JPS621525B2 - - Google Patents
Info
- Publication number
- JPS621525B2 JPS621525B2 JP57044194A JP4419482A JPS621525B2 JP S621525 B2 JPS621525 B2 JP S621525B2 JP 57044194 A JP57044194 A JP 57044194A JP 4419482 A JP4419482 A JP 4419482A JP S621525 B2 JPS621525 B2 JP S621525B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- pressure
- carbon dioxide
- natural gas
- desorption
- 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
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
- 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
Landscapes
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
本発明は天然ガス中に含まれる炭酸ガスなどの
酸性ガスをプレツシヤースイング法（交互圧力変
動法）により除去する方法に関するものである。
天然ガスはクリーンエネルギーとして価値ある
エネルギー源でありその需要はますます高まつて
来ている。
しかし地中より採掘された天然ガスは採掘場所
により変動はあるが、通常メタンガスが大部分で
ある。その他にエチレン、エタン、プロパン等の
ガスを２〜10％、炭酸ガスを0.5〜50％、硫化水
素等１〜３％程度含んでおり、中でも炭酸ガスは
不燃性ガスであり、天然ガスの発熱量を低くする
ので好ましくない。
また、硫化水素等のイオウ化合物は装置腐触の
原因となり燃料として好ましくない。
上記の理由により採掘した天然ガスをそのまゝ
使用することは好ましくなく、これらの酸性ガス
を除去する必要があり、従来その除去法としてア
ルカリ吸収液、例えばアミン水溶液や炭酸カリウ
ム水溶液で吸収し、加熱再生する化学吸収法、加
圧水により吸収し、減圧放散する水吸収法などが
知られている。しかし前者は再生時に大量の熱エ
ネルギーを必要とし、後者は物理吸収のため30
Kg/cm2G程度の高圧にする必要があり除去コスト
が高くついている。これに対して本発明者らは吸
着剤を利用したプレツシヤースイング法により炭
酸ガス等を低コストで除去する方法を見出したも
のである。即ち本発明の要旨は天然ガス中の炭酸
ガス等をプレツシヤースイング法により除去する
方法である。
本発明の方法によれば吸着圧力も低く、必要エ
ネルギーは天然ガスを加圧するのに必要な電力の
みであり、天然ガス自体圧力がある場合はこれも
不要となる。また天然ガス自体を送り出すために
は当然加圧する必要があり、本発明の装置を出る
天然ガスは以後の装置入口圧力とほぼ同じにする
必要があるので、本装置のためのみに電力を消費
することにはならない。いずれにしても本発明の
方法により低コストで炭酸ガス等を除去すること
ができる。本発明のプレツシヤースイング法の吸
着圧力は高圧になればなるほど単位吸着剤あたり
の吸着量が多くなり、装置上小型化できる利点が
あるが、昇圧に必要な電力使用量、及び昇圧機の
コストが高くなるので吸着圧力をあまり高くする
ことは得策でない。しかし天然ガスの元圧が高圧
である場合はわざわざ降圧する必要のないことは
云うまでもない。昇圧する場合には全体コストよ
り考えて２〜10Kg/cm2G程度が好ましい。
吸着剤としてはカーボンモレキユラーシーブ、
ゼオラト系モレキユラーシーブ、シリカゲル等が
使用できるが、カーボンモレキユラーシーブを使
用する場合は水分に対する抵抗性が大きいのでガ
ス中に水分のある場合でも前以つてガスを乾燥す
る必要がない。また細孔径３Åのものを使用する
場合、炭酸ガスのみを吸着し他の炭化水素は全く
吸着しないので分離効果が非常によい。なお脱着
時も他の吸着剤に比べ吸着した炭酸ガスが容易に
脱着するため非常に有利である。
天然ガス中には一般に硫化水素等のイオウ化合
物が含まれており、これらの除去も必要である。
この場合はこれら化合物を吸脱着しやすいカーボ
ンモレキユラーシーブを充填した脱硫塔を炭酸ガ
スを吸着する吸着塔の前に設置し、吸着塔と同じ
サイクルでプレツシヤースイングを行ない除去す
ることが可能である。
以下第１図に示すフローシートに従つて本発明
を説明する
天然ガス１はサクシヨンタンク２を通して圧縮
機３で所要圧力に昇圧される。天然ガスが所要の
圧力以上の圧力を持つている場合は当然のことな
