JPH0153259B2 - - Google Patents
Info
- Publication number
- JPH0153259B2 JPH0153259B2 JP56054365A JP5436581A JPH0153259B2 JP H0153259 B2 JPH0153259 B2 JP H0153259B2 JP 56054365 A JP56054365 A JP 56054365A JP 5436581 A JP5436581 A JP 5436581A JP H0153259 B2 JPH0153259 B2 JP H0153259B2
- Authority
- JP
- Japan
- Prior art keywords
- source
- alumina
- catalyst
- silica
- metal oxide
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 239000010457 zeolite Substances 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 14
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000007323 disproportionation reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 15
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- -1 phosphorus compound Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- CIISBYKBBMFLEZ-UHFFFAOYSA-N 1,2-oxazolidine Chemical compound C1CNOC1 CIISBYKBBMFLEZ-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GOPUCFKUFOFEIC-UHFFFAOYSA-N 2-methyl-1,3-oxazolidine Chemical compound CC1NCCO1 GOPUCFKUFOFEIC-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- FFNCEXOZZTUYQX-UHFFFAOYSA-N 4-methylmorpholin-3-amine Chemical compound CN1CCOCC1N FFNCEXOZZTUYQX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000511343 Chondrostoma nasus Species 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RAGLTCMTCZHYEJ-UHFFFAOYSA-K azanium;chromium(3+);disulfate Chemical compound [NH4+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RAGLTCMTCZHYEJ-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- XHWNEBDUPVMPKI-UHFFFAOYSA-N oxazetidine Chemical compound C1CON1 XHWNEBDUPVMPKI-UHFFFAOYSA-N 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はトルエンの不均化反応によるパラキシ
レンの製造方法に関し、詳しくは特定の触媒の存
在下で、トルエンの不均化反応を行なうことによ
り、パラキシレンを選択的に効率よく製造する方
法に関する。
従来から、ZSM−５系の結晶性アルミノシリ
ケートゼオライト触媒を用いてトルエンの不均化
反応を行ない、パラキシレンを含むキシレン混合
物を製造する方法は知られている（特開昭50−
96532号公報）。しかしこの方法ではパラキシレン
の選択率が充分でないため、さらに上記触媒をリ
ン化合物で変性する（米国特許第4016219号明細
書）、リンの酸化物と酸化マグネシウムで変性す
る（米国特許第4011276号明細書）、ニツケル置換
する（米国特許第4052476号明細書）、プレコーキ
ングする（米国特許第4097543号明細書）などの
後処理が行なわれているが、これらの方法を実施
するには、後処理の設備と工程がさらに必要であ
り、手数と費用がかさみ工業的には有利な方法と
言い難い。
そこで本発明者らは上記従来法の欠点を解消
し、簡単な工程で調製できる結晶性のZSM型ゼ
オライト触媒を用いて、トルエンからパラキシレ
ンを選択的にかつ効率よく製造する方法を開発す
べく鋭意研究を重ねた。その結果、特定のZSM
型ゼオライト触媒を用いることにより目的を達成
しうることを見出し、本発明を完成するに至つ
た。
すなわち本発明は、(A)シリカ源、(B)アルカリ金
属酸化物源および／またはアルカリ土類金属酸化
物源、(C)クロム酸化物源またはクロム酸化物源と
アルミナ源および環員として窒素、酸素を含有す
る複素環式化合物を水と共に混合して得た混合物
を加熱して調製した下記のＸ線回折パターンで示
され、かつ(C)成分としてアルミナを用いる場合、
シリカ／アルミナ比が少なくとも10（モル比）で
あるZSM型ゼオライト触媒の存在下で、300〜
500℃の温度でトルエンの不均化反応を行なうこ
とを特徴とするパラキシレンの製造方法を提供す
るものである。
The present invention relates to a method for producing para-xylene by a disproportionation reaction of toluene, and more particularly, a method for selectively and efficiently producing para-xylene by carrying out a disproportionation reaction of toluene in the presence of a specific catalyst. . A method for producing a xylene mixture containing para-xylene by carrying out a disproportionation reaction of toluene using a ZSM-5 crystalline aluminosilicate zeolite catalyst has been known (Japanese Unexamined Patent Application Publication No. 1979-1999).
