JPH03238019A - Purification of high temperature reductive gas - Google Patents
Purification of high temperature reductive gasInfo
- Publication number
- JPH03238019A JPH03238019A JP2032549A JP3254990A JPH03238019A JP H03238019 A JPH03238019 A JP H03238019A JP 2032549 A JP2032549 A JP 2032549A JP 3254990 A JP3254990 A JP 3254990A JP H03238019 A JPH03238019 A JP H03238019A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- gas
- zeolite
- temperature
- adsorbed
- 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.)
- Pending
Links
- 230000002829 reductive effect Effects 0.000 title abstract 5
- 238000000746 purification Methods 0.000 title description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 64
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010457 zeolite Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 69
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 16
- 239000003245 coal Substances 0.000 description 12
- 238000002309 gasification Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000003464 sulfur compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011275 tar sand 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高温還元性ガスの中のアンモニアを除去する
方法に関する６更に詳述すると、本発明は、石炭ガス化
プロセスにおける精製ガスのような高温高圧の還元性ガ
スに含まれるアンモニアをそのまま乾式で連続的に除去
する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for removing ammonia in a high temperature reducing gas. The present invention relates to a dry method for continuously removing ammonia contained in a high-temperature, high-pressure reducing gas.
（従来の技術）
近年、石油資源の枯渇、価格の高騰から燃料又は原料の
多用化か必須となり、石炭や重質油（タールサンド油、
オイルシ玉−ル油、大慶原油、マヤ原油あるいは減圧残
油等）の利用技術の開発が進められている。例えば、石
炭をガス化炉でガス化し、このガス化生成ガスを燃料と
して複合発電の高圧ガスタービンを稼動させることが従
来提案されている。(Prior art) In recent years, due to the depletion of petroleum resources and soaring prices, it has become necessary to use more fuels or raw materials, and coal, heavy oil (tar sand oil,
Development of technologies for utilizing crude oil (oil silica oil, Daqing crude oil, Maya crude oil, vacuum residual oil, etc.) is underway. For example, it has been proposed in the past to gasify coal in a gasifier and operate a high-pressure gas turbine for combined power generation using the resulting gas as fuel.
このガス化生成ガスは、原料の石炭や重質油によっても
異なるが、数１００〜数１０００ ｐｐｍの硫化水素（
Ｈ２Ｓ）や硫化カルボニル（００３）等の硫黄化合物を
含む。この硫黄化合物は、公害を防止するため、あるい
は後流機器の腐食を防止するため除去する必要がある６
更に、上述のガス中にはガス化する際に石炭中の窒素分
の一部がアンモニア（ＮＨ３）に転換するため、硫黄化
合物と同様に数１０〜数１０００ ｐｐｎ＋のアンモニ
ア等の窒素化合物を不純物として含む。この窒素化合物
は、燃焼の過程で窒素酸化物（ＮＯｘ）に転換すること
から公害対策上生成ガス中から取り除くことが望まれる
。Although this gasification product gas differs depending on the raw material coal and heavy oil, it contains several hundred to several thousand ppm of hydrogen sulfide (
Contains sulfur compounds such as H2S) and carbonyl sulfide (003). These sulfur compounds need to be removed to prevent pollution or to prevent corrosion of downstream equipment6.
In addition, some of the nitrogen in the coal is converted to ammonia (NH3) during gasification, so nitrogen compounds such as ammonia of several tens to several thousand ppn+ are added as impurities, similar to sulfur compounds. Included as Since these nitrogen compounds are converted into nitrogen oxides (NOx) during the combustion process, it is desirable to remove them from the generated gas as a pollution control measure.
従来、硫黄化合物の除去方法としては、乾式法が熱経済
的に有利であることから、酸化鉄などの金属酸化物を主
成分とする吸収剤に高温でガスを接触させ、金属酸化物
を金属硫化物として除去する方法が一般的である。しか
し、この硫黄化合物の除去方法では高温還元性ガス中の
アンモニアは除去されない。Conventionally, as a method for removing sulfur compounds, the dry method is thermoeconomically advantageous, so gas is brought into contact at high temperature with an absorbent whose main component is a metal oxide such as iron oxide. A common method is to remove it as sulfide. However, this method of removing sulfur compounds does not remove ammonia in the high-temperature reducing gas.
