JP2004049987A - Compression tableted molded object of chabazite crystalline silicoaluminophasphase molecular sieve, and molding method therefor - Google Patents
Compression tableted molded object of chabazite crystalline silicoaluminophasphase molecular sieve, and molding method therefor Download PDFInfo
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- JP2004049987A JP2004049987A JP2002208593A JP2002208593A JP2004049987A JP 2004049987 A JP2004049987 A JP 2004049987A JP 2002208593 A JP2002208593 A JP 2002208593A JP 2002208593 A JP2002208593 A JP 2002208593A JP 2004049987 A JP2004049987 A JP 2004049987A
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- molecular sieve
- shabasite
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- silicoaluminophosphate molecular
- crystalline silicoaluminophosphate
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000000465 moulding Methods 0.000 title claims abstract description 32
- 238000007906 compression Methods 0.000 title claims abstract description 29
- 230000006835 compression Effects 0.000 title claims abstract description 29
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 title abstract 3
- 229910052676 chabazite Inorganic materials 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 150000003956 methylamines Chemical class 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007891 compressed tablet Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007932 molded tablet Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 4
- 238000007323 disproportionation reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 47
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000011230 binding agent Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000002994 raw material Substances 0.000 description 9
- 239000003826 tablet Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004927 clay Chemical class 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229910052570 clay Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体、該成型体の製造方法、及び該成型体を触媒として用いたメチルアミン類の製造方法に関する。詳細には、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末を予備成型し、該予備成型体を破砕整粒した後に圧縮打錠するという、いわゆる圧縮打錠成型法を用いることで、工業用触媒として使用に耐えうる十分な機械的強度を有し、且つ高い触媒活性を有する圧縮成型体を製造する方法に関する。
【０００２】
【従来の技術】
シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブは、メチルアミン類の製造反応、メタノールからオレフィン類を製造する反応等の固体触媒として有用である。工業的にこれらの製造反応は、反応管内に固体触媒を充填または多段に配置し、原料を反応管内に流通して生成物を得るという固定床流通型の反応形式が用いられている。そのため、反応管内に充填または設置する触媒は、原料等の流通を妨げないような形と大きさを持ったものでなければならない。しかし、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブは、通常、平均粒径が０．１μｍから２００μｍ程度の微粉末であり、かさ密度も０．３から０．７ｇ／ｃｍ３程度と非常にかさ高いため、このままでは固定床流通型反応における実用触媒として用いることが出来ず、何らかの方法で数ミリ以上の形と大きさの触媒成型体とする必要がある。
【０００３】
粉末触媒を成型体にする場合、触媒使用時に破砕や粉化が生じないように、十分な触媒強度を有すること、また、成型体とすることで触媒活性の低下が起こらないことが特に重要であり、一般に、粉末の固体粉末触媒の成型は圧縮打錠成型法、造粒成型法、押し出し成型法等が用いられる。金属酸化物等からなる非晶質固体酸触媒類では、圧縮打錠成型法によって充分な機械強度と触媒性能を持った成型体が得られている。しかし、ゼオライト系モレキュラーシーブや非ゼオライト系アルミノリン酸塩モレキュラーシーブ類はそれ自身では成型性が無いため、圧縮打錠成型を行なうことができず、造粒成型法や押出し成型法により球状や円柱状の成型体にする方法がとられている。これら方法では、触媒粉末を結着するためにバインダーが必要で、バインダーとして合成雲母、アルミナ、シリカ、あるいはカオリン、タルク等の粘土化合物類が一般的に用いられる。しかし、これらバインダーの添加によりモレキュラシーブの有効な細孔が塞がれ触媒活性が低下したり、またアルミナや粘土化合物などはバインダー自身にも酸点が存在し、それが副反応の活性点となって反応選択率の低下を招く場合が多々ある。また、それらを防止する適当なバインダーを選定できたとしても、バインダーの使用量はモレキュラシーブ粉末に対して少なくとも１０重量％以上、通常１５から３０ｗｔ％が必要なため、得られる成型体中の有効な触媒量は添加したバインダー分だけ確実に低下する。したがって十分な反応を行なうためにより多くの触媒を要するという大きな欠点がある。
【０００４】
そこで、これら問題点を伴なうことなく数ミリ以上の形と大きさを持つゼオライト系モレキュラーシーブや非ゼオライト系アルミノリン酸塩モレキュラーシーブ類の成型体を製造する方法として、以下に示す方法が提案されてきた。
例えば、ＵＳＰ３，１１９，９５６号では、造粒成型法や押出し成型法におけるバインダー添加により生ずる触媒活性の低下を抑えるため、触媒中にバインダーを添加し成型した後、高温処理して該バインダーを除去する方法が提案されている。この方法では、ゼオライト粉末触媒にカオリンバインダーを添加して、押出し成型等で顆粒状、ペレット状とした後、焼成処理によりバインダーを除去してゼオライト成型体触媒を調製する。しかしながら、この方法は、目的とする成型体を得るまでに要する加工条件が複雑であり、焼成中に一部のバインダーが化学的に変化してしまったり、完全に除去されず焼成後も残存してしまったりするため、成型体の触媒性能が粉末の場合に比べ大きく低下してしまう問題点を有する。
【０００５】
