JPH0196011A - Production of zeolite containing copper - Google Patents
Production of zeolite containing copperInfo
- Publication number
- JPH0196011A JPH0196011A JP62251616A JP25161687A JPH0196011A JP H0196011 A JPH0196011 A JP H0196011A JP 62251616 A JP62251616 A JP 62251616A JP 25161687 A JP25161687 A JP 25161687A JP H0196011 A JPH0196011 A JP H0196011A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- copper
- tsz
- ammonia
- present
- 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.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 50
- 239000010949 copper Substances 0.000 title claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052802 copper Inorganic materials 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 7
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 moisture Chemical compound 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、石油化学１石油精製、公害防止分野における
触媒、吸着剤の製造に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the production of catalysts and adsorbents in the field of petrochemistry, petroleum refining, and pollution prevention.
その中でも特に工業プラント、自動車等から排出される
排ガス中のＮＯｘを分解する公害防止用触媒に関する。Among these, the present invention particularly relates to a pollution prevention catalyst that decomposes NOx in exhaust gas emitted from industrial plants, automobiles, and the like.
［従来の技術］
公害防止用触媒として、今まで市販触媒を含めた広範な
分解触媒の探索が行なわれているが見るべき成果は得ら
れていない、これは排ガスの主成分であるＮＯの分解速
度が非常に遅い為である。[Prior art] A wide range of decomposition catalysts, including commercially available catalysts, have been searched for as catalysts for pollution prevention, but no significant results have been obtained. This is because the speed is very slow.
現状では、Ｎ Ｈ３などの還元剤を触媒と併用する還元
脱硝プロセスが企業化されている。しかしこのプロセス
では、還元剤が必要であり、プロセスも複雑となり、更
に未反応還元剤を回収、あるいは分解する為の装置が必
要となる。その点Ｎｏ直接接触分解は最も単純で経済的
なプロセスである。Currently, reductive denitrification processes that use reducing agents such as NH3 in combination with catalysts have been commercialized. However, this process requires a reducing agent, making the process complicated, and also requires a device to recover or decompose the unreacted reducing agent. In that respect, direct catalytic cracking is the simplest and economical process.
今までにもＮｏ直接接触分解反応において、Ｐｔ。Until now, Pt has been used in the direct catalytic cracking reaction of No.
Ｃｕ Ｏ、Ｃｏ ３０４などにＮＯ分解活性が認められ
たが、何れも分解生成物である酸素の被毒作用により充
分な活性が得られず、実用触媒とはなり得なかった。Although NO decomposition activity was observed in CuO, Co304, etc., sufficient activity could not be obtained due to the poisoning effect of oxygen, which is a decomposition product, and neither could be used as a practical catalyst.
最近、銅イオンを含有し、かつ特定の結晶構造を有する
ゼオライトが、Ｎｏ直接接触分解触媒として、処理ガス
中に水分や酸素が共存しても被毒されないＮｏ分解触ｔ
Ｊｉ、（特開昭６０−１２５２５０号）となる事が見出
されている。Recently, zeolite containing copper ions and having a specific crystal structure has been developed as a No direct catalytic cracking catalyst that is not poisoned even when moisture and oxygen coexist in the treated gas.
Ji, (Japanese Unexamined Patent Publication No. 125250/1982).
本発明は、特開昭６０−１２５２５０号公報の改良法を
提供するものでもある。The present invention also provides an improved method of JP-A-60-125250.
［本発明が解決しようとする問題点］
本発明の目的は、水分、酸素、二酸化イオウの共存によ
る被毒を受けず、更に低温においても、高活性な、定常
安定性の良い、従来にない特性を持つ触媒の製造方法を
提供することにある。[Problems to be Solved by the Present Invention] The object of the present invention is to provide a novel material that is not poisoned by the coexistence of moisture, oxygen, and sulfur dioxide, and has high activity and good steady-state stability even at low temperatures. The object of the present invention is to provide a method for producing a catalyst having specific characteristics.
