JP4545631B2 - Method for producing high-purity urea water - Google Patents
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- JP4545631B2 JP4545631B2 JP2005123491A JP2005123491A JP4545631B2 JP 4545631 B2 JP4545631 B2 JP 4545631B2 JP 2005123491 A JP2005123491 A JP 2005123491A JP 2005123491 A JP2005123491 A JP 2005123491A JP 4545631 B2 JP4545631 B2 JP 4545631B2
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- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004202 carbamide Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 229910021529 ammonia Inorganic materials 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
Description
本発明は、高純度尿素水に関する。 The present invention relates to high-purity urea water.
尿素の製造方法については成書も多く出版され（例えば、化学史研究 ＶＯＬ２０ ＮＯ３（１９９３）、Ｃhemical Ｅconomics Ｈandboook−ＳＲＩ（２００１年））、アンモニアと炭酸ガスから高圧法で製造されている。生成した尿素を水に溶解させ尿素水とするにことについても記載されている。例えば特許文献；特開平８−５７２６１号公報等。
近年、尿素水に関しても従前の用途である焼却場の脱硝触媒のアンモニア源としてではなく、さらに高純度が要求される高度な用途に用いられる高純度尿素水の社会的要請が高まっている。特に尿素水の導入配管の詰まりを誘引する物質を含まず、かつ、臭気の原因となるアンモニアの生成が少ない尿素水は内燃機関排気処理用ＮＯｘ還元触媒においてそのアンモニア源として切望されている（特開２００４−２９０８３６）。 In recent years, there has been an increasing social demand for high-purity urea water that is used not only as an ammonia source for a denitration catalyst in an incineration plant, which is a conventional application, but also for advanced applications that require higher purity. In particular, urea water that does not contain a substance that induces clogging of the urea water introduction pipe and generates less ammonia that causes odor is highly desired as an ammonia source in the NOx reduction catalyst for exhaust gas treatment of internal combustion engines (special feature). Open 2004-290836).
本発明は上記状況に鑑みてなされたもので、ＳＣＲ触媒を用いたスパーク点火やディーゼルエンジンなどの燃焼エンジンにおいて、ＮＯxを浄化する装置に連続的に供給するのに適した尿素水に係るものである。ディーゼルエンジン排気処理用ＳＣＲ触媒の長期連続運転に不具合を生じさせる可能性をミニマイズするための高純度尿素の製造方法に関わる。 The present invention has been made in view of the above situation, and relates to urea water suitable for continuous supply to a device for purifying NOx in a combustion engine such as a spark ignition using a SCR catalyst or a diesel engine. is there. The present invention relates to a method for producing high-purity urea for minimizing the possibility of causing problems in long-term continuous operation of a SCR catalyst for diesel engine exhaust treatment.
本発明は２０重量％〜６０重量％、１０〜６０℃で固体状尿素を電気伝導度が０．３ｍｓ/ｍ以下の水に溶解させ、かかる尿素水をろ過する工程及びオイル吸着剤で処理する工程からなることを特徴とする高純度尿素水の製造方法。 In the present invention, solid urea is dissolved in water having an electric conductivity of 0.3 ms / m or less at 20 to 60% by weight and 10 to 60 ° C., and the urea water is filtered and treated with an oil adsorbent. A method for producing high-purity urea water, comprising a step.
本発明により例えば内燃機関排気処理用ＮＯｘ還元触媒におけるアンモニア源として用いられる高純度の尿素水を製造することができる。 According to the present invention, for example, high-purity urea water used as an ammonia source in an NOx reduction catalyst for exhaust gas treatment of an internal combustion engine can be produced.
本発明に用いる固体状尿素は周知の方法（例えば、化学史研究 ＶＯＬ２０ ＮＯ３（１９９３）、Ｃhemical Ｅconomics Ｈandboook−ＳＲＩ（２００１年））で工業的に生産され市販されているものを特別な制限なく用いることができる。 As the solid urea used in the present invention, those commercially produced and marketed by a known method (for example, chemical history research VOL20 NO3 (1993), Chemical Economics Handboook-SRI (2001)) are used without any particular limitation. be able to.