ＥＰ０，０７６，０３４号では、反応性カオリン型粘土とＳｉＯ２、ＮａＯＨ等を混練し、回転成型して成型体とした後、水熱処理、焼成を行ってカオリンと反応させ、結晶質ゼオライトの成型体を得る方法が提案されている。さらに特公Ｈ０６−７６２０４では、アルミナまたはシリカアルミナの予備成型体と、五酸化リン、有機テンプレートを含む水溶液等を混合し水熱処理を行うことで、予備成型体自身中で非ゼオライト系アルミノリン酸塩モレキュラーシーブを合成し、予備成型体と同等の形と大きさを有する成型体を得る方法が提案されている。これらの方法は、極めて特殊かつ巧妙な方法であるが、製造条件が非常に複雑であり水熱処理時におけるモレキュラシーブ合成反応の安定性が通常の粉末原料を用いた場合に比べ乏しく、触媒として高度に構造が制御されたゼオライト系モレキュラシーブや非ゼオライト系アルミノリン酸塩モレキュラーシーブを安定して得ることは困難である。
【０００６】
【発明が解決しようとする課題】
本発明は、これら従来法の問題点を解決し、工業的触媒として使用に耐えうる十分な機械的強度を有し、かつ原料粉末の場合と同等な高い触媒活性を有するバインダーレスのシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ成型体を、効率的に製造する方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、バインダーレスのシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ成型体を製造する方法に関して、最も簡便かつ優れた方法は圧縮打錠成型法であることに着目し鋭意検討を重ねた。先述のように、金属酸化物等からなる非晶質固体酸触媒類では圧縮打錠成型方法が一般的な成型方法として用いられているが、ゼオライト系モレキュラーシーブや非ゼオライト系アルミノリン酸塩モレキュラーシーブ類を圧縮打錠成型する方法は従来不可能とされており、報告例もない。しかし本発明者らは、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの打錠成型方法について鋭意検討を重ねた結果、遂に当該モレキュラーシーブ原末中の含水率を１０ｗｔ％以下とし、滑剤と混合し、予備成型した後整粒し、それを圧縮打錠成型することで実用的な機械的強度を持つ成型体が得られることを見い出した。
さらに、本発明者らは圧縮打錠成型の条件を最適化し、該成型体密度を、０．９ から１．３（ｇ／ｃｍ３）、ＢＥＴ比表面積を４００（ｍ２／ｇ）以上の範囲に保った場合、前駆体である粉末と比べ、活性低下の殆どない優れた成型体が得られることを見い出し、本発明を完成するに至った。ここで”含水率”と”成型体密度”は以下のように定義される。
含水率（ｗｔ％）＝吸着した水の重量／完全に乾燥したモレキュラシーブ重量×１００
成型体密度（ｇ／ｃｍ３）＝触媒成型体１試料あたりの重量（ｇ）／触媒成型体１試料あたりの体積（ｃｍ３）
【０００８】
即ち、本発明は、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体、該成型体の製造方法、及び該成型体を触媒として用いたメチルアミン類の製造方法に関するものであり、
（１）含水率が１０ｗｔ％ 以下、平均粒子径が２００μｍ以下のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末を圧縮打錠成型し、得られる成型体密度が０．９ から１．３ｇ／ｃｍ３の範囲であり、比表面積が４００ ｍ２／ｇ以上であることを特徴とする、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体、
（２）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＳＡＰＯ−３４である、（１）記載の圧縮打錠成型体、
（３）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＭｇ、Ｃｓ、Ｓｒ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｙ 、Ｚｒ、Ｒｕ、Ｐｄ及びＰｔの中から選択された１種類以上の金属を含有する、（１）記載の圧縮打錠成型体、
（４）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＭｇ、Ｃｓ、Ｓｒ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｙ 、Ｚｒ、Ｒｕ、Ｐｄ及びＰｔの中から選択された１種類以上の金属で置換したものである、（１）記載の圧縮打錠成型体、
（５）含水率が１０ｗｔ％ 以下、平均粒子径が２００μｍ以下のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末に０．１から５ｗｔ％の滑剤を加え混合する工程、その混合物を０．５から５ＭＰａの範囲の圧力で予備成型し、その予備成型品を３０メッシュ以下の粒子に整粒する工程、そして、その整粒品を２０から２００ＭＰａの圧力で圧縮打錠成型する工程を経て、（１）記載の圧縮打錠成型体を得る、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末の成型方法、
（６）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＳＡＰＯ−３４である、（５）記載の成型方法、
（７）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＭｇ、Ｃｓ、Ｓｒ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｙ 、Ｚｒ、Ｒｕ、Ｐｄ及びＰｔの中から選択された１種類以上の金属を含有する、（５）記載の成型方法、
（８）シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブがＭｇ、Ｃｓ、Ｓｒ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｙ 、Ｚｒ、Ｒｕ、Ｐｄ及びＰｔの中から選択された１種類以上の金属で置換したものである、（５）記載の成型方法、
（９）（１）から（４）に記載のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ打錠成型体の存在下、メタノールとアンモニアを反応させることを特徴とするメチルアミン類の製造法、
（１０）（１）から（４）に記載のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ打錠成型体の存在下、メタノールとモノメチルアミンを反応させることを特徴とするメチルアミン類の製造方法、
（１１）（１）から（４）に記載のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ打錠成型体の存在下、モノメチルアミンの不均化反応を行なうことを特徴とするメチルアミン類の製造方法、
からなる。
【０００９】
【発明の実施の形態】
本発明で使用するシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブはＳＡＰＯ−３４、ＳＡＰＯ−４４、ＳＡＰＯ−４７の３種類が知られており、これらはケイ素化合物、アルミニウム化合物、リン化合物、有機テンプレート剤及び水からなる混合物を水熱処理することで合成される。そして水熱処理により得られる反応物から結晶成分を分離、洗浄、乾燥し、最終的に分子状酸素の存在下、３００℃以上で焼成処理を行なうことにより当該粉末が得られる（ＵＳＰ４，４４０，８７１号）。
本発明に使用する前記シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブには、Ｍｇ、Ｃｓ、Ｓｒ、Ｔｉ、Ｃｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｙ 、Ｚｒ、Ｒｕ、Ｐｄ及びＰｔの中から選択された１種類以上の金属を含有、もしくは該金属で置換したものを用いても良い。これら金属は目的の反応における触媒性能（反応活性、目的反応生成物の選択率、触媒寿命）の改善のために添加されるもので、極微量の添加でもその効果を発揮し、バインダーとしてはほとんど作用しない。これら金属を含有したシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの調製法は、該モレキュラシーブと該金属化合物を乾式法、または湿式法で混合する方法、水熱合成時に該金属化合物を添加しそれら金属をモレキュラシーブ中に含有させる方法等があり、特に制限されない。