［問題点を解決する為の手段および作用］本発明は、ゼ
オライトが本明細書第１表に示した粉末Ｘ線回折により
求めた格子面間隔（ｄ値）を持ち、該ゼオライトを銅イ
オン交換する際に水溶性銅塩及びアンモニアを含む水溶
液中で行うことにより、処理ガス中に水分、酸素、二酸
化イオウが共存しても、活性低下を起すことなく、定常
安定性を示す銅含有ゼオライトを製造する方法を提供す
るものである。[Means and effects for solving the problems] The present invention provides that the zeolite has a lattice spacing (d value) determined by powder X-ray diffraction shown in Table 1 of the present specification, and that the zeolite is subjected to copper ion exchange. By conducting the process in an aqueous solution containing a water-soluble copper salt and ammonia, we can produce a copper-containing zeolite that exhibits steady-state stability without decreasing activity even when moisture, oxygen, and sulfur dioxide coexist in the process gas. The present invention provides a method for manufacturing.
第 １ 表 以下、本発明の詳細な説明する。Table 1 The present invention will be explained in detail below.
本発明で触媒の基剤として用い得るゼオライトは、第１
表に示した格子面間隔（ｄ値）を持つ事か必須であるが
、その製造法は限定されるものではない。好ましくは、
本発明で使用されるゼオライトのＳｉＯ／Ａ！２０３モ
ル比は２０〜２００である。触媒の基剤として第１表に
示した格子面間隔（ｄ値）を持つゼオライトそのままで
はＮｏの触媒分解活性はほとんどない。The zeolite that can be used as a catalyst base in the present invention is
Although it is essential to have the lattice spacing (d value) shown in the table, the manufacturing method is not limited. Preferably,
SiO/A of the zeolite used in the present invention! The 203 molar ratio is 20-200. When zeolite having the lattice spacing (d value) shown in Table 1 is used as a catalyst base, it has almost no catalytic decomposition activity for No.
本発明の銅含有ゼオライトは、第１表に示した格子面間
隔（ｄ値）を持つゼオライト中の陽イオンを別イオンで
交換する際に、水溶性銅塩及びアンモニアを含む水溶液
を用いて、製造する事が、必須である。水溶性銅塩とし
ては、硫酸銅、塩化ｊ１１ 、酢酸銅、硝酸銅などが使
用でき、またアンモニアとしては、アンモニア水、アン
モニア含水化合物またはアンモニアガスを溶解した水溶
液などが使用できる。アンモニアの添加量は特に限定さ
れないが、ゼオライトを含むスラリー溶液中のｐＨが４
〜１２の範囲になるように添加する事が好ましい。水溶
液中の銅イオンの濃度は、目的とするゼオライトの銅イ
オン交換率によって任意に設定することが出初る。The copper-containing zeolite of the present invention uses an aqueous solution containing a water-soluble copper salt and ammonia when exchanging the cations in the zeolite having the lattice spacing (d value) shown in Table 1 with another ion. Manufacturing is essential. As the water-soluble copper salt, copper sulfate, j11 chloride, copper acetate, copper nitrate, etc. can be used, and as the ammonia, aqueous ammonia, an ammonia-containing compound, or an aqueous solution of ammonia gas can be used. The amount of ammonia added is not particularly limited, but if the pH of the slurry solution containing zeolite is 4.
It is preferable to add the amount in the range of 12 to 12. The concentration of copper ions in the aqueous solution can be arbitrarily set depending on the copper ion exchange rate of the target zeolite.
２十 銅イオンはＣｕ” 、Ｃｕ 、Ｃｕ０Ｈ。twenty Copper ions are Cu”, Cu, and Cu0H.
［Ｃｕ（ＮＨ３）４］２＋のいずれかの形態でゼオライ
ト中の陽イオンと交換している。またゼオライトの一部
は大過剰のＮＨ３分子が存在する為に、ＮＨ４型にもな
っている。[Cu(NH3)4]2+ is exchanged with the cation in the zeolite in any form. In addition, some of the zeolites are also in the NH4 type due to the presence of a large excess of NH3 molecules.
本発明では、１回の交換で銅イオン交換率が１００％以
上のものが得られる。In the present invention, a copper ion exchange rate of 100% or more can be obtained by one exchange.
イオン交換終了後、水洗、乾燥して銅含有ゼオライトが
得られる。銅含有量は高い程よいが、望ましくは０．０
３ｗｔ％以上で、さらに望ましくは１ ｗ ｔ％以上で
ある。銅含有量は高い程、ＮＯ分解活性が高い。After the ion exchange is completed, the copper-containing zeolite is obtained by washing with water and drying. The higher the copper content, the better, but preferably 0.0
The content is 3 wt% or more, more preferably 1 wt% or more. The higher the copper content, the higher the NO decomposition activity.