用いられる形状としては粒条、パウダー状いずれでも特に制限はないが、輸送の便宜や工業スケールでの取り扱いの容易さ等から粒状の尿素を用いることが好ましい。また、水に溶解させる速度を向上させるため適宜好ましい粒子径に調節することが好ましい。
尿素水の製造は尿素を水に溶解させることで行われる。一般的には尿素水は尿素濃度２０〜６０重量％、好ましくは２５〜５５重量％である。
There are no particular restrictions on the shape used, either in the form of granules or powder, but it is preferable to use granular urea for convenience of transportation and ease of handling on an industrial scale. Moreover, it is preferable to adjust to a preferable particle diameter as appropriate in order to improve the speed of dissolution in water.
The production of urea water is performed by dissolving urea in water. In general, urea water has a urea concentration of 20 to 60% by weight, preferably 25 to 55% by weight.
溶解後の温度は、好ましくは１０ないし６０℃、更に好ましくは１０ないし５０℃である。この濃度範囲の尿素をこの温度範囲で溶解させることで初めて高純度の尿素水が製造され、内燃機関排気処理用ＮＯx還元触媒のアンモニア源として使用可能な尿素水が得られることがわかった。尿素を水に添加すると尿素の溶解熱により温度が低下する。溶解温度が１０℃より低い場合には、尿素の溶解速度が小さくなり、極端な場合には尿素水そのものが凍結する危険性がある。溶解時の温度が６０℃よりはるかに高い場合には内燃機関排気処理用ＮＯx還元触媒のアンモニア源として用いた場合に臭気の点などで問題となることがわかった。これは、尿素の加水分解が促進されアンモニアの発生量が大きくなるものと推測している。作業環境上の問題から気相部のアンモニア濃度は日本産業衛生学会の許容濃度２５ｐｐｍを超えない事が望ましい。ここで気相部のアンモニア濃度は一般的な検知管で測定する。 The temperature after dissolution is preferably 10 to 60 ° C, more preferably 10 to 50 ° C. It was found that high-purity urea water was produced for the first time by dissolving urea in this concentration range in this temperature range, and urea water that could be used as an ammonia source for the NOx reduction catalyst for internal combustion engine exhaust treatment was obtained. When urea is added to water, the temperature decreases due to the heat of dissolution of urea. When the dissolution temperature is lower than 10 ° C., the dissolution rate of urea decreases, and in an extreme case, there is a risk that the urea water itself freezes. It has been found that when the temperature during melting is much higher than 60 ° C., it becomes a problem in terms of odor when used as an ammonia source for a NOx reduction catalyst for internal combustion engine exhaust treatment. This is presumed that urea hydrolysis is accelerated and the amount of ammonia generated is increased. Due to problems in the working environment, it is desirable that the ammonia concentration in the gas phase does not exceed the allowable concentration of 25 ppm of the Japan Society for Occupational Health. Here, the ammonia concentration in the gas phase is measured with a general detector tube.
尿素を溶解させる水は、電気伝導度が０．３ｍＳ／ｍ以下の純水を用いる。この電気伝導度を有する水を内燃機関排気処理用ＮＯx還元触媒のアンモニア源として用いた場合には、ディーゼルエンジンを連続運転した場合に尿素の供給配管に詰まりが発生しない点において好ましい。ここで、この純水は通常の製造方法、例えばイオン交換樹脂、逆浸透膜等を用いる周知の方法により得ることが出来る。水の電気伝導度が０．３ｍＳ／ｍよりはるかに高くなると無機電解質の増加により尿素の水への溶解度が影響されるため好ましくない。 As water for dissolving urea, pure water having an electric conductivity of 0.3 mS / m or less is used. When water having this electrical conductivity is used as the ammonia source of the NOx reduction catalyst for internal combustion engine exhaust treatment, it is preferable in that the urea supply pipe is not clogged when the diesel engine is continuously operated. Here, the pure water can be obtained by an ordinary production method, for example, a known method using an ion exchange resin, a reverse osmosis membrane or the like. If the electrical conductivity of water is much higher than 0.3 mS / m, the solubility of urea in water is affected by the increase in inorganic electrolyte, which is not preferable.