Publication No. 96532). However, since this method does not have sufficient selectivity for paraxylene, the catalyst is further modified with a phosphorus compound (U.S. Pat. No. 4,016,219) or with a phosphorus oxide and magnesium oxide (U.S. Pat. No. 4,011,276). Post-treatments such as nickel substitution (U.S. Pat. No. 4,052,476) and pre-coking (U.S. Pat. No. 4,097,543) have been carried out. It is difficult to say that this method is industrially advantageous because additional equipment and processes are required, which increases labor and cost. Therefore, the present inventors aimed to overcome the drawbacks of the above conventional methods and develop a method for selectively and efficiently producing paraxylene from toluene using a crystalline ZSM type zeolite catalyst that can be prepared in a simple process. I have done extensive research. As a result, certain ZSM
The inventors have discovered that the object can be achieved by using a zeolite type catalyst, and have completed the present invention. That is, the present invention provides (A) a silica source, (B) an alkali metal oxide source and/or an alkaline earth metal oxide source, (C) a chromium oxide source or a chromium oxide source and an alumina source, and nitrogen as a ring member. , is shown in the following X-ray diffraction pattern prepared by heating a mixture obtained by mixing an oxygen-containing heterocyclic compound with water, and when alumina is used as component (C),
In the presence of a ZSM type zeolite catalyst with a silica/alumina ratio of at least 10 (molar ratio),
The present invention provides a method for producing paraxylene, which is characterized by carrying out a disproportionation reaction of toluene at a temperature of 500°C.
【表】【table】
【表】
本発明の方法に用いるZSM型ゼオライト触媒
は(A)シリカ、(B)アルカリ金属酸化物および／また
はアルカリ土類金属酸化物および(C)クロム酸化物
またはクロム酸化物とアルミナよりなり、かつ(C)
成分としてクロム酸化物をアルミナを用いる場合
にシリカ／アルミナ比が少なくとも10（モル比）
でなければならない。より好ましくは(A)、(B)およ
び(C)成分の組成比が１：0.01〜50：２×10+7〜0.1
（モル比）のものである。
本発明の方法に用いる上述の如きZSM型ゼオ
ライト触媒を調製するにあつては、通常の結晶性
ゼオライトの合成に用いられるシリカ源、アルカ
リ金属酸化物源、アルカリ土類金属酸化物源、ク
ロム酸化物源、アルミナ源などと水とからなる混