がら圧縮機は不要である。昇圧されたガスはクー
ラー４で冷却水分を低下させた後脱硫塔５、吸着
塔６に導入される。脱硫塔、吸着塔を１セツトと
してプレツシヤースイング装置は最低２塔より構
成される。塔数が多くなれば回収率も上昇する
が、設備費も上るので通常は２―６塔で構成され
る場合が多い。本プレツシヤースイング装置によ
りイオウ化合物は脱硫塔で吸着され、炭酸ガスは
吸着塔で吸着されて吸着塔を出た天然ガスはイオ
ウ化合物、炭酸ガスが除去されており製品タンク
７を通して８精製天然ガスとして送り出される。
一方脱硫塔、吸着塔で吸着されたイオウ化合
物、炭酸ガスは真空ポンプ９によつて減圧脱着さ
れる。大気圧脱着の場合は当然真空ポンプは不要
である。
天然ガス中の炭酸ガス濃度が低い場合は、脱着
ガス中のメタン、エタン等の炭化水素の割合が多
くなるため脱着工程で排出される。
初めのガスすなわち、脱着時の初めからの脱着
ガスの量が脱着ガス全体量の70％に到るまでの量
をサクシヨンタンク１にリサイクルして炭化水素
のロスを少なくする。このようにリサイクルした
後の部分のガス１０がとり出される。
以下さらに具体的に本発明の実施態様を説明す
る。
メタン80％、エタン４％、炭酸ガス15％、硫化
水素１％、水分飽和の天然ガスを昇圧機で2.5Kg/
cm2Ｇに昇圧し、市販の活性炭を脱硫塔に充填し市
販の孔経３Åのカーボンモレキユラーシーブを吸
着塔に充填した３塔式のプレツシヤースイング装
置に導入する。吸着塔は第１表に示す様に吸着工
程２分、均圧圧程１分、減圧脱着及び昇圧工程が
夫々１分であり１リサイクル６分で運転される。
The present invention relates to a method for removing acidic gases such as carbon dioxide contained in natural gas by a pressure swing method (alternate pressure fluctuation method). Natural gas is a valuable source of clean energy, and its demand is increasing. However, the majority of natural gas extracted from underground is usually methane gas, although this varies depending on the extraction location. In addition, it contains 2 to 10% of gases such as ethylene, ethane, and propane, 0.5 to 50% of carbon dioxide gas, and 1 to 3% of hydrogen sulfide. Among them, carbon dioxide is a nonflammable gas, and natural gas generates heat. This is not preferable because it lowers the amount. Furthermore, sulfur compounds such as hydrogen sulfide cause equipment corrosion and are not preferred as fuel. For the above reasons, it is not preferable to use mined natural gas as is, and it is necessary to remove these acidic gases. Conventionally, the removal method is to absorb with an alkaline absorption liquid, such as an amine aqueous solution or a potassium carbonate aqueous solution. Chemical absorption methods that involve heating and regeneration, and water absorption methods that involve absorbing with pressurized water and dissipating under reduced pressure are known. However, the former requires a large amount of thermal energy during regeneration, and the latter requires 30% due to physical absorption.