また、本発明の態様として上記で得られた尿素水をろ過する工程が必須である。これらの固形物は配管等から混入する僅かな異物、或いは上記処理により極微量混入する処理剤等と推定している。内燃機関排気処理用アンモニア還元触媒装置では排気ガス中のＮＯｘを還元する触媒の上流側に尿素水を含む還元剤を供給する還元剤供給装置が含まれている。この還元剤供給装置ではろ過することによりしない場合に比べて、一層、還元剤供給装置に装備されている導入配管の詰まりが軽減される。従って、ろ過した尿素水を用いることにより内燃機関処理用アンモニア還元装置の負荷を軽減することができる。ろ過器としては、ストレーナー等で十分である。ストレーナーとしてはバケット型等を使用でき、異物の大きさによりメッシュ型スクリーン、繊維成型型、不織布プリーツ型等のエレメントを用いる。好ましくはろ過精度０．５〜５００μｍのエレメント等を用いることができる。 Moreover, the process of filtering the urea water obtained above as an aspect of this invention is essential. These solids are presumed to be a slight amount of foreign matter mixed in from pipes or the like, or a processing agent mixed in a trace amount by the above processing. The ammonia reduction catalyst device for exhaust gas treatment of an internal combustion engine includes a reducing agent supply device that supplies a reducing agent containing urea water upstream of a catalyst that reduces NOx in exhaust gas. In this reducing agent supply device, clogging of the introduction pipe equipped in the reducing agent supply device is further reduced as compared with a case where the reducing agent supply device does not perform filtration. Therefore, the load of the ammonia reduction device for internal combustion engine processing can be reduced by using the filtered urea water. A strainer or the like is sufficient as the filter. As the strainer, a bucket type or the like can be used, and an element such as a mesh type screen, a fiber molding type, or a nonwoven fabric pleat type is used depending on the size of the foreign matter. Preferably, an element having a filtration accuracy of 0.5 to 500 μm can be used.
本発明の態様として２０重量％〜６０重量％、１０〜６０℃で固体状尿素を電気伝導度が０．３ｍｓ/ｍ以下の水に溶解させることで得られた尿素水をオイル吸着剤で処理する工程が必須である。これにより一層、高純度の尿素水を得ることが可能である。オイル吸着剤で処理することにより尿素水の表面に油膜を形成し、長期にわたる貯蔵において貯蔵容器表面での薄膜状の析出を阻止できる。このオイル含量は当該炭化水素系オイルは塩酸酸性下、四塩化炭素に油分を抽出分離した後に赤外吸収を測定することで定量することができる。オイル吸着剤（例えばケイソウ土、活性炭、オイル吸着樹脂）で処理することによりオイル含量は５０ｐｐｍ以下、好ましくは５ｐｐｍ以下、さらに好ましくは３ｐｐｍ以下とするのが好ましい。 As an aspect of the present invention, urea water obtained by dissolving solid urea in water having an electric conductivity of 0.3 ms / m or less at 20 to 60% by weight and 10 to 60 ° C. is treated with an oil adsorbent. The process to do is essential. As a result, it is possible to obtain a highly pure urea solution. By treating with an oil adsorbent, an oil film is formed on the surface of the urea water, and thin film deposition on the surface of the storage container can be prevented during long-term storage. The oil content can be quantified by measuring the infrared absorption after extracting and separating the oil from carbon tetrachloride under acidity of hydrochloric acid. By treating with an oil adsorbent (for example, diatomaceous earth, activated carbon, oil adsorbing resin), the oil content is preferably 50 ppm or less, preferably 5 ppm or less, and more preferably 3 ppm or less.
ここで気相部のアンモニア濃度は一般的な検知管で測定した。また、尿素水中の異物は尿素水をろ紙でろ過し、ろ紙を水洗後、乾燥させ、顕微鏡により観察することで、その数を確認する事ができる。 Here, the ammonia concentration in the gas phase was measured with a general detector tube. The number of foreign substances in urea water can be confirmed by filtering the urea water with a filter paper, washing the filter paper with water, drying it, and observing it with a microscope.