合物を用いればよく、さらにこの混合物に環員と
して窒素、酸素を含有する複素環式化合物を添加
する。
ここでシリカ源としては、結晶性ゼオライトの
製造に通常使用されるものであれば特に制限はな
く、シリカ粉末、ケイ酸、コロイド状シリカ、溶
解シリカなどを任意に使用できる。溶解シリカと
しては、Na2OまたはK2O1モルに対してSiO21〜
５モルを含有する水ガラスケイ酸塩、アルカリ金
属ケイ酸塩などがあげられる。
さらに、アルカリ金属酸化物源としては、水酸
化ナトリウム、水酸化カリウムなどが用いられ、
またケイ酸ナトリウム、アルミン酸ナトリウムと
してシリカあるいはアルミナの供給源を兼ねるこ
ともできる。特にアルカリ金属としてはナトリウ
ムが望ましい。
また、アルカリ土類金属酸化物源としては、硝
酸塩、塩化物、例えば硝酸カルシウム、塩化カル
シウムなどがある。本発明に用いる触媒では、(B)
成分としてアルカリ金属酸化物、アルカリ土類金
属酸化物を含有するものであるが、これらはどち
らか一方のみでもよく、両者が併存していてもよ
い。
(C)成分の必須成分であるクロム酸化物源として
は、硝酸塩、塩化物、硫酸アンモニウム塩、例え
ば硝酸クロム、塩化クロム、硫酸クロムアンモニ
ウムなどをあげることができる。
また、アルミナ源としては、結晶性ゼオライト
の製造に通常使用されているものであればよく、
特に限定はないが、一般に硫酸塩、硝酸塩のごと
きアルミニウムの塩、例えば硫酸アルミニウム、
アルミン酸ナトリウムあるいはコロイド状アルミ
ナ、アルミナなどが用いられる。
本発明の方法に用いる触媒では、上記のクロム
酸化物およびアルミナは共に(C)成分を構成するも
のであるが、前述した如くクロム酸化物は(C)成分
として必須のものである。しかしアルミナは必要
に応じて用いればよく、必須成分ではない。
本発明の方法に用いる触媒を調製するに際して
は、上述の原料成分と共に、環員として窒素、酸
素を含有する複素環式化合物を用いることが有効
である。ここで複素環式化合物としては、モルホ
リン、オキサゾリジン、イソオキサゾリジン、オ
キサゼチジン、１―オキサ―５―アザシクロウン
デカン、１―オキサ―４―アザシクロドデカンあ
るいはこれらの誘導体を例示することができる。
これらのうち、モルホリン、アミノメチルモルホ
リン、Ｎ―アミノプロピルモルホリンなどのモル
ホリン類、オキサゾリジン、２―メチルオキサゾ
リジンなどのオキサゾリジン類が望ましい。これ
ら複素環式化合物としては、水に可溶性のものが
有利に用いられる。この複素環式化合物の添加量
は、シリカ（SiO2）１モルに対して0.01〜50モ
ル、好ましくは0.1〜10モルの範囲で決定される。
なお、この複素環式化合物は、触媒調製過程、特
に焼成過程で分解あるいは蒸発してしまい、それ
自身は触媒中にほとんど含有されていないが、ゼ
オライトの結晶化剤として働き得られる触媒の構
造を決定する上で効果的に作用するものである。
本発明に用いる触媒を調製するには、上述の如
き原料を混合し、これを結晶性ゼオライトが生成
するに必要な温度および時間加熱すればよい。な
お、この際、必要に応じて結晶化を促進するため
に塩化リチウムなどの鉱化剤を加えることもでき
る。触媒調製の具体的条件としては、反応温度80
〜300℃、好ましくは120〜200℃の範囲とし、反
応時間10〜50時間に選定して、また反応圧力は通
常自己圧力下とする。さらに反応系は通常は撹拌
下におかれ、雰囲気な必要により不活性ガスで置
換してもよい。
結晶性ゼオライトの生成が完了した反応混合物
は、室温にまで冷却した後、濾過、デカンテーシ
ヨン、遠心分離などにより結晶を分離し、水で十
分に洗浄し結晶を得る。この結晶を通常100℃以
上で数時間程度乾燥し、さらに空気中で300〜700
℃の範囲の温度にて２〜48時間程度焼成して活性
化したり、あるいは結晶性ゼオライト中に存在す
るアルカリ金属イオンの一部をアンモニウムイオ
ンで交換した後、焼成するかまたは塩酸でイオン
交換することによりＨ型の結晶性ゼオライトなど
とする。
本発明の方法は、かくして得られたZSM型ゼ
オライト触媒を用いて、トルエンの不均化反応を
行ない、高い選択性でパラキシレンを製造するも
のである。
本発明の方法の条件をより具体的に説明すれ
ば、まずトルエンを原料として、これを上述の調
製法にて入手したZSM型ゼオライト触媒の存在
下で、常圧にて300〜500℃の温度で反応させるこ
とにより行なわれる。ここで原料トルエンに対す
る触媒の量は特に制限はないが、通常は触媒量で
充分である。また、反応はバツチ式で行なうこと
もできるが、流通式で行なうことも可能である。
上述の本発明の方法によれば、比較的低温下で
反応が効率よく進行し、トルエンの転化率が高
く、しかも目的とするパラキシレンの選択率が著