以上のように製造したシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブは平均粒子径が２００μｍ以下、通常は１０μｍ程度の粉末となる場合がほとんどである。
【００１０】
次に、このようにして得られたシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末の含水率が１０ｗｔ％以下、好ましくは３ｗｔ％以下となるようにする。本発明者らは圧縮打錠成型を行なう前に、モレキュラシーブ粉末に吸着した水分を上記の量に制御することが極めて重要であり、該モレキュラーシーブ粉末の含水率が１０ｗｔ％以下のものを、続く圧縮打錠成型に用いることで実用的な強度を持つ打錠成型体が得られることを見出した。含水量１０ｗｔ％を超えるものを圧縮打錠成型した場合は、成型体の強度は著しく低いものとなってしまう。一方、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブは極めて吸湿性が高く、大気雰囲気下、室温で放置しておくと、容易にその温度、圧力における飽和吸着量まで水分を吸着してしまう。通常、該モレキュラシーブの室温・常圧下における飽和水分吸着率は１０から３５ｗｔ％にも達する。もし、該モレキュラシーブが１０ｗｔ％以上の含水率であったならば、乾燥処理により吸着した水分の除去を行なう必要がある。吸着した水分はそのほとんどが物理的吸着水であるため、一般的な乾燥機を用い、１００℃から１５０℃程度の温度で該モレキュラシーブ粉末を処理すれば、容易に水分を除去することができる。また、先述のとおり、該モレキュラシーブ粉末は製造の最終工程において、分子状酸素の存在下、３００℃以上の温度で焼成処理を行なうことが一般的である。このような焼成処理直後の該モレキュラシーブは実質的に含水率がゼロであり、この粉末をすぐに圧縮打錠工程に使用するか、もしくはこの粉末を水分の無い状態で密閉保管すれば該モレキュラシーブの吸湿を防ぐことができ、この乾燥処理を省くことができる。
【００１１】
次いで、このようにして得られた含水率が１０ｗｔ％以下、平均粒子径が２００μｍ以下のシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末を圧縮打錠成型に供する。当該モレキュラシーブは非常に平均粒子径が小さくかさ高い。また成型ダイからの離型性が悪いため、そのまま圧縮打錠成型機にて打錠成型することができず、以下の３つの工程が必要となる。
（１）滑剤とシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末の混合工程
（２）予備成型、整粒工程
（３）圧縮打錠成型工程
以下、工程別に実施法の詳細を記述する。
【００１２】
（１）滑剤とシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末の混合工程
打錠成型では、最終的に成型ダイから成型体を取り出すことが必要になるが、該モレキュラシ−ブは成型ダイからの離型性が悪いため、離型剤として滑剤を添加することが必要である。滑剤として、例えばステアリン酸の無機塩類や人造黒鉛等が用いられる。滑剤の添加量は当該モレキュラーシーブに対し０．１ から５ ｗｔ％ が適当である。これら滑剤を該モレキュラーシーブと均一に混合し、打錠成型用の原料粉末を調製する。
【００１３】
（２） 予備成型、整粒工程
先述の方法で製造したシャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブ粉末は粒径が２００μｍ以下であり、かさ密度は０．３から０．７ｇ／ｃｍ３程度と非常にかさ高い。このため、このまま圧縮打錠成型を行なっても十分な強度と適当な成型体密度を持つ成型体を得ることができない。そこで予備成型と整粒操作を行ない、打錠成型に適したかさ密度と粒径を有する予備成型体を調製することが必要となる。予備成型はロールコンパクティング型、またはロールプリケッテイング型圧縮成型機等を用い０．５から５ＭＰａの圧力で行なう。ロールコンパクテング型成型機を用いた場合、シート状の予備成型体が得られ、これを更に破砕、整粒する。整粒後の予備成型体粒度は打錠機金型への充填性から３０メッシュ以下とするが、特に２０メッシュ以下に調整するのが好ましい。通常、ロールコンパクティング型成型機には粉砕機および整粒用スクリーンが一体となっており、一連の上記操作は容易に行なうことができる。
【００１４】
（３）圧縮打錠成型工程
このようにして得られた予備成型体を回転型、または単発型圧縮打錠成型機を用い打錠成型する。工業的には多量の成型体を効率的に製造できる回転型圧縮打錠成型機が適している。これら打錠成型機のダイの中に先に調製した予備成型体を充填し、上下のパンチで圧縮打錠成型する。打錠圧力は２０から２００ＭＰａ以下、好ましくは４０から１００ＭＰａ の範囲で行なう。打錠成型体の形状は直径、長さとも２から１０ｍｍの円柱タブレットのものが一般的であり、打錠体を充填する反応管のサイズ、目的とする反応の種類、成型体の生産性等を十分に勘案し、最も適した打錠成型体のサイズを選択すればよい。
【００１５】
本発明者らは、最終的に得られた成型体密度を０．９ から１．３（ｇ／ｃｍ３）とし、成型体のＢＥＴ 比表面積を４００ｍ２／ｇ以上とすることが、この成型体を反応触媒として用いた場合の触媒活性の低下を引き起こさない点から極めて重要であることを見出した。成型体密度がこの範囲よりはずれると、また成型体のＢＥＴ表面積が４００ｍ２／ｇ以下となると、得られる成型体の触媒活性は著しく低下する。成型体密度は予備成型体のかさ密度、ダイへの充填量、打錠成型圧力等に依存し、これらを調整、最適化することで成型体密度を０．９ から１．３（ｇ／ｃｍ３）に制御することができる。またＢＥＴ表面積は先の該モレキュラシーブ中の含水率や予備成型、打錠圧力に依存し、これらを制御することでＢＥＴ表面積が４００ｍ２／ｇ以上に保つことができる。
【００１６】
以上の打錠成型操作は、該モレキュラーシーブができるだけ吸湿しないよう、低湿度下ですばやく行なう必要がある。可能であれば、各装置を乾燥窒素雰囲気下とし各操作を行なうことが好ましい。
【００１７】
このようにして、工業用触媒として、使用に耐えうる十分な機械的強度を有し、かつ原料粉末の場合と同等な高い触媒活性を有するバインダーレスのシャバサイト型結晶質アルミノリン酸塩モレキュラーシーブ成型体を製造することができる。本発明の方法により得られた該打錠成型体は、工業的には固定床流通式反応器に充填しメタノールとアンモニア、および／またはメタノールとモノメチルアミンを原料としたメチルアミン合成反応、および／またはモノメチルアミンの不均化反応によるメチルアミン合成反応の触媒として用いることができ、本発明の工業的な意義は極めて大きい。
【００１８】
次に本発明の具体的態様を実施例、及び比較例をもって更に詳細に説明する。尚、原料粉体、成型体の各物性値は以下の方法で測定した。
・平均粒径：湿式レーザー回折型粒度分布計（ＨＯＲＩＢＡ ＬＡ−５００）で測定した。
・成型体密度：得られた成型体５０個（ｎ＝５０）をおのおの精密重量測定し、その平均値より算出した。
・圧壊強度：破壊強度測定器（大倉理研 ＤＨＴ−２００）で測定した（ｎ＝５０）。
・粉化率：カゴ試験型粉化率測定装置（千穂田精衡株式会社）で測定した（直径１００ｍｍ 、高さ９０ｍｍの１４メッシュＳＵＳ 製の円筒状スクリーン内に１０ｇの成型体を入れ、円筒を１６０ｒｐｍで１０分間回転させた後、粉化率を測定した）。
・ＢＥＴ比表面積：窒素吸着／脱着等温線測定装置（ＱＡＮＴＡＣＨＲＯＭＥ社 Ａｕｔｏｓｏｒｂ−６）を用い、Ｍｕｌｔｉ−ｐｏｉｎｔ法で測定した。
また、本実施例、比較例では得られた成型体をメタノールとアンモニアからのメチルアミン合成反応触媒として用い、触媒性能を評価した。評価方法は、触媒 ２．５ｇをステンレス製円筒状反応管に充填し、アンモニアとメタノ−ルの１：１重量混合物を ５．１９ｇ／ｈの速度で供給して、反応圧力２ＭＰａ、温度３２０ ℃条件下、メチルアミン合成反応を行った。尚、時空間速度 （ＧＨＳＶ）は約９００から１２００ｈ−１である。原料流通後１２時間後の反応生成物を水に捕集し、ガスクロマトグラフィーにより反応成績を調べた。生成物のメチルアミンはモノメチルアミン、ジメチルアミン、トリメチルアミンの三種があり、工業的にはジメチルアミンの選択率が高い触媒が望まれている。尚、記載する略語は以下の通りである
・モノメチルアミン：ｍＭＡ
・ジメチルアミン ：ｄＭＡ
・トリメチルアミン：ｔＭＡ
【００１９】
【実施例】
実施例１