一方、アンモニアの除去方法としては、ガスを水に通し
てアンモニアを水に解かす湿式法が一般的である。アン
モニアは水に吸収され易いため、ガス精製をスクラバー
などの湿式方法で行う場合には容易に除去できる。しか
し、この湿式法ではアンモニアが高温（１００℃以上）
では水に解けないため低温で処理しなければならないこ
とから、石炭ガス化燃料の温度が下がり、石炭ガス化複
合発電システムにおける熱効率を低下させる問題を伴う
。このため、ガス化複合発電システムにおけるガス精製
はドライ（乾式）状態で行う方法が要望され、燃焼排ガ
ス中の窒素酸化物を排煙脱硝装置を設置することにより
除去することが従来考えられている。On the other hand, a common method for removing ammonia is a wet method in which gas is passed through water to dissolve ammonia in water. Since ammonia is easily absorbed by water, it can be easily removed when gas purification is performed using a wet method such as a scrubber. However, in this wet method, ammonia is heated to a high temperature (over 100℃).
However, since it cannot be dissolved in water, it must be treated at low temperatures, which causes the problem of lowering the temperature of the coal gasification fuel and reducing the thermal efficiency of the coal gasification combined cycle power generation system. For this reason, there is a demand for a dry method for gas purification in gasification combined cycle power generation systems, and conventionally it has been considered to remove nitrogen oxides from the combustion exhaust gas by installing a flue gas denitrification device. .
（発明が解決しようとする課題）
しかしながら、排煙脱硝装置は、燃焼後の膨張したガス
を処理するため、高温高圧状態の還元性ガスを利用する
上述の石炭ガス化複合発電システムに適用する場合、精
製ガスの約数十倍程度（例えば２０ｋｇ／ｃＪＧで６０
倍）のボリュームのガスを処理しなければならないため
、装置規模としても脱硫装置部と同程度の大きさになる
ことが予想され、装置建設費用が嵩み経済的に好ましく
ない。(Problems to be Solved by the Invention) However, in order to treat expanded gas after combustion, the flue gas denitrification device is applied to the above-mentioned coal gasification combined cycle system that uses reducing gas in a high temperature and high pressure state. , about several dozen times that of purified gas (for example, 60 kg/cJG
Since it is necessary to process a volume of gas that is twice as large as that of the desulfurizer, it is expected that the scale of the equipment will be comparable to that of the desulfurization equipment, which is economically undesirable because the construction cost of the equipment will increase.
しかも、燃焼排ガス中のＮＯｘは極めて低濃度であり、
大部分はＮｏの形であるため除去は極めて困難である。Moreover, the concentration of NOx in the combustion exhaust gas is extremely low,
Since most of it is in the form of No, it is extremely difficult to remove it.
そこで、本発明は、高温還元性ガス中のアンモニアを高
温高圧下にて乾式で除去し、アンモニアを濃縮して回収
する精製方法を提供し、排煙脱硝装置を不要にして装置
建設費用の削減を達成することを目的とする。Therefore, the present invention provides a purification method that dryly removes ammonia in high-temperature reducing gas under high temperature and high pressure, concentrates and recovers ammonia, and eliminates the need for flue gas denitrification equipment, reducing equipment construction costs. The purpose is to achieve the following.
（課題を解決するための手段）
かかる目的を達成するため、本発明の高温還元性ガスの
精製方法は、ゼオライトを充填した反応器を複数塔使用
し、高温還元性ガス中に含まれるアンモニアを１００〜
１５０℃の高温で前記ゼオライトに吸着させて除去する
除去工程と、前記ゼオライトに吸着されたアンモニアを
前記ゼオライトに吸着される成分を含まないガスを用い
かつ前記反応器温度若しくは圧力を変化させることによ
って前記ゼオライトより脱離させる再生工程とを交互に
実施し、アンモニアを除去した高温還元性ガスを得る一
方、前記再生工程で発生するアンモニア含有ガスからア
ンモニアを回収するようにしている。(Means for Solving the Problem) In order to achieve the above object, the method for purifying high-temperature reducing gas of the present invention uses a plurality of reactors filled with zeolite to remove ammonia contained in the high-temperature reducing gas. 100～
a removal step of adsorbing and removing ammonia on the zeolite at a high temperature of 150° C.; and removing the ammonia adsorbed on the zeolite by using a gas that does not contain components adsorbed on the zeolite and changing the temperature or pressure of the reactor. A regeneration step in which the zeolite is desorbed is alternately carried out to obtain a high-temperature reducing gas from which ammonia has been removed, while ammonia is recovered from the ammonia-containing gas generated in the regeneration step.
