JP4599989B2 - Ammonia production method and denitration method - Google Patents
Ammonia production method and denitration method Download PDFInfo
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- JP4599989B2 JP4599989B2 JP2004313282A JP2004313282A JP4599989B2 JP 4599989 B2 JP4599989 B2 JP 4599989B2 JP 2004313282 A JP2004313282 A JP 2004313282A JP 2004313282 A JP2004313282 A JP 2004313282A JP 4599989 B2 JP4599989 B2 JP 4599989B2
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- 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
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Description
本発明は、ディーゼルエンジン自動車から出る排ガスのような低温自動車排ガス中の窒素酸化物の選択的還元による脱硝方法、この脱硝方法に用いるアンモニアの製造方法に関するものである。 The present invention denitration method by selective reduction of the low-temperature automotive nitrogen oxides in the exhaust gas, such as flue gas leaving the diesel engine automobiles are those concerning the manufacturing how ammonia used in this denitration process.
従来、排ガスの脱硝技術として、下記（１）〜（４）の方法が知られている。 Conventionally, the following methods (1) to (4) are known as exhaust gas denitration techniques.
（１）排気ガスが流通する配管内にゼオライト粒子が充填された気化器容器を配置し、気化器容器内に配管外方より尿素水と水を注入する液送配管と水配管を設け、排気ガスから供給される熱によって尿素を還元剤としてのアンモニアに分解して気化器容器により配管内に排出し、アンモニアと排ガスとを混合した後に脱硝触媒と接触させる方法（特許文献１参照）。 (1) A vaporizer container filled with zeolite particles is placed in a pipe through which exhaust gas flows, and a liquid feed pipe and a water pipe for injecting urea water and water from the outside of the pipe are provided in the vaporizer container. A method in which urea is decomposed into ammonia as a reducing agent by heat supplied from a gas, discharged into a pipe by a vaporizer vessel, and mixed with ammonia and exhaust gas, and then contacted with a denitration catalyst (see Patent Document 1).
この方法は、尿素水以外に水を必要とし、自動車に適用する場合には脱硝装置の外に水タンクを搭載する必要があり、現実的でない。 This method requires water in addition to urea water, and when applied to an automobile, it is necessary to mount a water tank outside the denitration device, which is not practical.
（２）脱硝触媒反応器前流側の排ガス煙道に高温ガス供給配管を連結し、高温ガス供給配管に尿素水を注入する手段を設け、高温ガス供給配管の尿素注入手段との連結部の後流に尿素分解触媒反応器を設ける方法（特許文献２参照）。 (2) A high temperature gas supply pipe is connected to the exhaust gas flue upstream of the denitration catalyst reactor, and a means for injecting urea water into the high temperature gas supply pipe is provided. A method of providing a urea decomposition catalyst reactor in the downstream (see Patent Document 2).
この装置では高温ガスの温度が３００−５００℃であり、この温度域では加水分解反応と共に熱分解反応も進行するため、アンモニアの生成率が悪いばかりか、副生成物の析出による脱硝触媒の目詰まりや配管の閉塞などが起こる。 In this apparatus, the temperature of the high-temperature gas is 300 to 500 ° C., and in this temperature range, the thermal decomposition reaction proceeds together with the hydrolysis reaction. Clogging or piping blockage occurs.
（３）尿素水と尿素加水分解触媒溶液を混合した後、この混合液を加熱して気液分離を行ない、分離されたアンモニアを含む気体を排ガス中に注入する方法（特許文献３参照）。 (3) After mixing urea water and urea hydrolysis catalyst solution, this mixed solution is heated to perform gas-liquid separation, and a gas containing separated ammonia is injected into the exhaust gas (see Patent Document 3).
この方法では、気液分離装置を設けるため、装置が複雑となる。また、尿素水と尿素加水分解触媒溶液の混合液を加熱するため、加熱に要するエネルギーが多くなる。 In this method, since the gas-liquid separation device is provided, the device becomes complicated. Moreover, since the liquid mixture of urea water and a urea hydrolysis catalyst solution is heated, the energy required for heating increases.
