure to atmospheric pressure, and then the pressure is further reduced to vacuum. Note that when the pressure is reduced to atmospheric pressure, a part of it may be recovered as product gas b, and the remainder may be removed as purge gas c. The degree of vacuum in this step 3 is appropriately set in the range of 0 to 760 torr to match the adsorption amount, desorption amount, or desorption rate of CO, CO 2 , and N 2 . As described above, the gas discharged from the tower in step 2 becomes product gas b, which is used as it is as a fuel or as an additive for producing alternative natural gas. In addition, the CO, CO 2 and N 2 concentrated gases desorbed from the tower in step 3 by depressurization are used as purge gas c.
It is used as a chemical raw material, etc. Function In the present invention, CO, CO 2 and N 2 components and product gas b are separated from raw material gas a by a pressure swing operation under heating in a column packed with a clinoptilolite adsorbent. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Example 1 Raw material gas a having the composition shown in the raw material gas column of Table 1 was introduced into a clinoptilolite-based adsorbent packed tower filled with commercially available naturally produced clinoptilolite as an adsorbent, and the following PSA under operating conditions
The cycle was repeated. Operating conditions Gas flow rate 800c.c./min Filling rate 240c.c. (21mmφ×690mmH) Pressure 7Kg/ cm2G Tower internal temperature 80℃ PSA cycle Pressure increase 60torr→7Kg/ cm2G (Product gas b used ) Adsorption 7min Atmospheric pressure reduction 7Kg/cm 2 G → 0Kg/cm 2 G Vacuum pressure reduction 0Kg/cm 2 G → 60torr Product gas b derived from the clinoptilolite adsorbent packed column at the 30th cycle execution The composition of the gas is shown in the column of product gas in Table 1. Comparative Example 1 For comparison, the conditions were exactly the same as in Example 1 except that the temperature inside the column was 20°C and the adsorption time was 16 minutes.
Table 1 also shows the results when the PSA cycle was repeated twice. Comparative Example 2 For comparison, the same raw material gas a as above was introduced into a column packed with a commercially available zeolite adsorbent MS-5A as an adsorbent, and it was treated under exactly the same conditions as in Example 1.
Table 1 also shows the results when the PSA cycle was repeated five times.
【表】
第１表からわかるように、実施例１においては
サイクル30回目においてもCO2、O2は100％、N2
は50％除去され、その結果製品ガスｂにはCOが
含まれないばかりか、ガスカロリーが増大した。
一方、塔内温度を20℃としたときは、わずか２
回目で有毒なCOが製品ガスｂ中に含まれるよう
になつた。
また、吸着剤として市販のゼオライト吸着剤
MS−5Aを用いた比較例２においては、CO、
CO2は100％除去されるが、製品ガスｂとして回
収すべきCH4、C2H6がかなり吸着されている。
その結果、製品ガスｂのカロリーは原料ガスａの
カロリーよりもかえつて低くなつている。
発明の効果
本発明は、以上のような工程配列からなるの
で、各工程操作が円滑かつ効率良くなし得、また
目的とする高カロリーの製品ガスが収率良く回収
される。
よつて、本発明の方法を実施することにより、
H2、CO、CO2、N2等を含む炭化水素ガスから従
来より一層簡略化された工程で有毒なCOを含ま
ない高カロリーガスが安価に製造されるので、そ
の工業的意義は大きい。
また、高カロリーの製品ガスの製造に際し、ク
リノプチロライト系吸着剤充填塔から分離される
CO、CO2、N2濃縮ガスは、化学原料等に利用す
ることができるので、この点でも有利である。[Table] As can be seen from Table 1, in Example 1, even at the 30th cycle, CO 2 and O 2 were 100%, and N 2
was removed by 50%, and as a result, product gas b not only did not contain CO, but also increased gas calories. On the other hand, when the temperature inside the tower is 20℃, only 2
For the second time, toxic CO was included in product gas B. In addition, commercially available zeolite adsorbents are used as adsorbents.
In Comparative Example 2 using MS-5A, CO,
Although 100% of CO 2 is removed, a considerable amount of CH 4 and C 2 H 6 to be recovered as product gas b is adsorbed.
As a result, the calorie of product gas b is actually lower than the calorie of raw material gas a. Effects of the Invention Since the present invention consists of the above-described process arrangement, each process operation can be performed smoothly and efficiently, and the target high-calorie product gas can be recovered with a high yield. Therefore, by carrying out the method of the present invention,
It has great industrial significance because a high-calorie gas that does not contain toxic CO can be produced at low cost from a hydrocarbon gas containing H 2 , CO, CO 2 , N 2 , etc. through a process that is simpler than before. In addition, when producing high-calorie product gas, it is separated from clinoptilolite-based adsorbent-filled towers.
CO, CO 2 and N 2 concentrated gases can be used as chemical raw materials, so they are advantageous in this respect as well.