（作用）
したがって、高温還元性ガス中のアンモニアは、１００
℃〜１５０℃の高温下でゼオライトに吸着・固定化され
て除去される（除去工程）。そして、アンモニアが除か
れた精製ガスはガスタービンやその他の燃焼装置等に供
給される。また、ゼオライＩ・に−固定化されたアンモ
ニアは、ゼオライトに吸着される成分を含まないガスを
通しながらセオライト温度若しくはガス圧力を変化させ
ることにより、吸着剤より脱離させ回収する（再生工程
）。(Function) Therefore, ammonia in the high temperature reducing gas is 100
It is adsorbed and immobilized on zeolite and removed at a high temperature of 150°C to 150°C (removal step). The purified gas from which ammonia has been removed is then supplied to a gas turbine or other combustion device. In addition, the ammonia fixed on Zeolite I is desorbed from the adsorbent and recovered by changing the zeolite temperature or gas pressure while passing a gas that does not contain components adsorbed on the zeolite (regeneration step). .
アンモニアを脱離させたゼオライトは、再度高温還元性
ガス中のアンモニアの除去に用いられる。The zeolite from which ammonia has been removed is used again to remove ammonia from high-temperature reducing gases.
以上のアンモニア除去工程とゼオライト再生工程を複数
の反応塔で切替えて運転することにより連続的なガス精
製運転を行う。Continuous gas purification operation is performed by switching and operating the above ammonia removal step and zeolite regeneration step in a plurality of reaction towers.
（実施例）
以下、本発明の構成を図面に示す実施例に基づいて詳細
に説明する。(Example) Hereinafter, the configuration of the present invention will be described in detail based on an example shown in the drawings.
第１図に本発明方法を実施する精製装置の一例を概要図
で示す。該図において、符号２は熱交換器、６は脱しん
装置、１１．１２は反応塔、２２は再生ガス温度調節器
、２３は再生ガス循環プロワ、２４はアンモニア分離器
、３１は圧力調節器、１４．１５．１６，１７，１８．
１９．２０及び２１はガス流路切替えバルブ、１．３，
４，５゜７．８，９，１０．２’５，２６，２７．２８
２９およ３０は各装置を接続するライン（配管）であ
る。FIG. 1 shows a schematic diagram of an example of a purification apparatus for carrying out the method of the present invention. In the figure, 2 is a heat exchanger, 6 is a desulfurization device, 11.12 is a reaction tower, 22 is a regeneration gas temperature regulator, 23 is a regeneration gas circulation blower, 24 is an ammonia separator, and 31 is a pressure regulator. , 14.15.16, 17, 18.
19.20 and 21 are gas flow path switching valves, 1.3,
4,5°7.8,9,10.2'5,26,27.28
29 and 30 are lines (pipes) connecting each device.
ここで、脱しん装置６としては、多孔質セララミックフ
ィルタ、バグフィルタ若しくはグラニュラ−充填材の使
用が好ましい。Here, as the desulfurization device 6, it is preferable to use a porous ceramic filter, a bag filter, or a granular filler.
また、各反応塔１１．１２にはゼオライト１３が充填さ
れている。ゼオライト１３としては、その組成、形状等
に特に限定されるものではないが、Ｈ＋基を有するＨ型
ゼオライトの使用が最も好ましい。Moreover, each reaction column 11.12 is filled with zeolite 13. The zeolite 13 is not particularly limited in its composition, shape, etc., but it is most preferable to use an H-type zeolite having an H+ group.
以上のように構成した高温還元性ガスの精製システムに
おいて、Ｈ型ゼオライトを使用する場合につきアンモニ
ア除去工程及びゼオライト再生工程を説明する。In the high-temperature reducing gas purification system configured as described above, the ammonia removal step and the zeolite regeneration step will be explained in the case where H-type zeolite is used.