シャバサイト型結晶質アルミノリン酸塩モレキュラーシーブとして、水熱処理時にＴｉを添加し、テンプレート剤としてテトラエチルアンモニウムヒドロキシドを用い製造したＴｉＳＡＰＯ−３４粉末を１００ ℃で１６時間乾燥して含水率を１．１ｗｔ％とした。この粉末の平均粒径は２．１μｍであった。ＴｉＳＡＰＯ−３４の乾燥重量に対して１．５ｗｔ％の人造黒鉛を添加し、混合した。次に、ロ−ラーコンパクティング型圧縮成型機（フロイント産業社製）を用いて１．５ＭＰａの圧力下、予備成型処理を施し、得られた予備成型体を破砕した後１６メッシュに整粒した。これを、回転型圧縮打錠成型機（菊水製作所製）を用いて８０ＭＰａの圧力下で打錠成型し、直径３．２ｍｍ×高さ３．２ｍｍの円柱タブレットの成型体を得た。得られた成型体の物性値は以下のとおりであった。
成型体密度：１．０９（ｇ／ｃｍ３）
圧壊強度：１４．８（ＭＰａ）
粉化率：２．５（ｗｔ％）
ＢＥＴ 比表面積：４７０（ｍ２／ｇ）
尚、圧壊強度と粉化率は工業用触媒として使用に耐えうる機械的強度を有するか否かの指標となり、強度５ＭＰａ以上、粉化率５ｗｔ％以下の値であれば実用触媒として十分な強度である。本実施例で製造した成型体の強度はいずれもこれらの値を満足しており、工業用触媒として用いる上で何ら問題ない水準であった。また、この成型体のメチルアミン合成反応成績は以下の通りであり、触媒活性（メタノール転化率）、ｄＭＡの選択率はともに高いものであった。
メタノール転化率：９８．２％
アミン選択率：ｍＭＡ／ｄＭＡ／ｔＭＡ＝３２ ／６４／４（ｗｔ％）
以上の結果を表１にまとめた。
【表１】
比較例１
実施例１で製造したＴｉＳＡＰＯ−３４を粉末のまま用いて、実施例１と同様にメチルアミン合成反応を行なった。結果を表１に示す。反応成績は実施例１の場合とほぼ同等であり、実施例１の成型体は成型前のＴｉＳＡＰＯ−３４と比べ、活性低下や選択率の変化は起きていないことが明らかである。尚、このような微細な粉末触媒を用いたメチルアミン合成反応は実験室的に実施することは可能であるが、工業的に大きな固定床流通反応管で実施することは不可能である。
【００２１】
実施例２、３、比較例２、（含水率の影響）
ＴｉＳＡＰＯ−３４粉末の含水率を４．８ｗｔ％（実施例２）、１０．０ｗｔ％（実施例３）、２５．６ｗｔ％（比較例２）のものを用いた以外は、実施例１と同様な操作で成型体を得て、メチルアミン合成反応活性を調べた。結果を表１に示す。成型体密度はいずれも１．０９〜１．１０ｇ／ｃｍ３）であり、実施例１とほぼ同等の成型体密度であった。これらの結果より、ＴｉＳＡＰＯ−３４粉末の含水率が高くなるに従って、顕著に成型体の圧壊強度が低下し、粉化率が高くなってしまう現象が観察され、ＴｉＳＡＰＯ−３４粉末の含水率が１０ｗｔ％より多くなると、触媒としての要求強度から大きく外れた実用には耐えられない水準の成型体となった。またＢＥＴ比表面積は含水率が多くなるに従って、低下する傾向がある。
比較例２において、メチルアミン合成反応での触媒活性（メタノール添加率）は、８７．９％であり、他のものと比較して低かった。またＢＥＴ比表面積も３８９（ｍ２／ｇ）と小さいものであった。ｄＭＡの選択率はいずれも実施例１と同様に高いものであった。
【００２２】
実施例４、５、比較例３、（成型体密度の影響）
回転式圧縮打錠成機の成型圧力を４０ＭＰａ（実施例４）、１００ＭＰａ（実施例５）、１５０ＭＰａ（比較例３）とした以外は、実施例１と同様な操作で成型体を得て、メチルアミン合成反応活性を調べた。結果を表２に示す。この操作の結果得られた触媒の成型体密度は実施例４で１．００ｇ／ｃｍ３、実施例５で１．３０ｇ／ｃｍ３、比較例３で１．３５ｇ／ｃｍ３であった。成型体強度はいずれも工業用触媒として用いる上で何ら問題ない水準であったが、比較例３では、ＢＥＴ表面積が低下し、メチルアミン合成反応での触媒活性（メタノール添加率）は、他のものと比較して低かった。
【表２】
実施例６〜９、（モレキュラシーブの影響）
水熱合成時にＴｉを添加しない系で合成（実施例６）、水熱合成時にＴｉを添加せずテンプレート剤としてシクロヘキシルアミンを用いた系で合成（実施例７）、水熱合成時にＴｉを添加せずテンプレート剤としてｓｅｃ−ブチルアミンを用いた系で合成（実施例８）、水熱合成時のＴｉのかわりにＺｒを添加した系で合成（実施例９）した以外は実施例１と同様な操作で成型体を得、メチルアミン合成反応活性を調べた。結果を表３に示す。各実施例で合成されたＳＡＰＯはそれぞれ、ＳＡＰＯ−３４（実施例６）、ＳＡＰＯ−４４（実施例７）、ＳＡＰＯ−４７（実施例８）、ＺｒＳＡＰＯ−３４（実施例９）であり、合成段階での各ＳＡＰＯの平均粒子径はすべて４μｍ以下であった。得られた成型体の密度は１．０８から１．１ｇ／ｃｍ３であり、成型体強度はいずれも工業的触媒として用いる上で何ら問題ない水準であった。また成型体のＢＥＴ表面積はすべて４００ｍ２／ｇ以上であり、メチルアミン合成反応での触媒活性（メタノール添加率）、ｄＭＡ選択率ともに高いものであった。
【表３】
比較例４〜８、（押出し成型法との比較）
実施例１と同様な方法で製造したＴｉＳＡＰＯ−３４粉末１０ｇに任意の種類と量のバインダーを添加し、水１０ｇを用いて混練した。この混錬物を、注射筒を用いて押出した後、１１０℃で４時間乾燥し、直径３．２ｍｍ×高さ３．２ｍｍ の成型体にそろえた。この成型体を空気中、６００℃で４時間焼成し、押出し成型品触媒を得、実施例１と同様な方法で成型体強度を測定したのち、メチルアミン合成反応活性を調べた。各比較例で使用したバインダーの種類と量は以下の通りである。
比較例４：膨潤性合成雲母（ＭＥ−１００コープケミカル社製）をＴｉＳＡＰＯ−３４粉末に対して１５ｗｔ％添加
比較例５：膨潤性合成雲母（ＭＥ−１００コープケミカル社製）をＴｉＳＡＰＯ−３４粉末に対して２５ｗｔ％添加
比較例６：カオリンをＴｉＳＡＰＯ−３４粉末に対して１５ｗｔ％添加
比較例７：アルミナをＴｉＳＡＰＯ−３４粉末に対して１５ｗｔ％添加
比較例８：アタパルジャイトをＴｉＳＡＰＯ−３４粉末に対して１５ｗｔ％添加
結果を表４に示す。この操作の結果得られた触媒の成型体強度はいずれも工業用触媒として用いる上で問題ない水準であったが、実施例１の打錠成型体に比較し弱いものであった。尚、比較例４，５よりバインダーの添加量を増やすことで成型体強度は改善される。メチルアミン合成反応での触媒活性（メタノール添加率）は、いずれも実施例１の打錠成型体に比べかなり低いものであった。これは、成型体中のＴｉＳＡＰＯ−３４触媒の絶対量が添加したバインダーにより少なくなっているためである。またカオリン、アルミナ、アタパルジャイトを用いた比較例６、７、８ではｄＭＡの選択性が低い。これは添加したバインダー自身の酸点により、アミン類の不均化反応が進行しｄＭＡの選択性が下がったものと考えられる。
【表４】
【発明の効果】
本発明の提供する方法に基づく、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体はバインダーレスであるため、バインダーの添加が必要な押出し成型品にみられた活性低下や目的反応物の選択率の低下が殆ど無く、また工業的な使用に耐えうる十分な成型体強度を有する。この様な成型体を製造する方法は、シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブを対象とする触媒成型の分野において極めて有用であり、本発明の意義は大きい。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a compression-molded tablet of shabasite-type crystalline silicoaluminophosphate molecular sieve, a method for producing the molded article, and a method for producing methylamines using the molded article as a catalyst. In detail, the so-called compression tableting method, in which shabasite-type crystalline silicoaluminophosphate molecular sieve powder is preformed, the preformed body is crushed and sized, and then compressed and compressed, is used. The present invention relates to a method for producing a compression-molded article having sufficient mechanical strength to withstand use as a catalyst for use and having high catalytic activity.