（４）尿素水溶液を接触加水分解触媒と２００℃以上の温度で接触させ、尿素の接触加水分解によりアンモニアを発生させる方法（特許文献４参照）。 (4) A method in which an aqueous urea solution is brought into contact with a catalytic hydrolysis catalyst at a temperature of 200 ° C. or higher to generate ammonia by catalytic hydrolysis of urea (see Patent Document 4).
この方法では接触温度が２００℃以上であるため、加水分解反応と共に熱分解反応も進行し、アンモニアの生成率が悪くなるばかりか、副生成物の析出による脱硝触媒の目詰まりや配管の閉塞などが起こる。
本発明は、上述した従来技術の問題点を克服することができる、排ガス中の窒素酸化物の選択的還元による脱硝方法、この脱硝方法に用いるアンモニアの製造方法を提供することを課題とする。 The present invention can overcome the problems of the prior art described above, the denitration method by selective reduction of nitrogen oxides in the exhaust gas, it is an object to provide Hisage a method for producing ammonia for use in the denitration process.
請求項１に係る発明は、尿素水を加圧気体によってミスト状にするかまたは水溶液の状態を保ちつつ１５０〜１９０℃の温度範囲で、酸化チタン担体に酸化夕ングステンを添加した構造、又は、酸化チタン担体に酸化タングステンを添加し、さらに五酸化バナジウムを担持した構造をなす尿素加水分解触媒と固液接触させ、尿素を加水分解してアンモニアを連続的に生成させることを特徴とする、尿素の加水分解によるアンモニアの製造方法である。
尿素水の尿素濃度は好ましくは１０〜５４．７ｗｔ％である。加圧気体は、例えば空気をコンプレッサで加圧したものであってよい。
The invention according to claim 1 is a structure in which urea oxide is added to a titanium oxide support in a temperature range of 150 to 190 ° C. while maintaining a state of an aqueous solution by making urea water mist with pressurized gas , or A urea characterized in that tungsten oxide is added to a titanium oxide support and is further brought into solid-liquid contact with a urea hydrolysis catalyst having a structure supporting vanadium pentoxide, whereby urea is hydrolyzed to generate ammonia continuously. It is a manufacturing method of ammonia by hydrolysis of.
The urea concentration of urea water is preferably 10 to 54.7 wt%. The pressurized gas may be, for example, air compressed by a compressor.
請求項２に係る発明は、還元剤としてアンモニアを用いて窒素酸化物を選択的に還元する脱硝方法において、還元剤として請求項１記載の方法によって製造したアンモニアを用いることを特徴とする、脱硝方法である。
The invention according to
９０℃以上で尿素を加水分解すると、下記の式で示すように、アンモニアと二酸化炭素を生成する。 When urea is hydrolyzed at 90 ° C. or higher, ammonia and carbon dioxide are generated as shown by the following formula.
（ＮＨ２）２ＣＯ＋Ｈ２０→２ＮＨ３＋Ｃ０２
(NH 2 ) 2 CO + H 2 0 → 2NH 3 +
本発明により、ディーゼルエンジン自動車から出る排ガスのような低温自動車排ガス中の窒素酸化物の選択的還元による脱硝方法、この脱硝方法に用いるアンモニアの製造方法を提供することができる。 The present invention can provide denitration method by selective reduction of nitrogen oxides cold car in the exhaust gas such as the exhaust gas leaving the diesel engine automobiles, manufacturing how ammonia used in this denitration process.
つぎに、本発明を具体的に説明するために、本発明の実施例を挙げる。 Next, in order to describe the present invention specifically, examples of the present invention will be given.
実施例１
図１において、低温自動車排ガスの排ガスライン（１）に脱硝触媒（２）が装填されている。この触媒は、例えば酸化チタン（ＴｉＯ２）担体に五酸化バナジウム（Ｖ２Ｏ５）を担持してなるものであってよい。脱硝触媒はいわゆるハニカム構造の支持体に支持されたものが好ましい。脱硝触媒（２）の装填量はエンジン排気量と同じく１４．３リットルである。
Example 1
In FIG. 1, a denitration catalyst (2) is loaded in an exhaust gas line (1) for low-temperature automobile exhaust gas. This catalyst may be formed, for example, by supporting vanadium pentoxide (V 2 O 5 ) on a titanium oxide (TiO 2 ) support. The denitration catalyst is preferably supported on a so-called honeycomb structure support. The loaded amount of the denitration catalyst (2) is 14.3 liters, the same as the engine displacement.