一般に、高温還元性ガス中には、石炭の種類やガス化条
件によって異なるが、ダスト以外に数１０〜数１０００
ＤＤＩＩＩの硫黄化合物、アンモニア及びハロゲン等
が含まれている。このうち硫黄化合物は一般に４００〜
６００℃の高温で酸化鉄などの金属酸化物と接触させて
除去される。そこで、本実施例ではアンモニア除去に先
立って、高温還元性ガス中の硫黄化合物を公知の脱硫装
置において除去する。In general, high-temperature reducing gas contains several tens to thousands of particles in addition to dust, although it varies depending on the type of coal and gasification conditions.
Contains DDIII sulfur compounds, ammonia, halogens, etc. Of these, sulfur compounds generally have a
It is removed by contacting it with metal oxides such as iron oxide at a high temperature of 600°C. Therefore, in this example, prior to ammonia removal, sulfur compounds in the high-temperature reducing gas are removed using a known desulfurization device.
ライン１を経て導入されるアンモニアを含有する高温還
元性ガス例えば石炭ガス化ガスは、熱交換器２でライン
３より導入した水との間で熱交換が行なわれ、ガス温度
をゼオライト１３がアンモニアを吸着するに最適な温度
即ち１５０℃付近まで下げられる。一方、高温還元性ガ
スとの熱交換によって得られた水蒸気はライン４を経て
熱利用設備等に供給され有効利用される。A high-temperature reducing gas containing ammonia, such as coal gasification gas, introduced through line 1 undergoes heat exchange with water introduced from line 3 in heat exchanger 2, and zeolite 13 adjusts the gas temperature to The temperature can be lowered to around 150°C, which is the optimum temperature for adsorbing. On the other hand, the water vapor obtained by heat exchange with the high-temperature reducing gas is supplied to heat utilization equipment etc. through line 4 and is effectively utilized.
更に、熱交換器２において所定の温度例えば１５０℃前
後にまで冷却された高温還元性ガスは、ガスライン５を
経て脱塵装置６に導入され、ダスト濃度１０■／ ！１
ｎ１９程度まで脱塵される。そして、ガス温度が１５０
℃以下、圧力が（石炭ガス化炉の形状や条件によっても
異なる）通常、常圧〜２５ｋｇ／ｃＪＧの高温還元性ガ
スとされる。Further, the high-temperature reducing gas cooled to a predetermined temperature, for example, around 150°C in the heat exchanger 2, is introduced into the dust removal device 6 via the gas line 5, and the dust concentration is 10/! 1
Dust is removed to about n19. And the gas temperature is 150
℃ or less, and the pressure (which varies depending on the shape and conditions of the coal gasifier) is usually a high temperature reducing gas of normal pressure to 25 kg/cJG.
脱塵後の石炭ガス化ガスは、流路切替えバルブ１４．１
５の操作によっていずれか一方の反応器１１．１２に供
給される。例えは、第１図の状態においては反応器１１
に石炭ガス化ガスは供給され、通常１５０℃以下好まし
くは１００〜１５０℃の範囲で、ゼオライト１３に接触
するように設定される。アンモニアは第３図に示すよう
に、温度１５０℃の時には、温度２００℃の時に比べて
アンモニアの吸着剤への吸着量か多いのがわかる。The coal gasification gas after dust removal is transferred to the flow path switching valve 14.1.
5, it is supplied to either reactor 11 or 12. For example, in the state shown in FIG.
Coal gasification gas is supplied to the zeolite 13 and is set to contact the zeolite 13 at a temperature usually below 150°C, preferably in the range of 100 to 150°C. As shown in FIG. 3, it can be seen that the amount of ammonia adsorbed onto the adsorbent is greater when the temperature is 150°C than when the temperature is 200°C.
依って、本実施例では、吸収工程を１５０℃で再生工程
を２００℃で行うことにより、効率的に高温還元性ガス
中のアンモニアを吸着除去し、かつゼオライト１３に吸
着させたアンモニアを脱離させて回収することが可能で
ある。例えば、Ｈ型ゼオライトは、石炭ガス中のアンモ
ニアを温度１５０℃の時には、吸着剤１ｇ当り１〜５Ｑ
１１１１ｏ１吸収する。したがって、反応器１１を通過
したガス化ガスは、含有するアンモニアをゼオライト１
３に吸着され、アンモニアが取り除かれた精製ガスとな
って、ライン９、流路切替えバルブ１８及びライン１０
を経て図示していないガスタービン若しくは燃焼装置等
に供給される。Therefore, in this example, by performing the absorption step at 150°C and the regeneration step at 200°C, ammonia in the high-temperature reducing gas can be efficiently adsorbed and removed, and ammonia adsorbed on the zeolite 13 can be desorbed. It is possible to recover it by letting it go. For example, H-type zeolite absorbs 1 to 5 Q of ammonia in coal gas per 1 g of adsorbent at a temperature of 150°C.