[0002]
[Prior art]
Shabasite-type crystalline silicoaluminophosphate molecular sieve is useful as a solid catalyst for a reaction for producing methylamines and a reaction for producing olefins from methanol. Industrially, these production reactions employ a fixed bed flow type reaction system in which a solid catalyst is filled in a reaction tube or arranged in multiple stages, and a raw material is passed through the reaction tube to obtain a product. Therefore, the catalyst to be filled or placed in the reaction tube must have a shape and a size that do not hinder the flow of the raw materials and the like. However, the shabasite-type crystalline silicoaluminophosphate molecular sieve is usually a fine powder having an average particle size of about 0.1 μm to 200 μm and a bulk density of 0.3 to 0.7 g / cm.3Since the catalyst is very bulky, it cannot be used as it is as a practical catalyst in a fixed bed flow type reaction, and it is necessary to form a molded catalyst having a shape and size of several millimeters or more by some method.
[0003]
When a powder catalyst is formed into a molded body, it is particularly important that the catalyst has sufficient catalyst strength so that crushing or pulverization does not occur when the catalyst is used, and that the molded body does not cause a decrease in catalytic activity. In general, the compression of a powdered solid powder catalyst is performed by a compression tableting method, a granulation method, an extrusion method, or the like. In the case of amorphous solid acid catalysts composed of a metal oxide or the like, a molded article having sufficient mechanical strength and catalytic performance has been obtained by compression tableting. However, zeolite-based molecular sieves and non-zeolitic aluminophosphate molecular sieves have no moldability by themselves, and therefore cannot be subjected to compression tableting, and can be formed into spherical or cylindrical shapes by granulation molding or extrusion molding. The method of making it into a molded body is taken. In these methods, a binder is required to bind the catalyst powder, and synthetic mica, alumina, silica, or clay compounds such as kaolin and talc are generally used as the binder. However, the addition of these binders blocks the effective pores of the molecular sieve and reduces the catalytic activity.Also, alumina and clay compounds have acid sites in the binder itself, which become active sites for side reactions. In many cases, the reaction selectivity decreases. Even if an appropriate binder to prevent such a problem can be selected, the amount of the binder to be used should be at least 10% by weight or more based on the molecular sieve powder, usually 15 to 30% by weight. The amount of catalyst is surely reduced by the amount of the added binder. Therefore, there is a significant disadvantage that more catalyst is required to perform a sufficient reaction.
[0004]
Therefore, the following method is proposed as a method for producing a molded body of zeolite-based molecular sieves and non-zeolitic aluminophosphate molecular sieves having a shape and size of several millimeters or more without these problems. It has been.
For example, in US Pat. No. 3,119,956, in order to suppress a decrease in catalytic activity caused by addition of a binder in a granulation molding method or an extrusion molding method, a binder is added to a catalyst, molded, and then subjected to a high temperature treatment to remove the binder. A way to do that has been proposed. In this method, a kaolin binder is added to a zeolite powder catalyst, and granulated or pelletized by extrusion or the like, and then the binder is removed by a calcination treatment to prepare a zeolite molded catalyst. However, in this method, the processing conditions required to obtain a target molded body are complicated, and some binders are chemically changed during firing, or are not completely removed and remain after firing. Therefore, there is a problem that the catalyst performance of the molded body is greatly reduced as compared with the case of powder.
[0005]
In EP 0,076,034, reactive kaolin-type clay and SiO2, NaOH, and the like, are kneaded and rotationally molded to form a molded body, and then subjected to hydrothermal treatment and firing to react with kaolin to obtain a molded body of crystalline zeolite. Further, in Japanese Patent Publication H06-76204, a non-zeolitic aluminophosphate is mixed in the pre-formed body itself by mixing a pre-formed body of alumina or silica-alumina with an aqueous solution containing phosphorus pentoxide and an organic template and performing hydrothermal treatment. There has been proposed a method of synthesizing a molecular sieve to obtain a molded body having the same shape and size as a preformed body. These methods are very special and subtle, but the production conditions are very complicated and the stability of the molecular sieve synthesis reaction during hydrothermal treatment is poorer than when using ordinary powdered raw materials. It is difficult to stably obtain a zeolite-based molecular sieve having a controlled structure or a non-zeolitic aluminophosphate molecular sieve.
[0006]
[Problems to be solved by the invention]
The present invention solves the problems of these conventional methods, has sufficient mechanical strength to withstand use as an industrial catalyst, and has a binderless shabasite type having high catalytic activity equivalent to that of raw material powder. An object of the present invention is to provide a method for efficiently producing a crystalline silicoaluminophosphate molecular sieve molding.
[0007]
[Means for Solving the Problems]
The present inventors have made intensive studies on the method of producing a binderless shabasite-type crystalline silicoaluminophosphate molecular sieve molded body, focusing on that the simplest and superior method is a compression tableting method. Stacked. As described above, the compression tableting method is used as a general molding method for amorphous solid acid catalysts composed of metal oxides and the like. However, zeolite-based molecular sieves and non-zeolitic aluminophosphate molecular sieves are used. It has heretofore been impossible to perform compression tableting on such products, and there have been no reports. However, the inventors of the present invention have conducted intensive studies on a tableting method of shabasite-type crystalline silicoaluminophosphate molecular sieve, and as a result, have finally reduced the water content in the molecular sieve bulk powder to 10 wt% or less, and It has been found that by mixing, pre-molding, sizing, and compressing and compression molding, a molded article having practical mechanical strength can be obtained.
Furthermore, the present inventors have optimized the conditions for compression tableting, and have set the density of the molded product from 0.9 ° to 1.3 (g / cm).3), BET specific surface area of 400 (m2/ G), it was found that an excellent molded body with almost no decrease in activity was obtained as compared with the powder as a precursor, and the present invention was completed. Here, "moisture content" and "mold density" are defined as follows.
Water content (wt%) = weight of adsorbed water / weight of completely dried molecular sieve × 100
Molding density (g / cm3) = Weight (g) per sample of molded catalyst / volume (cm) per sample of molded catalyst3)
[0008]
That is, the present invention relates to a compression-molded tablet of shabasite-type crystalline silicoaluminophosphate molecular sieve, a method for producing the molded article, and a method for producing methylamines using the molded article as a catalyst. Yes,
(1) Shabazite-type crystalline silicoaluminophosphate molecular sieve powder having a water content of 10% by weight or less and an average particle diameter of 200 μm or less is compression-compressed, and the density of the obtained molded body is 0.9 to 1.3 g. / Cm3And the specific surface area is 400 m2/ G or more, characterized in that it is a compression-molded tablet of shabasite-type crystalline silicoaluminophosphate molecular sieve,
(2) The compressed tablet molded product according to (1), wherein the shabasite-type crystalline silicoaluminophosphate molecular sieve is SAPO-34.