銅含有量ゼオライトのＳ ｉ Ｏ２／ Ａ！２０３上２
０は、使用したゼオライトのＳ ｉ Ｏ２／ＡＪ２２０
３モル比と実質的に変わらない、銅含有ゼオライトの結
晶構造もイオン交換前後で異なるものではなく、第１表
に示した格子面間隔（ｄ値）で特徴づけることができる
。S i O2/A of copper content zeolite! 203 top 2
0 is the zeolite used S i O2/AJ220
The crystal structure of the copper-containing zeolite, which has a molar ratio of 3, does not differ substantially before and after ion exchange, and can be characterized by the lattice spacing (d value) shown in Table 1.
本発明法による、銅含有ゼオライトがＮＯｘ接触分解反
応に極めて高い活性を示す理由については、明らかでな
いが、銅イオンとともにゼオライトにとりこまれたアン
モニア分子がＮＯｘ接触分解反応の前処理段階で脱離し
、部分的還元が起り、このＮＯｘ接触分解反応の活性サ
イトであるＣｕ＋が出来、Ｃｕ ” コＣｕ ”ｆ）
ｐ化還元サイクルがスムーズに行われ、高活性を持続さ
れるものと考えられる。Although it is not clear why the copper-containing zeolite produced by the method of the present invention exhibits extremely high activity in the NOx catalytic decomposition reaction, ammonia molecules incorporated into the zeolite together with copper ions are desorbed during the pretreatment stage of the NOx catalytic decomposition reaction. Partial reduction occurs and Cu+, which is the active site for this NOx catalytic decomposition reaction, is created, and Cu ``CoCu ''f)
It is thought that the p-oxidation reduction cycle is carried out smoothly and high activity is maintained.
本発明法による銅含有ゼオライトの持つ特異的結晶構造
とその構造安定性および耐熱性等が複合的に作用して酸
素、水分、二酸化イオウの共存下でも高い活性を示して
いると考えられる。It is thought that the specific crystal structure of the copper-containing zeolite produced by the method of the present invention, its structural stability, heat resistance, etc. act in a complex manner to exhibit high activity even in the coexistence of oxygen, moisture, and sulfur dioxide.
さらに、銅含有ゼオライトをＮＯｘ分解用触媒として使
用する場合の使用温度範囲は２００〜１０００℃の範囲
で、好ましくは３００〜７００°Ｃの範囲である。触媒
と処理ガスとの接触時間は特に限定されるものではない
。Further, when using the copper-containing zeolite as a catalyst for NOx decomposition, the operating temperature range is from 200 to 1000°C, preferably from 300 to 700°C. The contact time between the catalyst and the processing gas is not particularly limited.
［発明の効果］
本発明で得られる銅含有ゼオライトは、石油化学９石油
精製、公害防止分野における触媒、吸着剤として、その
中でもＮＯｘ分解除去触媒として、特に優れたＮＯｘ分
解活性を示す。[Effects of the Invention] The copper-containing zeolite obtained in the present invention exhibits particularly excellent NOx decomposition activity as a catalyst and adsorbent in the field of petrochemical oil refining and pollution prevention, and among them, as a NOx decomposition and removal catalyst.
本発明で得られた銅含有ゼオライトは、粘土鉱物等のバ
インダーを用いて成形して用いることもできる。The copper-containing zeolite obtained in the present invention can also be used by being shaped using a binder such as clay mineral.
また、本発明は、あらかじめゼオライトを成形し、その
成形体を水溶性銅塩及びアンモニアを含む水溶液で銅イ
オン交換してもよい。成形体の大きさは特に限定される
ものではない。Furthermore, in the present invention, zeolite may be shaped in advance, and the shaped body may be subjected to copper ion exchange with an aqueous solution containing a water-soluble copper salt and ammonia. The size of the molded body is not particularly limited.
以下、実施例及び比較例においてさらに詳細に説明する
。Hereinafter, it will be explained in more detail in Examples and Comparative Examples.