Absorbs 1111o1. Therefore, the gasified gas that has passed through the reactor 11 removes the ammonia contained in the zeolite 1.
3, the purified gas from which ammonia has been removed is passed through line 9, flow path switching valve 18, and line 10.
The gas is then supplied to a gas turbine, combustion device, etc. (not shown).
一方、高温還元性ガスが流されていない他方の反応塔１
２ではゼオライト１３に吸着されたアンモニアを離脱さ
せてゼオライト１３を再びアンモニア吸着に使用できる
ように再生させる作業か進められている。このアンモニ
アの離脱は、反応器１２へ導入されるガスを圧力調整器
３１によりアンモニア除去工程よりも減圧（常圧〜１０
ｋｓｒ／ｃＪＧに減圧）することによって、若しくは再
生ガス温度調節器２２により２００〜５００℃へと昇温
することによって、あるいは減圧と昇温を同時に行なう
ことによって行なわれる。再生ガスとしては特に限定を
受けるものではないが、ゼオライトに吸着される成分（
水分を除く）を含まないガスの使用が好ましい６ゼオラ
イト１３に吸着されていたアンモニアは、除去工程との
運転圧力差もしくは温度差によりゼオライト１３より脱
離し、吸着塔１２に導入された再生ガスと共に反応塔１
２０
より出る。再生工程で発生したアンモニアは、圧力調整
器３１で圧力が調整された後、アンモニア分離器２４に
導入され、再生ガスと分離される。On the other hand, the other reaction tower 1 to which high-temperature reducing gas is not flowing
2, work is underway to remove the ammonia adsorbed on the zeolite 13 and regenerate the zeolite 13 so that it can be used again for ammonia adsorption. This removal of ammonia is performed by reducing the pressure of the gas introduced into the reactor 12 by the pressure regulator 31 (normal pressure to 10%
ksr/cJG), or by raising the temperature to 200 to 500° C. using the regeneration gas temperature controller 22, or by simultaneously reducing the pressure and raising the temperature. There are no particular restrictions on the regeneration gas, but it may include components adsorbed by zeolite (
It is preferable to use a gas that does not contain water (excluding water) 6 The ammonia adsorbed on the zeolite 13 is desorbed from the zeolite 13 due to the operating pressure difference or temperature difference with the removal process, and is removed together with the regeneration gas introduced into the adsorption tower 12. Reaction tower 1
It comes out from 20. After the pressure of the ammonia generated in the regeneration process is adjusted by the pressure regulator 31, the ammonia is introduced into the ammonia separator 24 and separated from the regeneration gas.
そして、ライン３０を介して回収される。再生ガスは、
ライン２９、再生ガス循環ブロワ２３及びライン２５を
介して前述の所定温度に調整された後再度循環利用され
る。Then, it is collected via line 30. Regeneration gas is
After being adjusted to the above-mentioned predetermined temperature via line 29, regeneration gas circulation blower 23, and line 25, it is recycled and used again.
尚、上述の実施例は本発明の好適な実施の一例ではある
がこれに限定されるものではなく本発明の要旨を逸脱し
ない範囲において種々変形実施可能である。例えば、第
１図ではゼオライト系吸着剤１３が充填された同一構造
の反応塔１１．１２に流入するガスを交互に切替えるこ
とによってアンモニア除去工程と、ゼオライト再生工程
とを連続的に実施するようにしているが、特にこの固定
床式に限定されるものではなく、還元性ガス中のアンモ
ニアをＨ型ゼオライ１−系吸着剤で吸着除去後、再生工
程を繰り返すプロセスなら、流動床式、移動床式を問わ
ず適用できる。また、２塔以上の固定床式にも適応でき
るのはいうまでもない。It should be noted that although the above-described embodiment is an example of a preferred embodiment of the present invention, the present invention is not limited thereto, and various modifications can be made without departing from the gist of the present invention. For example, in FIG. 1, the ammonia removal process and the zeolite regeneration process are carried out continuously by alternately switching the gas flowing into the reaction towers 11 and 12 of the same structure filled with the zeolite adsorbent 13. However, it is not limited to this fixed bed type; if the process involves repeating the regeneration process after adsorbing and removing ammonia in the reducing gas with an H-type zeolite 1-based adsorbent, a fluidized bed type or a moving bed type can be used. It can be applied regardless of the formula. It goes without saying that it can also be applied to a fixed bed type with two or more towers.