(3) Shabasite-type crystalline silicoaluminophosphate molecular sieve 1 selected from Mg, Cs, Sr, Ti, Cr, Fe, Co, Cu, Zn, Y, Zr, Ru, Pd and Pt The compressed tablet molded product according to (1), containing at least one kind of metal,
(4) Shabasite-type crystalline silicoaluminophosphate molecular sieve is selected from Mg, Cs, Sr, Ti, Cr, Fe, Co, Cu, Zn, Y, Zr, Ru, Pd and Pt. (1) The compressed tablet molded product according to (1), which is substituted with at least one kind of metal.
(5) A step of adding 0.1 to 5% by weight of a lubricant to a shabasite-type crystalline silicoaluminophosphate molecular sieve powder having a water content of 10% by weight or less and an average particle diameter of 200 μm or less, and mixing the mixture. Preforming at a pressure in the range of 5 to 5 MPa, a step of sizing the preformed article to particles of 30 mesh or less, and a step of compression tableting the sized article at a pressure of 20 to 200 MPa. (1) A method for molding a shabazite-type crystalline silicoaluminophosphate molecular sieve powder, which obtains the compressed tablet molded article according to (1),
(6) The molding method according to (5), wherein the shabasite-type crystalline silicoaluminophosphate molecular sieve is SAPO-34.
(7) Shabasite type crystalline silicoaluminophosphate molecular sieve 1 selected from Mg, Cs, Sr, Ti, Cr, Fe, Co, Cu, Zn, Y, Zr, Ru, Pd and Pt The molding method according to (5), wherein the molding method contains more than one kind of metal,
(8) Shabasite-type crystalline silicoaluminophosphate molecular sieve 1 selected from Mg, Cs, Sr, Ti, Cr, Fe, Co, Cu, Zn, Y, Zr, Ru, Pd and Pt The molding method according to (5), wherein the metal is substituted with at least one kind of metal.
(9) A method for producing methylamines, comprising reacting methanol and ammonia in the presence of the shabasite-type crystalline silicoaluminophosphate molecular sieve tableting product according to (1) to (4). ,
(10) Production of methylamines characterized by reacting methanol and monomethylamine in the presence of the shabasite-type crystalline silicoaluminophosphate molecular sieve tableting product according to (1) to (4). Method,
(11) Methylamines characterized by performing a disproportionation reaction of monomethylamine in the presence of a shabasite-type crystalline silicoaluminophosphate molecular sieve tableting product according to (1) to (4). Manufacturing method,
Consists of
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Three types of SAPA-34, SAPO-44, and SAPO-47 are known as the shabasite-type crystalline silicoaluminophosphate molecular sieve used in the present invention, and these are silicon compounds, aluminum compounds, phosphorus compounds, and organic compounds. It is synthesized by subjecting a mixture consisting of the template agent and water to hydrothermal treatment. Then, the crystal component is separated from the reaction product obtained by the hydrothermal treatment, washed, dried, and finally subjected to a calcination treatment at 300 ° C. or more in the presence of molecular oxygen to obtain the powder (US Pat. No. 4,440,871). issue).
The chabazite-type crystalline silicoaluminophosphate molecular sieve used in the present invention includes Mg, Cs, Sr, Ti, Cr, Fe, Co, Cu, Zn, Y, Zr, Ru, Pd and Pt. Alternatively, a material containing one or more metals selected from the group consisting of or substituted with the metal may be used. These metals are added for the purpose of improving the catalytic performance (reaction activity, selectivity of the target reaction product, and catalyst life) in the target reaction. Does not work. The method of preparing the shabasite-type crystalline silicoaluminophosphate molecular sieve containing these metals includes a method of mixing the molecular sieve and the metal compound by a dry method or a wet method, and adding the metal compound during hydrothermal synthesis. There is a method of including those metals in molecular sieves, and the like is not particularly limited.
The shabasite-type crystalline silicoaluminophosphate molecular sieve produced as described above often becomes a powder having an average particle diameter of 200 μm or less, usually about 10 μm.
[0010]
Next, the water content of the thus obtained shabasite-type crystalline silicoaluminophosphate molecular sieve powder is adjusted to 10% by weight or less, preferably 3% by weight or less. It is very important for the present inventors to control the amount of water adsorbed on the molecular sieve powder to the above-mentioned amount before performing compression tableting, and the molecular sieve powder having a water content of 10 wt% or less, It has been found that a tableting product having practical strength can be obtained by using it for compression tableting. When a tablet having a water content exceeding 10% by weight is subjected to compression tableting, the strength of the molded article becomes extremely low. On the other hand, the shabasite-type crystalline silicoaluminophosphate molecular sieve has extremely high hygroscopicity, and when left at room temperature under an air atmosphere, easily absorbs moisture up to the saturated adsorption amount at the temperature and pressure. . Usually, the saturated water adsorption of the molecular sieve at room temperature and normal pressure reaches 10 to 35 wt%. If the molecular sieve has a water content of 10% by weight or more, it is necessary to remove moisture adsorbed by the drying treatment. Since most of the adsorbed water is physically adsorbed water, the water can be easily removed by treating the molecular sieve powder with a general dryer at a temperature of about 100 ° C. to 150 ° C. In addition, as described above, the molecular sieve powder is generally subjected to a baking treatment at a temperature of 300 ° C. or more in the presence of molecular oxygen in the final step of the production. The molecular sieve immediately after such a baking treatment has substantially zero moisture content, and if the powder is used immediately in the compression tableting process, or if the powder is tightly stored in the absence of moisture, the molecular sieve is Moisture absorption can be prevented, and this drying treatment can be omitted.
[0011]
Next, the thus obtained shabasite-type crystalline silicoaluminophosphate molecular sieve powder having a water content of 10 wt% or less and an average particle diameter of 200 μm or less is subjected to compression tableting. The molecular sieve has a very small average particle size and is bulky. In addition, since the releasability from the molding die is poor, it is not possible to perform tableting with a compression tableting machine as it is, and the following three steps are required.
(1) Step of mixing lubricant and shabasite type crystalline silicoaluminophosphate molecular sieve powder
(2) Preforming and sizing process
(3) Compression tablet molding process
Hereinafter, the details of the implementation method will be described for each step.
[0012]
(1) Step of mixing lubricant and shabasite type crystalline silicoaluminophosphate molecular sieve powder
In tablet molding, it is necessary to finally remove the molded body from the molding die. However, since the molecular sieve has poor releasability from the molding die, it is necessary to add a lubricant as a releasing agent. is there. As the lubricant, for example, inorganic salts of stearic acid, artificial graphite, and the like are used. The amount of the lubricant to be added is appropriately from 0.1% to 5% by weight based on the molecular sieve. These lubricants are uniformly mixed with the molecular sieve to prepare a raw material powder for tableting.