３２．５％になるように尿素を電気伝導度０．３ｍＳ/ｍ未満の水に溶解させた。その時の温度を溶解後で３０℃とし、２時間及び５時間同温度で放置した。 Urea was dissolved in water having an electric conductivity of less than 0.3 mS / m so as to be 32.5%. The temperature at that time was 30 ° C. after dissolution and left at the same temperature for 2 hours and 5 hours.
温度を５０℃とした以外は実施例１と同様に行った。 The same operation as in Example 1 was performed except that the temperature was 50 ° C.
温度を６０℃とした以外は実施例１と同様に行った。 The same operation as in Example 1 was performed except that the temperature was 60 ° C.
実施例１により調整した尿素水を室温で空間速度 １０ｈ−１で活性炭（Ｆ−４００（東洋カルゴン社製））に通した。 The urea water prepared in Example 1 was passed through activated carbon (F-400 (manufactured by Toyo Calgon)) at room temperature and a space velocity of 10 h-1.
実施例１により調整した尿素水を室温で空間速度 ２０００ｈ−１で珪藻土を通過させた。 The urea water prepared by Example 1 was allowed to pass through diatomaceous earth at a space velocity of 2000 h-1 at room temperature.
実施例１により調整した尿素水を室温で空間速度 ２０００ｈ−１でオイル除去フィルター（タフネルオイルブロッター（三井化学製））を通過させた。 The urea water prepared in Example 1 was passed through an oil removal filter (Toughnel Oil Blotter (Mitsui Chemicals)) at room temperature at a space velocity of 2000 h-1.
実施例３で調整した尿素水を更に、５μｍのフィルターを通過させた。 The urea water prepared in Example 3 was further passed through a 5 μm filter.
［比較例１］
温度を７０℃とした以外は実施例１と同様に行った。
実施例１〜２及び比較例１〜２での尿素溶解後の気相のアンモニア濃度を測定した結果を示した。尚、アンモニア濃度は室温に冷却後に測定した。
[Comparative Example 1]
The same operation as in Example 1 was performed except that the temperature was 70 ° C.
The result of having measured the ammonia concentration of the gaseous phase after urea melt | dissolution in Examples 1-2 and Comparative Examples 1-2 was shown. The ammonia concentration was measured after cooling to room temperature.
また、実施例１〜２及び４〜７の分析結果を表２に示した。 In addition, Table 2 shows the analysis results of Examples 1-2 and 4-7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007145796A (en) * | 2005-03-17 | 2007-06-14 | Mitsui Chemicals Inc | Urea water and denitrification apparatus using the same |
| JP5066852B2 (en) * | 2006-07-10 | 2012-11-07 | 日本化成株式会社 | Method for removing oil from solid urea containing oil |
| JP2008280263A (en) * | 2007-05-09 | 2008-11-20 | Mitsui Chemicals Inc | Method for producing highly pure urea water |
| WO2010092671A1 (en) * | 2009-02-10 | 2010-08-19 | ズードケミー触媒株式会社 | Agent and method for detoxifying metal hydride-containing exhaust gas |
| JP5338488B2 (en) * | 2009-06-03 | 2013-11-13 | 日本化成株式会社 | Method for producing high-purity urea water |
| JP2010280595A (en) * | 2009-06-03 | 2010-12-16 | Nippon Kasei Chem Co Ltd | Method for producing high-purity urea |
| JP6043398B2 (en) * | 2015-04-03 | 2016-12-14 | クラリアント触媒株式会社 | Detoxifying agent and method for exhaust gas containing metal hydride |
| JP2016169236A (en) * | 2016-06-27 | 2016-09-23 | 日本化成株式会社 | Method for producing high-purity urea water |
| CN112520919B (en) * | 2020-11-17 | 2022-05-27 | 珠海格力智能装备有限公司 | Water purification method and device based on urea machine |
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| JP2007145796A (en) * | 2005-03-17 | 2007-06-14 | Mitsui Chemicals Inc | Urea water and denitrification apparatus using the same |
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| JP2006298828A (en) | 2006-11-02 |
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