しく高い。さらに、上述の結晶性ゼオライト触媒
をそのまま用いればよく、使用に際して予めスチ
ーミング処理、リン処理等の特別の処理を施す必
要がなく、操作も簡便である。
それ故、本発明の方法はパラキシレンの有効か
つ経済的な製造法として石油化学工業の分野にお
いて広く利用されるものである。
次に本発明の実施例を示す。
実施例 １
(1) 触媒の調製
まず硫酸アルミニウム（18水塩）6.6ｇ、硝
酸クロム（９水塩）16.1ｇ、モルホリン8.9ｇ、
97％硫酸17.6ｇおよび水250mlからなる溶液
（）を調製した。一方、これとは別途に水ガ
ラス（和光純薬(株)製；SiO237.6wt％、
Na2O17.5wt％、水分44.9wt％）162ｇおよび水
300mlからなる溶液（）ならびに塩化ナトリ
ウム79ｇおよび水122mlからなる溶液（）を
調製した。
次いで上記溶液（）中へ溶液（）および
（）を室温で撹拌しながら同時に徐々に滴下
して混合物を得た。続いてこの混合物１を、
オートクレーブに入れ、170℃にて300r.p.m.の
回転数で撹拌し、自己圧力下で20時間反応させ
た。その後、反応混合物を冷却し、生成した
ZSM型ゼオライト触媒をデカンテーシヨンに
より約１の水で５回洗浄し、最後に濾過によ
りZSM型ゼオライト触媒を取り出し、更に120
℃で３時間乾燥したところ、52ｇのZSM型ゼ
オライト触媒が得られた。かくして得られた
ZSM型ゼオライト触媒の組成はSiO2100重量部
に対してNa2O9.9重量部、Cr2O31.9重量部、
Al2O31.2重量部であつた。このものを１規定硝
酸アンモニウム水溶液300mlに入れ、室温で一
昼夜イオン交換してアンモニウム型とした。さ
らに水洗、乾燥をしたのち、空気中550℃で６
時間焼成してＨ型とした。
(2) 不均化反応
ステンレススチール製の反応管に上記(1)で得
られたZSM型ゼオライト触媒を充填し、この
反応管に、トルエンを常圧、350℃、液時空間
速度2.8hr-1の条件で４時間通して反応を行な
つた。結果を第２表に示す。
実施例 ２
(1) 触媒の調製
硝酸クロム（９水塩）8.0ｇ、モルホリン8.9
ｇ、97％硫酸17.6ｇおよび水250mlからなる溶
液（）を調製し、また水ガラス（実施例１(1)
と同じもの）162ｇおよび水300mlからなる溶液
（）ならびに塩化ナトリウム79ｇおよび水122
mlからなる溶液（）を調製した。以下、実施
例１(1)と同様の条件で操作を行ないZSM型ゼ
オライト触媒を得た。得られたZSM型ゼオラ
イト触媒の組成はSiO2100重量部に対して
Cr2O31.3重量部およびNa2O6.0重量部であつ
た。
(2) 不均化反応
上記(1)で得られたZSM型ゼオライト触媒を
用いたこと以外は実施例１(2)と同様の条件で不
均化反応を行なつた。得られた結果を第２表に
示す。
比較例 １、２
触媒としてZSM―５系ゼオライト触媒を用い、
また反応温度、液時空間速度（WHSV）を所定
の条件にしたこと以外は、実施例１(2)と同様に不
均化反応を行なつた。得られた結果を第２表に示
す。
なおここで用いたZSM―５系ゼオライト触媒
は次のように調製した。すなわち、硫酸アルミニ
ウム（18水塩）7.52ｇ、テトラプロピルアンモニ
ウムブロマイド25ｇ、硫酸（97％）17.6ｇ、水
250mlを溶液としたものをＡ液とする。水ガラス
（SiO237.6重量％、Na2O17.5重量％、水44.9重量
％）162ｇと水300mlを溶液としたものをＢ液とす
る。塩化ナトリウム79ｇと水122mlを溶液とした
ものをＣ液とする。
Ｃ液を撹拌しながら、これに室温でＡ液、Ｂ液
を同時に徐々に滴下した。この混合物を１のオ
ートクレーブに入れ、回転数200r.p.mで撹拌しな
がら170℃、自己圧力下にて20時間反応させた。
反応混合物を冷却した後、１の水で５回洗浄し
次いで過により固形分を分離し、120℃で３時
間乾燥することによつて53.2ｇの触媒を得た。
比較例 ３
触媒としてSiO2−Al2O3−Na2O触媒を用いた
こと以外は、実施例１(2)と同様の条件で不均化反
応を行なつた。得られた結果を第２表に示す。な
おここで用いたSiO2−Al2O3−Na2O触媒は、前
記比較例１、２で用いたZSM―５系ゼオライト
触媒の調製法において、テトラプロピルアンモニ
ウムブロマイド25ｇの代わりにモルホリン8.7ｇ
を用いたこと以外は全く同じ条件で操作すること
によつて調製した。[Table] The ZSM type zeolite catalyst used in the method of the present invention consists of (A) silica, (B) an alkali metal oxide and/or alkaline earth metal oxide, and (C) chromium oxide or chromium oxide and alumina. , and (C)