排ガスライン（１）の外部に、尿素加水分解触媒（４）を装填した尿素加水分解反応器（３）が配置されている。同反応器（３）はその先端に、排ガスライン（１）内の脱硝触媒（２）装填部の上流に伸びるアンモニア導管（５）を有し、かつ同導管（５）の先端に脱硝触媒（２）装填部を臨むアンモニアノズル（６）を備えている。尿素加水分解反応器（３）はこれを一定温度に保つ電気ヒータ（７）を外装し、尿素加水分解触媒（４）は酸化チタン（ＴｉＯ２）担体に酸化夕ングステン（ＷＯ３）を添加した構造をなし、その装填量は６リットルである。尿素加水分解反応器（３）は電気ヒータ（７）で一定温度に保持される。電気ヒータ（７）の代わりにエンジン排熱で温度を保持してもよい。 A urea hydrolysis reactor (3) loaded with a urea hydrolysis catalyst (4) is disposed outside the exhaust gas line (1). The reactor (3) has an ammonia conduit (5) extending upstream of the loading portion of the denitration catalyst (2) in the exhaust gas line (1) at the tip thereof, and a denitration catalyst ( 2) An ammonia nozzle (6) facing the loading section is provided. The urea hydrolysis reactor (3) is equipped with an electric heater (7) for keeping it at a constant temperature, and the urea hydrolysis catalyst (4) is added with tungsten oxide (WO 3 ) to a titanium oxide (TiO 2 ) support. It has a structure and its loading is 6 liters. The urea hydrolysis reactor (3) is maintained at a constant temperature by an electric heater (7). The temperature may be maintained by engine exhaust heat instead of the electric heater (7).
尿素加水分解反応器（３）の内部において尿素加水分解触媒（４）装填部の上流に、尿素水タンク（８）からポンプ（９）によって圧送された尿素水を噴霧する尿素ノズル（１０）が尿素加水分解触媒（４）装填部を臨むように設けられている。尿素加水分解反応器（３）の内部において尿素ノズル（１０）の上流に、コンプレッサ（１１）からバルブ（１２）を経て圧送された空気を供給する空気供給口（１３）が設けられている。尿素水圧送用のポンプ（９）および空気供給量調整用のバルブ（１２）は、排ガス量、ＮＯｘ濃度および温度に関するデータに基づいてコントロールユニット（１４）でコントロールされる。 In the urea hydrolysis reactor (3), a urea nozzle (10) for spraying urea water pumped by the pump (9) from the urea water tank (8) is upstream of the urea hydrolysis catalyst (4) loading section. The urea hydrolysis catalyst (4) is provided so as to face the loading portion. Inside the urea hydrolysis reactor (3), an air supply port (13) for supplying air pumped from the compressor (11) through the valve (12) is provided upstream of the urea nozzle (10). The urea water pump (9) and the air supply amount adjusting valve (12) are controlled by the control unit (14) based on the data on the exhaust gas amount, NOx concentration and temperature.