［実施例］
実施例１（ゼオライトの合成）
撹拌状態にある実容積２１のオーバーフロータイプ反応
槽に、珪酸ソーダ水溶液（ＳｉＯ□１５３．４ ｇ ／
１ ； Ｎ ａ ２０ ； ４９．９ ｇ ／ ｆｌ
。[Example] Example 1 (Synthesis of zeolite) A sodium silicate aqueous solution (SiO□153.4 g /
1; Na20; 49.9 g/fl
.
Ａｌ１２０３ ； ０．８ ｇ／β）と硫酸を添加した
硫酸アルミニウム水溶液（Ａｆ Ｏ；３８．４ｓｒ／
１．Ｈ２３０４； ２７５．４ｔ／１）をそれぞれ３．
２４２／ｈｒ、０．８４２／ｈｒの速度で連続的に供給
した０反応温度は３０〜３２℃、スラリーのｐＨは６．
４〜６．６であった。排出スラリーを遠心分離機で固液
分離し、十分水洗後、Ｎ ａ２０ ； １ 、７２ ｖ
ｖ ｔ％、 Ａ Ｉ２２０３ ；２．５８ｗｔ％、５ｉ
０２ ；３９．３ｗｔ％。Al1203; 0.8 g/β) and aluminum sulfate aqueous solution to which sulfuric acid was added (AfO; 38.4sr/
1. H2304; 275.4t/1) respectively.
The reaction temperature was 30-32°C, and the pH of the slurry was 6.242/hr, and the slurry was continuously supplied at a rate of 0.842/hr.
It was 4-6.6. The discharged slurry was separated into solid and liquid using a centrifuge, and after thorough washing with water, Na20; 1,72 V
vt%, AI2203; 2.58wt%, 5i
02; 39.3wt%.
Ｉ２０ ； ５６−４ ｖｖ ｔ％の微粒状無定形アル
ミノ珪酸塩均一化合物を得た。該均一化合物２８４０ｇ
と１．３９ｗｔ％のＮａＯＨ水溶液５１６０ｇとを１０
１のオートクレーブに仕込み、１６０°Ｃで７２時間撹
拌下で結晶化した。生成物を固液分離後、水洗、乾燥し
て本触媒の基剤となるゼオライトＴＳＺ−８２１を得た
。化学分析の結果、その組成は無水ベースにおける酸化
物のモル比で表わして次の組成を有していた。A finely divided amorphous aluminosilicate homogeneous compound having a I20 of 56-4 vvt% was obtained. 2840g of the homogeneous compound
and 5160 g of 1.39 wt% NaOH aqueous solution at 10
The mixture was placed in an autoclave No. 1 and crystallized under stirring at 160°C for 72 hours. After solid-liquid separation of the product, it was washed with water and dried to obtain zeolite TSZ-821, which will serve as the base of the present catalyst. As a result of chemical analysis, its composition, expressed as molar ratio of oxides on an anhydrous basis, was as follows:
１．０５Ｎａ ０−ＡＩ２２０３−２３．３ＳｉＯ２
まな、その粉末Ｘ線図から求めたｄ値は基本的に第１表
に示した数値と同じであった。1.05Na 0-AI2203-23.3SiO2
The d value determined from the powder X-ray diagram was basically the same as the values shown in Table 1.
次にＴＳＺ−８２１を合成した時と同様の方法で、まず
５１０２及びＡρ２０３含有量の異なる微粒状無定形ア
ルミノ珪酸塩均一化合物を遺り、これを苛性ソーダ水溶
液中、撹拌下で加熱して結晶化し、本触媒の基剤となる
ゼオライト、ＴＳＺ−８４１，ＴＳＺ−８５１を得な。Next, using the same method as when TSZ-821 was synthesized, first leave a homogeneous fine-grain amorphous aluminosilicate compound with different contents of 5102 and Aρ203, and crystallize it by heating it in an aqueous solution of caustic soda with stirring. , to obtain zeolites TSZ-841 and TSZ-851, which are the base materials of the present catalyst.