When using chromium oxide and alumina as components, the silica/alumina ratio is at least 10 (molar ratio)
Must. More preferably, the composition ratio of components (A), (B) and (C) is 1:0.01 to 50:2×10 +7 to 0.1.
(molar ratio). In preparing the ZSM type zeolite catalyst as described above used in the method of the present invention, a silica source, an alkali metal oxide source, an alkaline earth metal oxide source, a chromium oxide source, and a chromium oxide source, which are used in the synthesis of ordinary crystalline zeolites, are used. A mixture consisting of an alumina source, an alumina source, etc., and water may be used, and a heterocyclic compound containing nitrogen and oxygen as ring members is further added to this mixture. Here, the silica source is not particularly limited as long as it is commonly used in the production of crystalline zeolite, and any silica powder, silicic acid, colloidal silica, dissolved silica, etc. can be used. As dissolved silica, SiO 2 1 to 1 mole of Na 2 O or K 2 O
Examples include water glass silicates and alkali metal silicates containing 5 mol. Furthermore, sodium hydroxide, potassium hydroxide, etc. are used as alkali metal oxide sources,
Moreover, it can also serve as a source of silica or alumina as sodium silicate or sodium aluminate. Particularly desirable as the alkali metal is sodium. In addition, alkaline earth metal oxide sources include nitrates and chlorides, such as calcium nitrate and calcium chloride. In the catalyst used in the present invention, (B)
Although it contains an alkali metal oxide and an alkaline earth metal oxide as components, either one of these may be used alone or both may coexist. Examples of the source of chromium oxide, which is an essential component of component (C), include nitrates, chlorides, and ammonium sulfate salts, such as chromium nitrate, chromium chloride, and chromium ammonium sulfate. In addition, the alumina source may be any one that is normally used in the production of crystalline zeolite.