Removal costs are high as it requires high pressure of around Kg/cm 2 G. In response to this problem, the present inventors have discovered a method of removing carbon dioxide gas and the like at low cost by a pressure swing method using an adsorbent. That is, the gist of the present invention is a method for removing carbon dioxide gas etc. from natural gas by the pressure swing method. According to the method of the present invention, the adsorption pressure is also low, and the only energy required is the electric power required to pressurize the natural gas, which is also unnecessary if the natural gas itself has pressure. In addition, in order to send out the natural gas itself, it is naturally necessary to pressurize it, and the natural gas leaving the device of the present invention needs to be at approximately the same pressure as the inlet of the device thereafter, so electricity is consumed only for this device. It doesn't matter. In any case, carbon dioxide gas and the like can be removed at low cost by the method of the present invention. The higher the adsorption pressure of the pressure swing method of the present invention, the more the amount of adsorption per unit adsorbent increases, and there is an advantage that the equipment can be made smaller. It is not advisable to increase the adsorption pressure too high because it increases the cost. However, it goes without saying that if the original pressure of natural gas is high, there is no need to take the trouble to lower the pressure. When increasing the pressure, it is preferable to use about 2 to 10 kg/cm 2 G in consideration of the overall cost. Carbon molecular sieve is used as adsorbent.
Zeolat-based molecular sieves, silica gel, etc. can be used, but when carbon molecular sieves are used, they have high resistance to moisture, so there is no need to dry the gas in advance even if there is moisture in the gas. Furthermore, when using a material with a pore diameter of 3 Å, only carbon dioxide gas is adsorbed and other hydrocarbons are not adsorbed at all, so the separation effect is very good. Furthermore, during desorption, the adsorbed carbon dioxide is easily desorbed compared to other adsorbents, which is very advantageous. Natural gas generally contains sulfur compounds such as hydrogen sulfide, which also need to be removed.
In this case, it is recommended to install a desulfurization tower filled with carbon molecular sieve that easily adsorbs and desorbs these compounds in front of the adsorption tower that adsorbs carbon dioxide gas, and perform pressure swing in the same cycle as the adsorption tower to remove them. It is possible. The present invention will be described below in accordance with the flow sheet shown in FIG. 1. Natural gas 1 passes through a suction tank 2 and is pressurized to a required pressure by a compressor 3. Naturally, if the natural gas has a pressure higher than the required pressure, a compressor is not required. The pressurized gas is introduced into a desulfurization tower 5 and an adsorption tower 6 after cooling water content in a cooler 4 is reduced. A pressure swing device is composed of at least two towers, each consisting of a desulfurization tower and an adsorption tower. The recovery rate increases as the number of towers increases, but equipment costs also increase, so the system is usually configured with 2-6 towers. With this pressure swing device, sulfur compounds are adsorbed in the desulfurization tower, carbon dioxide gas is adsorbed in the adsorption tower, and the natural gas that leaves the adsorption tower has sulfur compounds and carbon dioxide removed, and passes through the product tank 7 to the purified natural gas. It is sent out as a gas. On the other hand, the sulfur compounds and carbon dioxide adsorbed in the desulfurization tower and adsorption tower are desorbed under reduced pressure by the vacuum pump 9. Of course, in the case of atmospheric pressure desorption, a vacuum pump is not required. When the carbon dioxide concentration in natural gas is low, the proportion of hydrocarbons such as methane and ethane in the desorption gas increases and is therefore discharged during the desorption process. The initial gas, that is, the amount of desorption gas from the beginning of the desorption process up to 70% of the total amount of desorption gas is recycled to the suction tank 1 to reduce loss of hydrocarbons. The gas 10 after being recycled in this way is taken out. Embodiments of the present invention will be described in more detail below. 80% methane, 4% ethane, 15% carbon dioxide, 1% hydrogen sulfide, and water-saturated natural gas in a booster at 2.5kg/
The pressure was raised to cm 2 G, and the mixture was introduced into a three-column pressure swing apparatus in which a desulfurization tower was filled with commercially available activated carbon and an adsorption tower was filled with a commercially available carbon molecular sieve with a pore diameter of 3 Å. As shown in Table 1, the adsorption tower is operated for 2 minutes for the adsorption process, 1 minute for the pressure equalization process, 1 minute each for the depressurization desorption and pressure increase processes, and 6 minutes for one recycle.