第１図は、本発明の工程の流れを示したフロー
シートである。
１，２，３……工程、ａ……原料ガス、ｂ……
製品ガス、ｃ……パージガス。
FIG. 1 is a flow sheet showing the process flow of the present invention. 1, 2, 3...Process, a...Source gas, b...
Product gas, c... purge gas.
Claims (1)
水素等の燃焼成分とよりなる原料ガスａを、50〜
200℃の加温条件下にクリノプチロライト系吸着
剤を充填した吸着塔を通過させることにより、主
として非燃焼成分およびCOを分離除去して、CO
を含まない高カロリーの製品ガスｂとなすことを
特徴とする高カロリーガスの製造法。 ２ 吸着操作が、50〜200℃の加温条件下におけ
る非平衡圧操作によるものである特許請求の範囲
第１項記載の製造法。 ３ クリノプチロライト系吸着剤が、天然に産出
するクリノプチロライトを原料とするもの、また
は合成法によつて得られるクリノプチロライトを
原料とするものである特許請求の範囲第１項記載
の製造法。 ４ CO2、N2等の非燃焼成分と、H2、CO、炭化
水素等の燃焼成分とよりなる原料ガスａを、50〜
200℃の加温条件下にクリノプチロライト系吸着
剤を充填した吸着塔を通過させることにより、主
として非燃焼成分およびCOを分離除去して、CO
を含まない高カロリーの製品ガスｂとなすにあた
り、 (1) 原料ガスａをクリノプチロライト系吸着剤充
填塔に導入するに先立ち、同塔より導出される
製品ガスｂまたは原料ガスａ自身により同塔を
昇圧する工程、 (2) 原料ガスａを加温下にあるクリノプチロライ
ト系吸着剤充填塔に導入することにより原料ガ
スａ中に含まれるCO、CO2、N2成分を吸着さ
せると共に、これらの成分が除去された製品ガ
スｂを同塔から導出させる工程、 (3) クリノプチロライト系吸着剤充填塔において
吸着されたCO、CO2、N2成分を減圧操作によ
り脱離させてパージガスｃとして除去する工
程、 を遂行することを特徴とする特許請求の範囲第１
項記載の製造法。[Claims] 1. Raw material gas a consisting of non-combustible components such as CO 2 and N 2 and combustible components such as H 2 , CO and hydrocarbons is
By passing through an adsorption tower filled with clinoptilolite adsorbent under heating conditions of 200℃, non-combustible components and CO are mainly separated and removed.
A method for producing a high-calorie gas, characterized in that the product gas b is a high-calorie product containing no. 2. The production method according to claim 1, wherein the adsorption operation is performed by non-equilibrium pressure operation under heating conditions of 50 to 200°C. 3. Claim 1, wherein the clinoptilolite-based adsorbent is made from naturally occurring clinoptilolite or from clinoptilolite obtained by a synthetic method. Manufacturing method described. 4 Raw material gas a consisting of non-combustible components such as CO 2 and N 2 and combustible components such as H 2 , CO and hydrocarbons is
By passing through an adsorption tower filled with clinoptilolite adsorbent under heating conditions of 200℃, non-combustible components and CO are mainly separated and removed.
(1) Before introducing raw material gas a into the clinoptilolite-based adsorbent-packed column, the product gas b or raw material gas a itself extracted from the column is (2) Introducing raw material gas a into a column packed with clinoptilolite adsorbent under heating to adsorb CO, CO 2 and N 2 components contained in raw material gas a. (3) removing the CO, CO 2 and N 2 components adsorbed in the clinoptilolite-based adsorbent-packed column by decompression operation; Claim 1, characterized in that the step of separating the gas and removing it as a purge gas c is performed.
Manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60099260A JPS61255995A (en) | 1985-05-09 | 1985-05-09 | Production of high-calorie gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60099260A JPS61255995A (en) | 1985-05-09 | 1985-05-09 | Production of high-calorie gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61255995A JPS61255995A (en) | 1986-11-13 |
| JPH0519598B2 true JPH0519598B2 (en) | 1993-03-17 |
Family
ID=14242741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60099260A Granted JPS61255995A (en) | 1985-05-09 | 1985-05-09 | Production of high-calorie gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61255995A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0652047B1 (en) * | 1993-11-10 | 1999-10-27 | Agency of Industrial Science and Technology of Ministry of International Trade and Industry | Method for separation of nitrogen and carbon dioxide by use of ceramic materials as separating agent |
| US5587003A (en) * | 1995-03-21 | 1996-12-24 | The Boc Group, Inc. | Removal of carbon dioxide from gas streams |
| US20050137443A1 (en) * | 2003-12-19 | 2005-06-23 | Gorawara Jayant K. | Regenerative removal of trace carbon monoxide |
| JP2010090860A (en) * | 2008-10-10 | 2010-04-22 | Mitsubishi Heavy Ind Ltd | Gas engine using low calory gaseous fuel |
-
1985
- 1985-05-09 JP JP60099260A patent/JPS61255995A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61255995A (en) | 1986-11-13 |
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