Although not particularly limited, aluminum salts such as sulfates and nitrates, such as aluminum sulfate,
Sodium aluminate, colloidal alumina, alumina, etc. are used. In the catalyst used in the method of the present invention, both the above-mentioned chromium oxide and alumina constitute component (C), and as described above, chromium oxide is essential as component (C). However, alumina may be used as needed and is not an essential component. When preparing the catalyst used in the method of the present invention, it is effective to use a heterocyclic compound containing nitrogen and oxygen as ring members in addition to the above-mentioned raw material components. Examples of the heterocyclic compound include morpholine, oxazolidine, isoxazolidine, oxazetidine, 1-oxa-5-azacycloundecane, 1-oxa-4-azacyclododecane, and derivatives thereof.
Among these, morpholines such as morpholine, aminomethylmorpholine and N-aminopropylmorpholine, and oxazolidines such as oxazolidine and 2-methyloxazolidine are preferred. As these heterocyclic compounds, those soluble in water are advantageously used. The amount of the heterocyclic compound added is determined in the range of 0.01 to 50 mol, preferably 0.1 to 10 mol, per 1 mol of silica (SiO 2 ).
Note that this heterocyclic compound decomposes or evaporates during the catalyst preparation process, especially during the calcination process, and is hardly contained in the catalyst itself, but it changes the structure of the catalyst and can act as a crystallizing agent for zeolite. It is effective in making decisions. In order to prepare the catalyst used in the present invention, the raw materials as described above may be mixed and heated at a temperature and for a time necessary to form crystalline zeolite. Note that at this time, a mineralizing agent such as lithium chloride may be added to promote crystallization if necessary. The specific conditions for catalyst preparation include a reaction temperature of 80°C.
The temperature is selected to be in the range of ~300°C, preferably 120 to 200°C, the reaction time is selected to be 10 to 50 hours, and the reaction pressure is usually under autogenous pressure. Furthermore, the reaction system is usually kept under stirring, and the atmosphere may be replaced with an inert gas if necessary. After the reaction mixture in which the production of crystalline zeolite has been completed is cooled to room temperature, the crystals are separated by filtration, decantation, centrifugation, etc., and thoroughly washed with water to obtain crystals. These crystals are usually dried at temperatures above 100°C for several hours, and then dried at 300 to 700°C in the air.
It is activated by firing at a temperature in the range of ℃ for about 2 to 48 hours, or after exchanging some of the alkali metal ions in the crystalline zeolite with ammonium ions, it is calcined or ion-exchanged with hydrochloric acid. In this way, H-type crystalline zeolite is obtained. The method of the present invention uses the thus obtained ZSM type zeolite catalyst to carry out a disproportionation reaction of toluene to produce paraxylene with high selectivity. To explain the conditions of the method of the present invention more specifically, first, toluene is used as a raw material, and in the presence of the ZSM type zeolite catalyst obtained by the above-mentioned preparation method, it is heated at a temperature of 300 to 500 °C at normal pressure. This is done by reacting with There is no particular restriction on the amount of catalyst relative to the raw material toluene, but the amount of catalyst is usually sufficient. Furthermore, although the reaction can be carried out in batch mode, it is also possible to carry out in flow mode. According to the method of the present invention described above, the reaction proceeds efficiently at a relatively low temperature, the conversion rate of toluene is high, and the selectivity of the target para-xylene is extremely high. Furthermore, the above-mentioned crystalline zeolite catalyst can be used as it is, and there is no need for special treatment such as steaming treatment or phosphorus treatment before use, and the operation is simple. Therefore, the method of the present invention is widely used in the petrochemical industry as an effective and economical method for producing paraxylene. Next, examples of the present invention will be shown. Example 1 (1) Preparation of catalyst First, 6.6 g of aluminum sulfate (18 hydrate), 16.1 g of chromium nitrate (9 hydrate), 8.9 g of morpholine,
A solution () consisting of 17.6 g of 97% sulfuric acid and 250 ml of water was prepared. On the other hand, separately from this, water glass (manufactured by Wako Pure Chemical Industries, Ltd.; SiO 2 37.6wt%,
Na 2 O 17.5wt%, moisture 44.9wt%) 162g and water
A solution consisting of 300 ml () and a solution consisting of 79 g sodium chloride and 122 ml water were prepared. Next, solutions () and () were simultaneously gradually added dropwise into the above solution () while stirring at room temperature to obtain a mixture. Next, mix this mixture 1 with
The mixture was placed in an autoclave, stirred at 170° C. at a rotational speed of 300 rpm, and reacted under autogenous pressure for 20 hours. Thereafter, the reaction mixture was cooled and the produced
The ZSM type zeolite catalyst was washed 5 times with about 120 ml of water by decantation, and finally the ZSM type zeolite catalyst was taken out by filtration.