１
（発明の効果〉
以上のように、本発明においては、ゼオライＩ・を充填
した反応器を２塔以上使用し、除去・再生工程を切り替
えて運転することにより、高温還元性ガス中のアンモニ
アを高温下で連続的に乾式除去する。ゼオライトに吸着
されたアンモニアは、再生工程において脱離され回収さ
れる。1 (Effects of the Invention) As described above, in the present invention, ammonia in high-temperature reducing gas is The ammonia adsorbed on the zeolite is removed and recovered in the regeneration process.
したがって、本発明によると、高温還元性ガス例えば石
炭ガス化燃料中のアンモニアを乾式で除去することがで
き、システム全体の熱効率の低下を招かずに、しかもガ
スタービン燃焼器内で生成されるアンモニアに起因する
ＮＯｘをなくしてＮＯｘの発生量を著しく低減すること
が可能となる。Therefore, according to the present invention, it is possible to dry remove ammonia in a high-temperature reducing gas, such as coal gasified fuel, without causing a decrease in the thermal efficiency of the entire system, and without reducing the ammonia produced in the gas turbine combustor. This makes it possible to significantly reduce the amount of NOx generated by eliminating NOx caused by this.
また、燃焼排ガス中のＮＯｘ排除方法として従来、−船
釣な触媒式排煙脱硝方法に比べると、燃料そのものから
アンモニアを除去するため、体積比で１／３、複合発電
システムの稼動圧力（約２０ｋｇ ／ ａＪ ｃ ）を
考慮に入れると１／６０のガス処理量で従来と同じ脱硝
効果を得ることかでき、触媒交換時間の大幅な延長を可
能にして極めて経済的２
でかつシステム運転が容易なものとなる。In addition, compared to the conventional catalytic exhaust gas denitration method, which is a method for removing NOx from combustion exhaust gas, because ammonia is removed from the fuel itself, the operating pressure of the combined power generation system (approximately 20kg/aJc), it is possible to obtain the same denitrification effect as conventional methods with 1/60 of the gas throughput, making it possible to significantly extend the catalyst replacement time, making it extremely economical2 and easy to operate the system. Become something.
第１図は本発明の高温還元性ガスの精製方法を実施する
装置の一実施例を示すブロック図である。
第２図はアンモニア除去サイクルとゼオライト再生サイ
クルのタイムスゲジュールで、（Ａ）は反応塔１１を、
（Ｂ）は反応塔１２を夫々示す。
第３図はアンモニア吸収量と温度変化との関係を示すグ
ラフである。
１１．１２・・・反応器（反応塔）、
１３・・・ゼオライト。FIG. 1 is a block diagram showing an embodiment of an apparatus for implementing the high temperature reducing gas purification method of the present invention. Figure 2 shows the time schedule of the ammonia removal cycle and the zeolite regeneration cycle; (A) shows the reaction tower 11;
(B) shows the reaction tower 12, respectively. FIG. 3 is a graph showing the relationship between the amount of ammonia absorbed and temperature change. 11.12... Reactor (reaction tower), 13... Zeolite.