その化学組成は無水ベースにおける酸化物のモル比で表
わして次の組成を有していた。Its chemical composition, expressed as the molar ratio of oxides on an anhydrous basis, had the following composition:
ＴＳＺ−８４１：１．４１Ｎａ ０−Ａｉ＋２０３−
４０、４ Ｓ ｉ Ｏ２
”Ｉ’５Ｚ−８５１： １．６５Ｎａ２０− ＡＲ２０
３・４９．８Ｓｉ０２
また、これらのゼオライトの粉末Ｘ線回折図から求めた
、ｄ値は基本的に第１表に示した数値と同じであった。TSZ-841: 1.41Na 0-Ai+203-
40, 4 S i O2 ”I'5Z-851: 1.65Na20- AR20
3.49.8Si02 Furthermore, the d values determined from the powder X-ray diffraction patterns of these zeolites were basically the same as the values shown in Table 1.
実施例２（銅含有ゼオライトの調製）
実施例１で得られたＴＳＺ−８２１、ＴＳＺ−８４１、
ＴＳＺ−８５１をそれぞれ１０ｇ採取して、ゼオライト
中のＡ１原子数に対し等しい銅原子数になるようにＯ，
１ｍｏρ／β酢酸鋼水溶酢酸入水溶液温にて撹拌し、２
．５％ＮＨ３水を添加し、スラリーｐＨ１０，５になる
ように調整した。Example 2 (Preparation of copper-containing zeolite) TSZ-821, TSZ-841 obtained in Example 1,
10g of each TSZ-851 was collected, and O,
Stir at 1moρ/β acetic acid steel aqueous solution temperature, 2
．． 5% NH3 water was added to adjust the slurry pH to 10.5.
その後、目的とするゼオライトの銅イオン交換率になる
まで、室温で撹拌した。固液分離後、十分水洗し１００
’Ｃで１０時間乾燥した。得られた銅含有ゼオライトを
それぞれＴＳＺ−８２１−Ａ。Thereafter, the mixture was stirred at room temperature until the desired copper ion exchange rate of the zeolite was reached. After solid-liquid separation, wash thoroughly with water
'C for 10 hours. The obtained copper-containing zeolites were respectively designated as TSZ-821-A.
ＴＳＺ−８２１−Ｂ、’ｒ’５Ｚ−８４１−Ｃ。TSZ-821-B, 'r'5Z-841-C.
ＴＳＺ−８５１−Ｄとする。化学分析によって求めた銅
含有ゼオライトの銅イオン交換率を第２表に示す、銅イ
オン交換率は、二価の銅として交換していると仮定して
求めた。It is designated as TSZ-851-D. The copper ion exchange rate of the copper-containing zeolite determined by chemical analysis is shown in Table 2. The copper ion exchange rate was determined on the assumption that the copper ion exchange rate was exchanged as divalent copper.
第 ２ 表
実施例３（銅含有ゼオライトの調製）
実施例１で得られたＴＳＺ−８２１を１０＋ｒ採取して
、ゼオライト中のＡｆｆｉ原子数に対し等しい銅原子数
になるように０．１ｍｏβ／β酢酸銅水溶液を入れ、室
温にて撹拌し、２．５％ＮＨ３水を添加し、スラリーｐ
Ｈ６，０になるように調整した。Table 2 Example 3 (Preparation of copper-containing zeolite) 10+r samples of TSZ-821 obtained in Example 1 were added to 0.1 moβ/β so that the number of copper atoms was equal to the number of Affi atoms in the zeolite. Add copper acetate aqueous solution, stir at room temperature, add 2.5% NH3 water, and slurry p
Adjusted to H6.0.
その後、室温にて１２時間撹拌しな。固液分雅後十分水
洗し、１００℃で１０時間乾燥した。得られた銅含有ゼ
オライトをＴＳＺ−８２１−Ｅとする。化学分析によっ
て求めた銅含有ゼオライトの銅イオン交換率を第３表に
示す。Then stir at room temperature for 12 hours. After solid-liquid separation, it was thoroughly washed with water and dried at 100°C for 10 hours. The obtained copper-containing zeolite is designated as TSZ-821-E. Table 3 shows the copper ion exchange rate of the copper-containing zeolite determined by chemical analysis.