After drying at ℃ for 3 hours, 52 g of ZSM type zeolite catalyst was obtained. thus obtained
The composition of the ZSM type zeolite catalyst is 100 parts by weight of SiO 2 , 9.9 parts by weight of Na 2 O, 1.9 parts by weight of Cr 2 O 3 ,
The amount of Al 2 O 3 was 1.2 parts by weight. This product was placed in 300 ml of a 1N ammonium nitrate aqueous solution and subjected to ion exchange at room temperature overnight to obtain an ammonium form. After further washing with water and drying, it was heated to 550℃ in the air.
It was baked for a period of time to form an H shape. (2) Disproportionation reaction A stainless steel reaction tube was filled with the ZSM type zeolite catalyst obtained in (1) above, and toluene was added to the reaction tube at normal pressure, 350°C, and a liquid hourly space velocity of 2.8 hours . The reaction was carried out under conditions 1 for 4 hours. The results are shown in Table 2. Example 2 (1) Preparation of catalyst Chromium nitrate (nase hydrate) 8.0g, morpholine 8.9g
A solution () consisting of 17.6 g of 97% sulfuric acid and 250 ml of water was prepared, and water glass (Example 1 (1)
A solution consisting of 162 g () and 300 ml of water () and 79 g of sodium chloride and 122 g of water
A solution () consisting of ml was prepared. The following operation was carried out under the same conditions as in Example 1 (1) to obtain a ZSM type zeolite catalyst. The composition of the obtained ZSM type zeolite catalyst is based on 100 parts by weight of SiO 2
They were 1.3 parts by weight of Cr 2 O 3 and 6.0 parts by weight of Na 2 O. (2) Disproportionation reaction A disproportionation reaction was carried out under the same conditions as in Example 1 (2) except that the ZSM type zeolite catalyst obtained in (1) above was used. The results obtained are shown in Table 2. Comparative Examples 1 and 2 Using ZSM-5 zeolite catalyst as a catalyst,
Further, a disproportionation reaction was carried out in the same manner as in Example 1(2), except that the reaction temperature and liquid hourly space velocity (WHSV) were set to predetermined conditions. The results obtained are shown in Table 2. The ZSM-5 zeolite catalyst used here was prepared as follows. That is, 7.52 g of aluminum sulfate (18 hydrate), 25 g of tetrapropylammonium bromide, 17.6 g of sulfuric acid (97%), and water.
The solution containing 250 ml is called Solution A. A solution of 162 g of water glass (37.6% by weight of SiO 2 , 17.5% by weight of Na 2 O, 44.9% by weight of water) and 300 ml of water is called liquid B. Solution C is a solution of 79 g of sodium chloride and 122 ml of water. While stirring Solution C, Solutions A and B were gradually added dropwise to it simultaneously at room temperature. This mixture was placed in an autoclave No. 1, and reacted for 20 hours at 170° C. under autogenous pressure while stirring at a rotation speed of 200 rpm.
After the reaction mixture was cooled, it was washed five times with 1 portion of water, and the solid content was separated by filtration and dried at 120° C. for 3 hours to obtain 53.2 g of catalyst. Comparative Example 3 A disproportionation reaction was carried out under the same conditions as in Example 1(2) except that a SiO 2 -Al 2 O 3 -Na 2 O catalyst was used as the catalyst. The results obtained are shown in Table 2. The SiO 2 -Al 2 O 3 -Na 2 O catalyst used here was prepared by replacing 25 g of tetrapropylammonium bromide with 8.7 g of morpholine in the method for preparing the ZSM-5 zeolite catalyst used in Comparative Examples 1 and 2.