【表】
吸着工程の塔を出たガスは、炭酸ガス0.1％を
含んでおり、ほぼ完全に炭酸ガスは除去されてい
た。又、硫化水素も10ppm以下（水分も露点−
35℃以下）になつており十分な精製が行なわれて
いた。
一方均圧後真空ポンプを用いて100Torr迄減圧
脱着されたガスのうち脱着時、最初のガスはメタ
ン成分を多く含んでいるので圧縮機入口にリサイ
クルされる。このリサイクル量は全脱着ガスの約
70％である。脱着後半のガスは放出される。
このガス中のメタン成分は２％以下であり、メ
タンロスはほとんどない。
この脱着ガスは高純度のCO2ガスであり、脱硫
後液化炭酸ガスの原料として十分利用できるもの
である。
この場合の運転に必要なエネルギーは約0.2K
Ｗ／Ｎm3処理ガスであり他の炭酸ガス除去法に比
べはるかに経剤的であり、又精製と乾燥が同時に
実施できるので非常に有利である。[Table] The gas leaving the tower in the adsorption process contained 0.1% carbon dioxide gas, and carbon dioxide gas had been almost completely removed. Also, hydrogen sulfide is less than 10 ppm (moisture has a dew point of -
(below 35°C), indicating that sufficient purification had been carried out. On the other hand, among the gases desorbed by reducing the pressure to 100 Torr using a vacuum pump after pressure equalization, the first gas at the time of desorption contains a large amount of methane, so it is recycled to the compressor inlet. This recycled amount is approximately
It is 70%. Gas in the latter half of desorption is released. The methane component in this gas is 2% or less, and there is almost no methane loss. This desorption gas is highly pure CO 2 gas, which can be fully used as a raw material for liquefied carbon dioxide gas after desulfurization. The energy required for operation in this case is approximately 0.2K
Since it is a W/Nm 3 processing gas, it is much more economical than other carbon dioxide removal methods, and it is very advantageous because purification and drying can be carried out at the same time.
第１図は本発明の方法を説明するフローシート
である。
FIG. 1 is a flow sheet illustrating the method of the present invention.
Claims (1)
スを、吸着剤として平均細孔径約３Åのカーボン
モレキユラーシーブを用いたプレツシヤースイン
グ法により吸着、脱着し、脱着時の初めからの脱
着ガスの量が脱着ガス全体量の70％に到るまでの
量を原料ガスにリサイクルすることにより除去
し、回収する方法。 ２ プレツシヤースイング法の吸着圧力が大気圧
以上５Kg/cm2G以下である特許請求の範囲１記載
の方法。 ３ プレツヤースイング法の脱着圧力が0.5Kg/cm2
Ｇ以下真空までである特許請求の範囲１記載の方
法。 ４ 天然ガスの温度を40℃以下にして処理する特
許請求の範囲１記載の方法。 ５ 脱硫機構を備えたプレツシヤースイング装置
を用いて特許請求の範囲１記載の方法により炭酸
ガスと同時に硫化水素、二硫化炭素、有機イオウ
等のイオウ化合物を除去する方法。 ６ 脱硫剤として活性炭を用いる特許請求の範囲
５記載の方法。[Claims] 1. Acid gas such as carbon dioxide contained in natural gas is adsorbed and desorbed by a pressure swing method using a carbon molecular sieve with an average pore diameter of about 3 Å as an adsorbent, A method of removing and recovering up to 70% of the total amount of desorbed gas from the beginning of desorption by recycling it into raw material gas. 2. The method according to claim 1, wherein the adsorption pressure in the pressure swing method is at least atmospheric pressure and at most 5 Kg/cm 2 G. 3 The desorption pressure of the pre-swing method is 0.5Kg/cm 2
2. The method according to claim 1, wherein the pressure is less than G or less. 4. The method according to claim 1, wherein the natural gas is treated at a temperature of 40°C or less. 5. A method for removing sulfur compounds such as hydrogen sulfide, carbon disulfide, and organic sulfur simultaneously with carbon dioxide gas by the method according to claim 1 using a pressure swing device equipped with a desulfurization mechanism. 6. The method according to claim 5, in which activated carbon is used as the desulfurization agent.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57044194A JPS58159830A (en) | 1982-03-18 | 1982-03-18 | Method for removing carbon dioxide in natural gas |
| CA000401166A CA1202576A (en) | 1982-01-12 | 1982-04-16 | Process for separating carbonic acid gas from methane- rich gas |
