JP2006122792A - Urea hydrolysis catalyst, ammonia manufacturing method, and denitration method - Google Patents

Urea hydrolysis catalyst, ammonia manufacturing method, and denitration method Download PDF

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JP2006122792A
JP2006122792A JP2004313282A JP2004313282A JP2006122792A JP 2006122792 A JP2006122792 A JP 2006122792A JP 2004313282 A JP2004313282 A JP 2004313282A JP 2004313282 A JP2004313282 A JP 2004313282A JP 2006122792 A JP2006122792 A JP 2006122792A
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ammonia
denitration
hydrolysis catalyst
exhaust gas
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JP4599989B2 (en
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Susumu Hizuya
進 日数谷
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Hitachi Zosen Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a denitration method by selective reduction of nitrogen oxides in a low-temperature automobile exhaust gas such as an exhaust gas discharged from a diesel-engine automobile, an ammonia manufacturing method used for this denitration method, and a urea hydrolysis catalyst to be used for this ammonia manufacturing method. <P>SOLUTION: In the ammonia manufacturing method, ammonia is continuously manufactured by hydrolyzing urea, while making a urea water in a mist state by a pressurized gas or keeping it in a water solution, by bringing the urea water into solid-liquid contact with a urea hydrolysis catalyst having a structure such that a tungstic oxide is added to a titanium oxide carrier, or the tungstic oxide is added to the titanium oxide carrier and further a vanadium pentoxide is supported on the carrier, in the temperature range of 130-200°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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、およびこのアンモニア製造方法に用いる尿素加水分解触媒に関するものである。   The present invention relates to a denitration method by selective reduction of nitrogen oxides in low-temperature automobile exhaust gas such as exhaust gas emitted from a diesel engine vehicle, a method for producing ammonia used in this denitration method, and a urea hydrolysis catalyst used in this ammonia production method It is about.

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 outside the pipe are installed 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) A method of mixing urea water and a urea hydrolysis catalyst solution, heating the mixed liquid to perform gas-liquid separation, and injecting the separated ammonia-containing gas 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 more, and ammonia is generated 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。
特開２００１−２７１１２号公報 特開平１０−Ｈ８４５６号公報 特開平８−７１３７２号公報 特開平１１−１７１５３５号公報 In this method, since the contact temperature is 200 ° C. or higher, the thermal decomposition reaction proceeds together with the hydrolysis reaction, and not only the ammonia production rate is deteriorated, but also the clogging of the denitration catalyst due to the precipitation of by-products and the blockage of the piping Happens.
JP 2001-271112 A JP-A-10-H8456 JP-A-8-71372 JP 11-171535 A

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、およびこのアンモニア製造方法に用いる尿素加水分解触媒を提供することを課題とする。   The present invention can overcome the above-mentioned problems of the prior art, a denitration method by selective reduction of nitrogen oxides in exhaust gas, a method for producing ammonia used in this denitration method, and urea used in this ammonia production method It is an object to provide a hydrolysis catalyst.

請求項１に係る発明は、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ことを特徴とする、尿素加水分解触媒である。   The invention according to claim 1 is characterized in that it has a structure in which tungsten oxide is added to a titanium oxide support or a structure in which tungsten oxide is added to a titanium oxide support and vanadium pentoxide is supported. It is a decomposition catalyst.

請求項２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１３０〜２００℃の温度範囲で特許請求範囲１記載の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製造方法である。   In the invention according to claim 2, the urea water is made into a mist form with a pressurized gas or kept in an aqueous solution state in a solid-liquid contact with the urea hydrolysis catalyst according to claim 1 in a temperature range of 130 to 200 ° C. A method for producing ammonia by hydrolysis of urea, wherein urea is hydrolyzed to produce ammonia continuously.

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 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３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ＮＯｘ選択還元法において、アンモニアとして請求項２記載の方法によって生成させたものを用いることを特徴とする、脱硝方法である。   The invention according to claim 3 is characterized in that, in the NOx selective reduction method for selectively reducing nitrogen oxides using ammonia as a reducing agent, ammonia produced by the method according to claim 2 is used. This is a denitration method.

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 in the following formula.

（ＮＨ２）２ＣＯ ＋ Ｈ２０ → ２ＮＨ３ ＋ Ｃ０２ (NH 2 ) 2 CO + H 2 0 → 2NH 3 + C 0 2

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、およびこのアンモニア製造方法に用いる尿素加水分解触媒を提供することができる。   INDUSTRIAL APPLICABILITY According to the present invention, a denitration method by selective reduction of nitrogen oxides in low-temperature automobile exhaust gas such as exhaust gas emitted from a diesel engine vehicle, a method for producing ammonia used in this denitration method, and a urea hydrolysis catalyst used in this ammonia production method Can be provided.

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 amount of the denitration catalyst (2) loaded 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 denitration catalyst (2) loading section in the exhaust gas line (1) at the tip, and a denitration catalyst (5) at the tip of the conduit (5). 2) Equipped with an ammonia nozzle (6) facing the loading section. 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。   Inside 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 disposed upstream of the urea hydrolysis catalyst (4) loading section. The urea hydrolysis catalyst (4) is provided so as to face the loading section. 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 adjustment 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 configured as described above, 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 urea mist are brought into solid-liquid contact, and urea is hydrolyzed at a temperature of 170 ° C. to generate ammonia. . The produced 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
The urea hydrolysis catalyst (4) was replaced with a titanium oxide (TiO 2 ) support added with tungsten oxide (WO 3 ), and further replaced with a structure carrying vanadium pentoxide (V 2 O 5 ). 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 catalyst 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.

尿素加水分解反応器を備えた脱硝装置を概略的に示す断面図である。It is sectional drawing which shows schematically the denitration apparatus provided with the urea hydrolysis reactor. 温度とアンモニア生成率の関係を示すグラフである。It is a graph which shows the relationship between temperature and ammonia production rate.

符号の説明Explanation of symbols

(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 (3)

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ことを特徴とする、尿素加水分解触媒。   A urea hydrolysis catalyst characterized by having a structure in which tungsten oxide is added to a titanium oxide support, or a structure in which tungsten oxide is added to a titanium oxide support and vanadium pentoxide is supported. 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１３０〜２００℃の温度範囲で特許請求範囲１記載の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製造方法。   The urea water is made into a mist with a pressurized gas, or is kept in an aqueous solution state and brought into solid-liquid contact with the urea hydrolysis catalyst according to claim 1 in a temperature range of 130 to 200 ° C., thereby hydrolyzing urea and ammonia. A process for producing ammonia by hydrolysis of urea, characterized in that 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ＮＯｘ選択還元法において、アンモニアとして請求項２記載の方法によって生成させたものを用いることを特徴とする、脱硝方法。
A NOx selective reduction method for selectively reducing nitrogen oxides using ammonia as a reducing agent, wherein the ammonia produced by the method according to claim 2 is used as ammonia.
JP2004313282A 2004-10-28 2004-10-28 Ammonia production method and denitration method Expired - Fee Related JP4599989B2 (en)

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JP2009262098A (en) * 2008-04-28 2009-11-12 Ne Chemcat Corp Exhaust gas clarifying method using selective reduction catalyst
JP2010514546A (en) * 2006-12-23 2010-05-06 アルツケム トロストベルク ゲゼルシャフト ミット ベシュレンクテル ハフツング Selective catalytic reduction of nitrogen oxides in automobile exhaust
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