[0013]
(2) Preliminary molding and sizing process
The shabasite-type crystalline silicoaluminophosphate molecular sieve powder produced by the method described above has a particle size of 200 μm or less and a bulk density of 0.3 to 0.7 g / cm.3Very bulky with degree. For this reason, even if compression tableting is performed as it is, a molded product having sufficient strength and an appropriate molded product density cannot be obtained. Therefore, it is necessary to perform preforming and sizing operations to prepare a preformed body having a bulk density and a particle size suitable for tableting. The preforming is performed at a pressure of 0.5 to 5 MPa using a roll compacting type or a roll pre-ketting type compression molding machine or the like. When a roll compacting molding machine is used, a sheet-shaped preform is obtained, which is further crushed and sized. The particle size of the preformed body after sizing is set to 30 mesh or less in view of the filling property into the tableting machine mold, but is particularly preferably adjusted to 20 mesh or less. Usually, a crusher and a screen for sizing are integrated with a roll compacting molding machine, and a series of the above operations can be easily performed.
[0014]
(3) Compression tablet molding process
The preformed body thus obtained is tablet-formed using a rotary or single-shot compression tableting machine. Industrially, a rotary compression tableting machine capable of efficiently producing a large amount of molded articles is suitable. The preforms prepared above are filled in the dies of these tableting machines, and compression tableting is performed with upper and lower punches. Tableting pressure is 20 to 200 MPa or less, preferably 40 to 100 MPa. Perform within the range. The shape of the tablet is generally a cylindrical tablet with a diameter and length of 2 to 10 mm. The size of the reaction tube for filling the tablet, the type of reaction desired, the productivity of the molded product, etc. And the size of the most suitable tableting product may be selected.
[0015]
The present inventors increased the density of the finally obtained molded body from 0.9 ° to 1.3 (g / cm).3) And the BET specific surface area of the molded body is 400 m2/ G or more has been found to be extremely important from the viewpoint that the catalyst activity does not decrease when this molded article is used as a reaction catalyst. If the density of the molded product is out of this range, the BET surface area of the molded product is 400 m2/ G or less, the catalyst activity of the obtained molded article is significantly reduced. The density of the compact depends on the bulk density of the preform, the filling amount in the die, the pressure for tableting, and the like. By adjusting and optimizing these, the density of the compact is 0.9 to 1.3 (g / cm).3) Can be controlled. The BET surface area depends on the water content in the molecular sieve, the preforming, and the tableting pressure. By controlling these, the BET surface area is 400 m.2/ G or more.
[0016]
The above tableting operation needs to be performed quickly under low humidity so that the molecular sieve absorbs as little moisture as possible. If possible, it is preferable to perform each operation in a dry nitrogen atmosphere.
[0017]
Thus, as an industrial catalyst, it has sufficient mechanical strength to withstand use, and has a binderless shabasite type crystalline aluminophosphate molecular sieve having the same high catalytic activity as that of the raw material powder. Body can be manufactured. The molded tablet obtained by the method of the present invention is industrially packed in a fixed-bed flow reactor, and a methylamine synthesis reaction using methanol and ammonia and / or methanol and monomethylamine as raw materials, and / or Alternatively, it can be used as a catalyst for a methylamine synthesis reaction by disproportionation reaction of monomethylamine, and the industrial significance of the present invention is extremely large.
[0018]
Next, specific embodiments of the present invention will be described in more detail with reference to Examples and Comparative Examples. The physical properties of the raw material powder and the molded body were measured by the following methods.
Average particle diameter: Measured with a wet laser diffraction type particle size distribution analyzer (HORIBA @ LA-500).
-Molded body density: 50 obtained molded bodies (n = 50) were each precisely weighed and calculated from the average value.
Crushing strength: Measured with a breaking strength measuring instrument (Okura Riken DHT-200) (n = 50).
Powdering rate: Measured by a basket test type powdering rate measuring device (Chihoda Seiko Co., Ltd.) (10 g of a molded body was placed in a cylindrical screen made of 14 mesh SUS) having a diameter of 100 mm and a height of 90 mm, and the cylinder was rotated at 160 rpm. After rotating for 10 minutes at, the powdering ratio was measured).
-BET specific surface area: Measured by a multi-point method using a nitrogen adsorption / desorption isotherm measuring apparatus (Autosorb-6 from QANTACHROME).
In Examples and Comparative Examples, the obtained molded articles were used as a catalyst for a reaction for synthesizing methylamine from methanol and ammonia, and the catalytic performance was evaluated. The evaluation method was as follows. A catalyst (2.5 g) was charged into a stainless steel cylindrical reaction tube, a 1: 1 weight mixture of ammonia and methanol was supplied at a rate of 5.19 g / h, a reaction pressure of 2 MPa, and a temperature of 320 ° C. Under the conditions, a methylamine synthesis reaction was performed. The space-time velocity (GHSV) is about 900 to 1200 h −1. The reaction product 12 hours after the flow of the raw materials was collected in water, and the reaction results were examined by gas chromatography. There are three types of product, methylamine, monomethylamine, dimethylamine and trimethylamine, and a catalyst having a high selectivity for dimethylamine is industrially desired. Abbreviations described are as follows:
・ Monomethylamine: mMA
・ Dimethylamine: dMA
・ Trimethylamine: tMA
[0019]
【Example】
Example 1
As a shabasite-type crystalline aluminophosphate molecular sieve, TiSAPO-34 powder produced by adding Ti during hydrothermal treatment and using tetraethylammonium hydroxide as a template agent is dried at 100 ° C. for 16 hours to have a water content of 1.1 wt. %. The average particle size of this powder was 2.1 μm. 1.5 wt% artificial graphite based on the dry weight of TiSAPO-34 was added and mixed. Next, using a roller compacting type compression molding machine (manufactured by Freund Corporation), a preforming treatment was performed under a pressure of 1.5 MPa, and the obtained preformed body was crushed and then sized to 16 mesh. . This was tableted under a pressure of 80 MPa using a rotary compression tableting machine (manufactured by Kikusui Seisakusho) to obtain a molded product of a columnar tablet having a diameter of 3.2 mm and a height of 3.2 mm. The physical properties of the obtained molded body were as follows.
Molding density: 1.09 (g / cm3)
Crush strength: 14.8 (MPa)
Powdering rate: 2.5 (wt%)
BET specific surface area: 470 (m2/ G)
The crushing strength and the powdering ratio are indicators of whether or not they have mechanical strength that can be used as an industrial catalyst. If the strength is 5 MPa or more and the powdering ratio is 5 wt% or less, sufficient strength as a practical catalyst is obtained. It is. The strengths of the molded articles produced in this example all satisfied these values, and were at a level that would not cause any problem when used as an industrial catalyst. The results of the methylamine synthesis reaction of this molded product were as follows, and both the catalytic activity (conversion of methanol) and the selectivity for dMA were high.
Methanol conversion: 98.2%
Amine selectivity: mMA / dMA / tMA = 32/64/4 (wt%)
Table 1 summarizes the above results.
[Table 1]
Comparative Example 1
A methylamine synthesis reaction was carried out in the same manner as in Example 1, except that the TiSAPO-34 produced in Example 1 was used as powder. Table 1 shows the results. The reaction results are almost the same as those in Example 1, and it is clear that the molded article of Example 1 has no activity reduction or change in selectivity as compared with TiSAPO-34 before molding. The methylamine synthesis reaction using such a fine powder catalyst can be carried out in a laboratory, but cannot be carried out industrially in a large fixed bed flow reactor.