第 ３ 表
実施例４（銅含有ゼオライトのＮＯ分解活性試験）実施
例２．３で調製した銅含有ゼオライトをプレス成形した
後、破砕して４２〜８０メツシユに整粒し、その１ｇを
常圧固定床流通式反応管に充填した。反応前に銅含有ゼ
オライトをヘリウムガス流通下で５°Ｃ／ｍｉｎの昇温
速度で５００℃まで昇温し、昇温後２時間その温度を維
持して前処理を行った。ＮＯを５０００ＰＰｍ含有する
ヘリウムガスを１５ｃｃ／ｍｉｎの流量で本触媒充填層
を通して反応させ、反応開始５０分後の各反応温度にお
けるＮＯ転化率を求めた。その結果を第４表に示す。Table 3 Example 4 (NO decomposition activity test of copper-containing zeolite) After the copper-containing zeolite prepared in Example 2.3 was press-molded, it was crushed and sized to 42 to 80 meshes, and 1 g of it was heated under normal pressure. It was filled into a fixed bed flow reaction tube. Before the reaction, the copper-containing zeolite was heated to 500° C. at a heating rate of 5° C./min under helium gas flow, and after heating, the temperature was maintained for 2 hours for pretreatment. Helium gas containing 5000 PPm of NO was reacted at a flow rate of 15 cc/min through this catalyst packed bed, and the NO conversion rate at each reaction temperature was determined 50 minutes after the start of the reaction. The results are shown in Table 4.
実施例５（銅含有ゼオライトの活性の安定性）銅含有ゼ
オライトＴＳＺ−８２１−Ｂ （銅イオン交換率１２３
％）を用いてＮｏ分解活性の持続安定性を試験した。実
施例４と同じ装置を用いて同様の方法で行い、反応温度
５００℃とした。転化率の経時変化を第１図に示す。Example 5 (Stability of activity of copper-containing zeolite) Copper-containing zeolite TSZ-821-B (copper ion exchange rate 123
%) was used to test the sustained stability of No decomposition activity. The reaction was carried out in the same manner as in Example 4 using the same apparatus, and the reaction temperature was 500°C. Figure 1 shows the change in conversion rate over time.
比較例１（比較ゼオライトの調製）
実施例１で得られた’Ｔ”５Ｉ−８２１、ＴＳＺ−８４
１、ＴＳＺ−８５１をそれぞれ１０ｇ採取して、ゼオラ
イト中のＡ！２原子数に対し等しい銅原子数になるよう
にＯｌｌ ｍ ｏ １ ／ （ｌ酢酸銅水溶：夜を入れ
、室温にて１２時間撹拌しな。固液弁Ｍ後、洗浄しこの
操作を３回繰り返した後、１００°Ｃで１０時間乾燥し
た。得られた比較ゼオライトをそれぞれＴＳＺ−８２１
−Ｆ、ＴＳＺ〜８４１−Ｇ。Comparative Example 1 (Preparation of Comparative Zeolite) 'T''5I-821 and TSZ-84 obtained in Example 1
1. Collect 10g of each TSZ-851, A! in zeolite! Oll m o 1 / (l copper acetate aqueous solution: Stir overnight at room temperature for 12 hours. After solid-liquid valve M, wash and repeat this operation 3 times. After repeating, it was dried at 100°C for 10 hours.The obtained comparative zeolites were each TSZ-821
-F, TSZ~841-G.
ＴＳＺ−８５１−Ｈとする。化学分析によって求めた比
較触媒の別イオン交換率を第５表に示す。It is called TSZ-851-H. Table 5 shows the different ion exchange rates of the comparative catalysts determined by chemical analysis.
第 ５ 表
比較例２（比較ゼオライトのＮｏ分解活性試験）比較例
１で調製した比較ゼオライトを、実施例４の方法に従っ
てＮＯ転化率を求めた。結果を第６表に示す。Table 5 Comparative Example 2 (No decomposition activity test of comparative zeolite) The NO conversion rate of the comparative zeolite prepared in Comparative Example 1 was determined according to the method of Example 4. The results are shown in Table 6.
第１図は、実施例５におけるＮＯ転化率の経時変化を示
す図である。FIG. 1 is a diagram showing the change in NO conversion rate over time in Example 5.