| AT82301989T ATE20831T1 (en) | 1982-01-12 | 1982-04-19 | PROCESS FOR SEPARATION OF DE CO2 FROM A METHANE-RICH GAS. |
| DE8282301989T DE3272104D1 (en) | 1982-01-12 | 1982-04-19 | Process for separating carbonic acid gas from methane-rich gas |
| EP19820301989 EP0083832B1 (en) | 1982-01-12 | 1982-04-19 | Process for separating carbonic acid gas from methane-rich gas |
| AU83115/82A AU550377B2 (en) | 1982-01-12 | 1982-04-29 | Separation of carbonic acid gas from methane rich gas |
| MX19282882A MX161080A (en) | 1982-01-12 | 1982-05-24 | PROCEDURE FOR SEPARATING GAS FROM CARBONIC ACID FROM GAS RICH IN METHANE |
| US06/581,208 US4581044A (en) | 1982-01-12 | 1984-02-21 | Process for separating carbonic acid gas from methane-rich gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57044194A JPS58159830A (en) | 1982-03-18 | 1982-03-18 | Method for removing carbon dioxide in natural gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58159830A JPS58159830A (en) | 1983-09-22 |
| JPS621525B2 true JPS621525B2 (en) | 1987-01-14 |
Family
ID=12684759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57044194A Granted JPS58159830A (en) | 1982-01-12 | 1982-03-18 | Method for removing carbon dioxide in natural gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58159830A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6430619A (en) * | 1987-07-27 | 1989-02-01 | Kansai Coke & Chemicals | Psa system |
| JPH02699A (en) * | 1987-10-24 | 1990-01-05 | Seibu Gas Kk | Removal of carbon dioxide and moisture from gas in town gas production process |
| JPH01176415A (en) * | 1987-12-31 | 1989-07-12 | Kansai Coke & Chem Co Ltd | Production of enriched gas by psa method |
| JPH02281096A (en) * | 1989-04-24 | 1990-11-16 | Seibu Gas Kk | Carbon dioxide and moisture remover for methane-enriched mixed gas |
| JP4898194B2 (en) | 2005-11-14 | 2012-03-14 | 大陽日酸株式会社 | Pressure fluctuation adsorption gas separation method and separation apparatus |
| US9574713B2 (en) | 2007-09-13 | 2017-02-21 | Battelle Energy Alliance, Llc | Vaporization chambers and associated methods |
| US9217603B2 (en) | 2007-09-13 | 2015-12-22 | Battelle Energy Alliance, Llc | Heat exchanger and related methods |
| US8899074B2 (en) | 2009-10-22 | 2014-12-02 | Battelle Energy Alliance, Llc | Methods of natural gas liquefaction and natural gas liquefaction plants utilizing multiple and varying gas streams |
| US9254448B2 (en) | 2007-09-13 | 2016-02-09 | Battelle Energy Alliance, Llc | Sublimation systems and associated methods |
| US10655911B2 (en) | 2012-06-20 | 2020-05-19 | Battelle Energy Alliance, Llc | Natural gas liquefaction employing independent refrigerant path |
| JP6013865B2 (en) * | 2012-10-10 | 2016-10-25 | メタウォーター株式会社 | Method and system for producing city gas |
| JP6013864B2 (en) * | 2012-10-10 | 2016-10-25 | メタウォーター株式会社 | Methane fermentation gas purification method and purification system |
| RU2015144454A (en) | 2013-03-19 | 2017-04-27 | Осака Гэс Ко., Лтд. | GAS CLEANING METHOD |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4077779A (en) * | 1976-10-15 | 1978-03-07 | Air Products And Chemicals, Inc. | Hydrogen purification by selective adsorption |
-
1982
- 1982-03-18 JP JP57044194A patent/JPS58159830A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58159830A (en) | 1983-09-22 |
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