[0021]
Examples 2 and 3, Comparative Example 2, (Effect of water content)
Same as Example 1 except that the moisture content of TiSAPO-34 powder was 4.8 wt% (Example 2), 10.0 wt% (Example 3), and 25.6 wt% (Comparative Example 2). A molded article was obtained by a simple operation, and the methylamine synthesis reaction activity was examined. Table 1 shows the results. The molded article density is 1.09 to 1.10 g / cm3), And the molded body density was substantially the same as that of Example 1. From these results, it was observed that as the water content of the TiSAPO-34 powder was increased, the crushing strength of the molded article was remarkably reduced and the powdering rate was increased, and the water content of the TiSAPO-34 powder was 10 wt. %, The molded product was far from the required strength as a catalyst and could not withstand practical use. Further, the BET specific surface area tends to decrease as the water content increases.
In Comparative Example 2, the catalytic activity (methanol addition rate) in the methylamine synthesis reaction was 87.9%, which was lower than the others. The BET specific surface area is 389 (m2/ G). The selectivity of dMA was as high as in Example 1.
[0022]
Examples 4 and 5, Comparative Example 3, (Effect of Density of Molded Body)
Except that the molding pressure of the rotary compression tableting machine was set to 40 MPa (Example 4), 100 MPa (Example 5), and 150 MPa (Comparative Example 3), a molded body was obtained by the same operation as in Example 1, The methylamine synthesis reaction activity was examined. Table 2 shows the results. The density of the molded body of the catalyst obtained as a result of this operation was 1.00 g / cm in Example 4.31.30 g / cm in Example 531.35 g / cm in Comparative Example 33Met. The strength of the molded body was at a level that did not cause any problem when used as an industrial catalyst. However, in Comparative Example 3, the BET surface area was reduced, and the catalytic activity (methanol addition ratio) in the methylamine synthesis reaction was lower than that of other catalysts. It was lower than the one.
[Table 2]
Examples 6 to 9, (Effect of molecular sieve)
Synthesis using a system without adding Ti during hydrothermal synthesis (Example 6), synthesis using a system using cyclohexylamine as a template without adding Ti during hydrothermal synthesis (Example 7), adding Ti during hydrothermal synthesis The same as Example 1 except that the synthesis was performed in a system using sec-butylamine as a template agent without using (Example 8) and in a system in which Zr was added instead of Ti in hydrothermal synthesis (Example 9). A molded product was obtained by the operation, and the methylamine synthesis reaction activity was examined. Table 3 shows the results. The SAPOs synthesized in each example are SAPO-34 (Example 6), SAPO-44 (Example 7), SAPO-47 (Example 8), and ZrSAPO-34 (Example 9), respectively. The average particle diameter of each SAPO at each stage was 4 μm or less. The density of the obtained molded body is 1.08 to 1.1 g / cm.3The strength of each of the molded products was at a level that did not cause any problem when used as an industrial catalyst. In addition, the BET surface area of all the moldings is 400m.2/ G or more, and both the catalytic activity (methanol addition rate) and dMA selectivity in the methylamine synthesis reaction were high.
[Table 3]
Comparative Examples 4 to 8, (Comparison with extrusion molding method)
An arbitrary type and amount of a binder were added to 10 g of the TiSAPO-34 powder produced in the same manner as in Example 1, and kneaded with 10 g of water. The kneaded product was extruded using a syringe, dried at 110 ° C. for 4 hours, and formed into a molded product having a diameter of 3.2 mm × a height of 3.2 mm. The molded body was calcined in air at 600 ° C. for 4 hours to obtain an extruded molded product catalyst. The molded body strength was measured in the same manner as in Example 1, and the methylamine synthesis reaction activity was examined. The kind and amount of the binder used in each comparative example are as follows.
Comparative Example 4: Addition of 15% by weight of swellable synthetic mica (manufactured by ME-100 Corp Chemical Co., Ltd.) to TiSAPO-34 powder
Comparative Example 5: 25% by weight of swellable synthetic mica (manufactured by ME-100 Corp Chemical Co.) was added to TiSAPO-34 powder.
Comparative Example 6: 15 wt% of kaolin was added to TiSAPO-34 powder.
Comparative Example 7: 15% by weight of alumina was added to TiSAPO-34 powder
Comparative Example 8: Attapulgite was added in an amount of 15% by weight based on TiSAPO-34 powder.
Table 4 shows the results. The strength of the molded body of the catalyst obtained as a result of this operation was at a level without any problem when used as an industrial catalyst, but was weaker than that of the tableting molded body of Example 1. In addition, the strength of the molded body is improved by increasing the amount of the binder added as compared with Comparative Examples 4 and 5. The catalytic activity (methanol addition rate) in the methylamine synthesis reaction was considerably lower than that of the tableting product of Example 1. This is because the absolute amount of the TiSAPO-34 catalyst in the molded body was reduced by the added binder. In Comparative Examples 6, 7, and 8 using kaolin, alumina, and attapulgite, the selectivity of dMA was low. It is considered that the disproportionation reaction of amines progressed due to the acid point of the added binder itself, and the selectivity of dMA was lowered.
[Table 4]
【The invention's effect】
Based on the method provided by the present invention, the compression-molded molded product of the shabasite-type crystalline silicoaluminophosphate molecular sieve is binderless, and thus has a reduced activity seen in an extruded product requiring the addition of a binder. There is almost no decrease in the selectivity of the target reactant, and the molded product has sufficient strength to withstand industrial use. The method for producing such a molded article is extremely useful in the field of catalyst molding for shabasite-type crystalline silicoaluminophosphate molecular sieves, and the present invention is significant.
Claims (11)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014501612A (en) * | 2010-12-22 | 2014-01-23 | クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Method for converting nitrogen-containing compounds |
| WO2014061569A1 (en) * | 2012-10-15 | 2014-04-24 | 三菱瓦斯化学株式会社 | Method for producing catalyst for use in production of methylamine compound, and method for producing methylamine compound |
| CN107159104A (en) * | 2017-05-12 | 2017-09-15 | 太原理工大学 | A kind of method for Chabazite molecular sieve compression moldings |
| WO2024007611A1 (en) * | 2022-07-08 | 2024-01-11 | 中化学环保催化剂有限公司 | Selective reduction catalyst, and treatment system and treatment method for gas containing nox |
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2002
- 2002-07-17 JP JP2002208593A patent/JP4182330B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014501612A (en) * | 2010-12-22 | 2014-01-23 | クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Method for converting nitrogen-containing compounds |
| WO2014061569A1 (en) * | 2012-10-15 | 2014-04-24 | 三菱瓦斯化学株式会社 | Method for producing catalyst for use in production of methylamine compound, and method for producing methylamine compound |
| US9180444B2 (en) | 2012-10-15 | 2015-11-10 | Mitsubishi Gas Chemical Company, Inc. | Method for producing catalyst for use in production of methylamine compound, and method for producing methylamine compound |
| JPWO2014061569A1 (en) * | 2012-10-15 | 2016-09-05 | 三菱瓦斯化学株式会社 | Method for producing catalyst for producing methylamines and method for producing methylamines |
| CN107159104A (en) * | 2017-05-12 | 2017-09-15 | 太原理工大学 | A kind of method for Chabazite molecular sieve compression moldings |
| WO2024007611A1 (en) * | 2022-07-08 | 2024-01-11 | 中化学环保催化剂有限公司 | Selective reduction catalyst, and treatment system and treatment method for gas containing nox |
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