It was prepared by operating under exactly the same conditions except that .
【表】【table】
Claims (1)
び／またはアルカリ土類金属酸化物源、(C)クロム
酸化物源またはクロム酸化物源とアルミナ源およ
び環員として窒素、酸素を含有する複素環式化合
物を水と共に混合して得た混合物を加熱して調製
した下記のＸ線回折パターンで示され、かつ(C)成
分としてアルミナを用いる場合、シリカ／アルミ
ナ比が少なくとも10（モル比）であるZSM型ゼオ
ライト触媒の存在下で、300〜500℃の温度でトル
エンの不均化反応を行なうことを特徴とするパラ
キシレンの製造方法。 【表】 【表】 ２ (A)シリカ、(B)アルカリ金属酸化物および／ま
たはアルカリ土類金属酸化物、(C)クロム酸化物ま
たはクロム酸化物とアルミナの組成比が、１：
0.01〜50：２×10-7〜0.1（モル比）であるZSM型
ゼオライト触媒を用いる特許請求の範囲第１項記
載の方法。[Claims] 1 (A) silica source, (B) alkali metal oxide source and/or alkaline earth metal oxide source, (C) chromium oxide source or chromium oxide source and alumina source and ring member If the following X-ray diffraction pattern is prepared by heating a mixture obtained by mixing a heterocyclic compound containing nitrogen and oxygen with water, and alumina is used as component (C), silica/alumina 1. A method for producing paraxylene, characterized in that the disproportionation reaction of toluene is carried out at a temperature of 300 to 500°C in the presence of a ZSM type zeolite catalyst having a ratio of at least 10 (molar ratio). [Table] [Table] 2 (A) silica, (B) alkali metal oxide and/or alkaline earth metal oxide, (C) chromium oxide or the composition ratio of chromium oxide and alumina is 1:
The method according to claim 1, using a ZSM type zeolite catalyst having a molar ratio of 0.01 to 50:2 x 10 -7 to 0.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56054365A JPS57169434A (en) | 1981-04-13 | 1981-04-13 | Preparation of paraxylene by heterogeneous reaction of toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56054365A JPS57169434A (en) | 1981-04-13 | 1981-04-13 | Preparation of paraxylene by heterogeneous reaction of toluene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57169434A JPS57169434A (en) | 1982-10-19 |
| JPH0153259B2 true JPH0153259B2 (en) | 1989-11-13 |
Family
ID=12968617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56054365A Granted JPS57169434A (en) | 1981-04-13 | 1981-04-13 | Preparation of paraxylene by heterogeneous reaction of toluene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57169434A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG90117A1 (en) * | 2000-03-28 | 2002-07-23 | Uop Llc | Selective aromatics disproportionation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5567521A (en) * | 1978-11-09 | 1980-05-21 | Mobil Oil | Crystalline aluminoosilicateezeolite catalyst* converting organic material by using same* and preparing same catalyst |
| JPS5624051A (en) * | 1980-08-01 | 1981-03-07 | Union Oil Co | Catalyst for acid catalysed hydrocarbon conversion reaction |
-
1981
- 1981-04-13 JP JP56054365A patent/JPS57169434A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5567521A (en) * | 1978-11-09 | 1980-05-21 | Mobil Oil | Crystalline aluminoosilicateezeolite catalyst* converting organic material by using same* and preparing same catalyst |
| JPS5624051A (en) * | 1980-08-01 | 1981-03-07 | Union Oil Co | Catalyst for acid catalysed hydrocarbon conversion reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57169434A (en) | 1982-10-19 |
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