上記構成の脱硝装置において、尿素加水分解反応器（３）に濃度３２．５ｗｔ％の尿素水を流量１〜３．５Ｌ／ｈでポンプ（９）で供給すると共に、その上流に、コンプレッサ（１１）からバルブ（１２）を経て流量８．５Ｎｍ３／ｈで加圧空気を供給し、尿素水を加圧空気によってミスト状にする。この尿素ミストを尿素加水分解触媒（４）装填部に連続的に導入し、尿素加水分解触媒（４）と尿素ミストを固液接触させ、温度１７０℃で尿素を加水分解し、アンモニアを生成させる。生成したアンモニアをアンモニア導管（５）を経てその先端のアンモニアノズル（６）から脱硝触媒（２）装填部に噴霧する。尿素水を加圧空気によってミスト状にする代わりに、尿素水を加圧気体によって水溶液の状態を保ちつつ尿素加水分解触媒反応帯域に導入してもよい。 In the denitration apparatus having the above configuration, urea water having a concentration of 32.5 wt% is supplied to the urea hydrolysis reactor (3) by a pump (9) at a flow rate of 1 to 3.5 L / h, and a compressor (11 ) Through a valve (12) and pressurized air is supplied at a flow rate of 8.5 Nm 3 / h, and urea water is made mist with pressurized air. This urea mist is continuously introduced into the urea hydrolysis catalyst (4) loading section, the urea hydrolysis catalyst (4) and the urea mist are brought into solid-liquid contact, and urea is hydrolyzed at a temperature of 170 ° C. to generate ammonia. . The generated ammonia is sprayed from the ammonia nozzle (6) at the tip of the ammonia through the ammonia conduit (5) to the denitration catalyst (2) loading section. Instead of making the urea water mist with pressurized air, the urea water may be introduced into the urea hydrolysis catalyst reaction zone while maintaining the state of the aqueous solution with the pressurized gas.
脱硝触媒（２）装填部では、供給されたアンモニアが還元剤として働き、排ガス中の窒素酸化物が選択的に窒素ガスに還元される。 In the denitration catalyst (2) loading section, the supplied ammonia acts as a reducing agent, and nitrogen oxides in the exhaust gas are selectively reduced to nitrogen gas.
実施例２
尿素加水分解触媒（４）を、酸化チタン（ＴｉＯ２）担体に酸化夕ングステン（ＷＯ３）を添加し、さらに五酸化バナジウム（Ｖ２Ｏ５）を担持した構造のものに代えた以外、実施例１と同じ操作を行った。
Example 2
Implementation was carried out except that the urea hydrolysis catalyst (4) was changed to a structure in which tungsten oxide (WO 3 ) was added to a titanium oxide (TiO 2 ) support and vanadium pentoxide (V 2 O 5 ) was supported. The same operation as in Example 1 was performed.
性能試験
実施例１および２の尿素加水分解触媒を用い、尿素加水分解反応器の温度を変え、生成したアンモニアの生成率を求めた。この結果を図２のグラフに示す。生成率（％）はアンモニア生成量（当量）／尿素（当量）×１００である。
Performance Test Using the urea hydrolysis catalysts of Examples 1 and 2, the temperature of the urea hydrolysis reactor was changed, and the production rate of produced ammonia was determined. The result is shown in the graph of FIG. The production rate (%) is ammonia production (equivalent) / urea (equivalent) × 100.
（１）：排ガスライン
（２）：脱硝触媒
（３）：尿素加水分解反応器
（４）：尿素加水分解触媒
（５）：アンモニア導管
（６）：アンモニアノズル
（７）：電気ヒータ
（８）：尿素水タンク
（９）：ポンプ
（１０）：尿素ノズル
（１１）：コンプレッサ
（１２）：バルブ
（１３）：空気供給口
（１４）：コントロールユニット
(1) : exhaust gas line (2) : denitration catalyst (3) : urea hydrolysis reactor (4) : urea hydrolysis catalyst (5) : ammonia conduit (6) : ammonia nozzle (7) : electric heater (8) : Urea water tank (9) : Pump (10) : Urea nozzle (11) : Compressor (12) : Valve (13) : Air supply port (14) : Control unit
Claims (2)
A denitration method for selectively reducing nitrogen oxides using ammonia as a reducing agent, wherein the ammonia produced by the method according to claim 1 is used as a reducing agent .
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| DE10022842A1 (en) * | 2000-05-10 | 2001-11-22 | Dmc2 Degussa Metals Catalysts | Structured catalyst for the selective reduction of nitrogen oxides using ammonia using a compound that can be hydrolyzed to ammonia |
| JP2004033991A (en) * | 2002-07-08 | 2004-02-05 | Mitsubishi Heavy Ind Ltd | Method of denitrifying combustion exhaust gas and denitrification catalyst for the same |
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| JP5885811B1 (en) * | 2014-11-21 | 2016-03-16 | 株式会社タクマ | Urea hydrolysis apparatus and control method thereof |
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