Claims (1)
元性ガス中に含まれるアンモニアを１００〜１５０℃の
高温で前記ゼオライトに吸着させて除去する除去工程と
、前記ゼオライトに吸着されたアンモニアを前記ゼオラ
イトに吸着される成分を含まないガスを用いかつ前記反
応器温度若しくは圧力を変化させることによって前記ゼ
オライトより脱離させる再生工程とを交互に実施し、ア
ンモニアを除去した高温還元性ガスを得る一方、前記再
生工程で発生するアンモニア含有ガスからアンモニアを
回収することを特徴とする高温還元性ガスの精製方法。A removal step in which ammonia contained in the high-temperature reducing gas is adsorbed and removed by the zeolite at a high temperature of 100 to 150°C using a plurality of reactors filled with zeolite, and ammonia adsorbed by the zeolite is removed by the A high-temperature reducing gas from which ammonia has been removed is obtained by alternately carrying out a regeneration step in which a gas that does not contain components adsorbed by the zeolite is desorbed from the zeolite by changing the temperature or pressure of the reactor. . A method for purifying a high-temperature reducing gas, comprising recovering ammonia from the ammonia-containing gas generated in the regeneration step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032549A JPH03238019A (en) | 1990-02-15 | 1990-02-15 | Purification of high temperature reductive gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032549A JPH03238019A (en) | 1990-02-15 | 1990-02-15 | Purification of high temperature reductive gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03238019A true JPH03238019A (en) | 1991-10-23 |
Family
ID=12362016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2032549A Pending JPH03238019A (en) | 1990-02-15 | 1990-02-15 | Purification of high temperature reductive gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03238019A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0661374A1 (en) * | 1993-12-30 | 1995-07-05 | Shell Internationale Researchmaatschappij B.V. | Process for removing nitrogen compounds from synthesis gas |
| US5711926A (en) * | 1996-05-14 | 1998-01-27 | Knaebel; Kent S. | Pressure swing adsorption system for ammonia synthesis |
| KR100403244B1 (en) * | 2001-04-06 | 2003-10-23 | 대백신소재주식회사 | A method of ammonia gas purification for manufacturing highly pure nitrogen trifluoride |
| KR100482935B1 (en) * | 1997-08-07 | 2005-08-17 | 미우라고교 가부시키카이샤 | Adsorption removal device of dioxin |
| JP2006193563A (en) * | 2005-01-11 | 2006-07-27 | Central Res Inst Of Electric Power Ind | Fuel gas-purifying apparatus |
| JP2014055094A (en) * | 2012-09-14 | 2014-03-27 | Japan Pionics Co Ltd | Ammonia purification apparatus, and regeneration method thereof |
| JP2018137149A (en) * | 2017-02-22 | 2018-08-30 | トヨタ自動車株式会社 | Fuel gas-supply method |
| JP2022533234A (en) * | 2019-05-24 | 2022-07-21 | インテグリス・インコーポレーテッド | Methods and systems for removing ammonia from gas mixtures |
-
1990
- 1990-02-15 JP JP2032549A patent/JPH03238019A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0661374A1 (en) * | 1993-12-30 | 1995-07-05 | Shell Internationale Researchmaatschappij B.V. | Process for removing nitrogen compounds from synthesis gas |
| EP0661375A1 (en) * | 1993-12-30 | 1995-07-05 | Shell Internationale Researchmaatschappij B.V. | Process for removing nitrogen compounds from synthesis gas |
| US5711926A (en) * | 1996-05-14 | 1998-01-27 | Knaebel; Kent S. | Pressure swing adsorption system for ammonia synthesis |
| KR100482935B1 (en) * | 1997-08-07 | 2005-08-17 | 미우라고교 가부시키카이샤 | Adsorption removal device of dioxin |
| KR100403244B1 (en) * | 2001-04-06 | 2003-10-23 | 대백신소재주식회사 | A method of ammonia gas purification for manufacturing highly pure nitrogen trifluoride |
| JP2006193563A (en) * | 2005-01-11 | 2006-07-27 | Central Res Inst Of Electric Power Ind | Fuel gas-purifying apparatus |
| JP4573650B2 (en) * | 2005-01-11 | 2010-11-04 | 財団法人電力中央研究所 | Fuel gas purification equipment |
| JP2014055094A (en) * | 2012-09-14 | 2014-03-27 | Japan Pionics Co Ltd | Ammonia purification apparatus, and regeneration method thereof |
| JP2018137149A (en) * | 2017-02-22 | 2018-08-30 | トヨタ自動車株式会社 | Fuel gas-supply method |
| JP2022533234A (en) * | 2019-05-24 | 2022-07-21 | インテグリス・インコーポレーテッド | Methods and systems for removing ammonia from gas mixtures |
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