Claims (3)
折により求めた格子面間隔（ｄ値）を持ち、該ゼオライ
トの銅イオン交換を水溶性銅塩及びアンモニアを含む水
溶液で行うことを特徴とする銅含有ゼオライトの製造方
法。 第１表(1) The zeolite has a lattice spacing (d value) determined by powder X-ray diffraction as shown in Table 1 of this specification, and the zeolite is subjected to copper ion exchange with an aqueous solution containing a water-soluble copper salt and ammonia. A method for producing a copper-containing zeolite, characterized by: Table 1
比が２０〜２００である特許請求の範囲第１項記載の方
法。(2) The method according to claim 1, wherein the zeolite has a SiO_2/Al_2O_3 molar ratio of 20 to 200.
ーのｐＨが４〜１２である特許請求の範囲第１項または
第２項記載の方法。(3) The method according to claim 1 or 2, wherein the pH of the slurry containing zeolite during copper ion exchange is 4 to 12.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251616A JP2555637B2 (en) | 1987-10-07 | 1987-10-07 | Method for producing copper-containing zeolite |
| DE8888116539T DE3872478T2 (en) | 1987-10-07 | 1988-10-06 | METHOD FOR PRODUCING A ZEOLITH CONTAINING COPPER AND METHOD FOR ITS APPLICATION. |
| EP88116539A EP0311066B1 (en) | 1987-10-07 | 1988-10-06 | Process for the production of copper-containing zeolite and the method of application thereof |
| US07/255,018 US4999173A (en) | 1987-10-07 | 1988-10-07 | Removal of nitric oxides by copper-containing zeolites |
| US07/537,824 US5110777A (en) | 1987-10-07 | 1990-06-14 | Copper-containing zeolites and their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62251616A JP2555637B2 (en) | 1987-10-07 | 1987-10-07 | Method for producing copper-containing zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0196011A true JPH0196011A (en) | 1989-04-14 |
| JP2555637B2 JP2555637B2 (en) | 1996-11-20 |
Family
ID=17225473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62251616A Expired - Fee Related JP2555637B2 (en) | 1987-10-07 | 1987-10-07 | Method for producing copper-containing zeolite |
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| Country | Link |
|---|---|
| JP (1) | JP2555637B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0359302A (en) * | 1989-07-28 | 1991-03-14 | Takuma Co Ltd | Low-nox burner |
| WO1991006508A1 (en) * | 1989-10-31 | 1991-05-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for nitrogen oxide decomposition and method of cleaning nitrogen oxide-containing exhaust gas |
| JPH03127629A (en) * | 1989-10-12 | 1991-05-30 | Mitsubishi Heavy Ind Ltd | Direct catalytic cracking catalyst for nitrogen oxides |
| JP2009046372A (en) * | 2007-08-23 | 2009-03-05 | Tochigi Prefecture | Metal nanoparticle, zeolite with dispersed metal nanoparticle and method for producing zeolite with dispersed metal nanoparticle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| JPS5711926A (en) * | 1980-05-27 | 1982-01-21 | Mobil Oil Corp | Conversion of organic compound using periodic table ib group element denatured zeolite catalyst |
-
1987
- 1987-10-07 JP JP62251616A patent/JP2555637B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| JPS5711926A (en) * | 1980-05-27 | 1982-01-21 | Mobil Oil Corp | Conversion of organic compound using periodic table ib group element denatured zeolite catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0359302A (en) * | 1989-07-28 | 1991-03-14 | Takuma Co Ltd | Low-nox burner |
| JPH03127629A (en) * | 1989-10-12 | 1991-05-30 | Mitsubishi Heavy Ind Ltd | Direct catalytic cracking catalyst for nitrogen oxides |
| WO1991006508A1 (en) * | 1989-10-31 | 1991-05-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for nitrogen oxide decomposition and method of cleaning nitrogen oxide-containing exhaust gas |
| EP0451291A1 (en) * | 1989-10-31 | 1991-10-16 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for nitrogen oxide decomposition and method of cleaning nitrogen oxide-containing exhaust gas |
| EP0451291B1 (en) * | 1989-10-31 | 1995-06-28 | Mitsubishi Jukogyo Kabushiki Kaisha | Catalyst for nitrogen oxide decomposition and method of cleaning nitrogen oxide-containing exhaust gas |
| JP2009046372A (en) * | 2007-08-23 | 2009-03-05 | Tochigi Prefecture | Metal nanoparticle, zeolite with dispersed metal nanoparticle and method for producing zeolite with dispersed metal nanoparticle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2555637B2 (en) | 1996-11-20 |
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