JPH01301658A - Production of pyrrole - Google Patents
Production of pyrroleInfo
- Publication number
- JPH01301658A JPH01301658A JP63131313A JP13131388A JPH01301658A JP H01301658 A JPH01301658 A JP H01301658A JP 63131313 A JP63131313 A JP 63131313A JP 13131388 A JP13131388 A JP 13131388A JP H01301658 A JPH01301658 A JP H01301658A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- furan
- ammonia
- molar ratio
- 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.)
- Pending
Links
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 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 4
- 238000004458 analytical method Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 Furthermore Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- WEQHQGJDZLDFID-UHFFFAOYSA-J thorium(iv) chloride Chemical compound Cl[Th](Cl)(Cl)Cl WEQHQGJDZLDFID-UHFFFAOYSA-J 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite 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
- Pyrrole Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、フランとアンモニアを水蒸気存在下で接触的
に反応させてピロールを製造する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing pyrrole by catalytically reacting furan and ammonia in the presence of steam.
ピロールは導電性高分子に誘導出来、新たらしい高分子
素材として注目を集めているものであり、これからの展
開に大きな期待がかかっている。Pyrrole can be induced into conductive polymers and is attracting attention as a new polymer material, and there are great expectations for its future development.
(従来の技術)
フランとアンモニアを原料としたピロールの合成反応は
次式の反応式に示されるように、酸素原子の置換反応に
基づくものとされている。(Prior Art) The synthesis reaction of pyrrole using furan and ammonia as raw materials is said to be based on a substitution reaction of oxygen atoms, as shown in the following reaction formula.
この反応に関する代表的文献は表1にみられるとおりで
ある。Representative references regarding this reaction are shown in Table 1.
触媒としてはアルミナ、シリカ・アルミナが用いられ、
更にこれら触媒にMoO2,CaO,BO2等を担持さ
せたものが紹介されている。又HatadaらはHY型
ゼオライトを用いている。Alumina, silica/alumina is used as a catalyst,
Furthermore, catalysts in which MoO2, CaO, BO2, etc. are supported on these catalysts have been introduced. Hatada et al. also use HY type zeolite.
以下余白
(発明が解決しようとする問題点)
ビロール製造技術の改良において、高い選択率、高い生
産性を示す触媒の開発が求められている。Margins below (Problems to be Solved by the Invention) In improving the virol production technology, there is a need for the development of catalysts that exhibit high selectivity and high productivity.
表1においてI(20を共存させる場合とH2Cを共存
させない場合とに大きく区分され、H2Cを共存させな
いで反応を行う場合、米国特許第2478452号明細
書に述べられている如く、触媒上にカーボンが析出し、
長時間の使用に耐えない問題がある。現にYu 、
K、 Yurevらの実験では100分間反応を行っ
たあと150分間かけて再生処理を行っているし、Ha
tadaらのパルス実験でもパルスの回数が増える毎に
活性が急速に低下している。In Table 1, it is broadly classified into cases in which I(20) coexists and cases in which H2C does not coexist. When the reaction is carried out without H2C coexisting, as described in U.S. Pat. No. 2,478,452, carbon is precipitated,
There is a problem that it cannot withstand long-term use. Actually Yu,
In the experiment of K. Yurev et al., the regeneration process was performed for 150 minutes after the reaction for 100 minutes.
In the pulse experiment by Tada et al., the activity rapidly decreased as the number of pulses increased.
こうした問題に対し米国特許第2600289号明細書
ではI−I 20を共存させる事により問題を解決して
おりその意義は大きく評価される。In US Pat. No. 2,600,289, the problem is solved by coexisting I-I 20, and its significance is highly evaluated.
ビロールをより安価に生産するためにはフランからビロ
ールへの選択率を高めることが重要である。フランが比
較的高価な原料であること、フラン、ビロールの沸点は
それぞれ31°C1130°Cと大きく離れており、未
反応フランと生成物ビロールの分離が容易であること、
また、過剰に用いるアンモニアは回収再利用が必要であ
り、未反応フランの回収再利用も同一システムが利用で
きること、さらに、従来技術によるとフランの選択率が
80〜95%(表1参照)であり、更に高い選択率を与
える触媒が望まれている。In order to produce virol at a lower cost, it is important to increase the selectivity from furan to virol. Furan is a relatively expensive raw material, the boiling points of furan and virol are significantly different from each other at 31°C and 1130°C, and it is easy to separate unreacted furan and product virol;
In addition, it is necessary to collect and reuse excess ammonia, and the same system can be used to collect and reuse unreacted furan.Furthermore, according to the conventional technology, the furan selectivity is 80 to 95% (see Table 1). However, there is a need for a catalyst that provides even higher selectivity.
(問題点を解決するための手段)
本発明者らはこうした観点から高い選択率を与える触媒
の開発を鋭意検討したところ、アルミナに対するシリカ
モル比(Si/A E )が20以上であるペンタシル
型の結晶性アルミノシリケートを触媒として用いた場合
、従来の技術を上回る反応成績を示すことを見出し、本
発明を生成するに至った。(Means for Solving the Problems) From this perspective, the present inventors conducted intensive studies on the development of a catalyst that provides high selectivity, and found that a pentasil-type catalyst with a silica to alumina molar ratio (Si/A E ) of 20 or more was developed. The present inventors have discovered that when crystalline aluminosilicate is used as a catalyst, the reaction results are superior to those of conventional techniques, leading to the creation of the present invention.
すなわち、本発明は、フランとアンモニアを水茎気存在
下で接触的に反応させてビロールを製造するに際し、ア
ルミナに対するシリカモル比(Si/AA)が20以上
であるペンタシル型の結晶性アルミノシリケートを触媒
として用いること−5=
を特徴とするピロールの製造法に関するものである。That is, the present invention uses a pentasil-type crystalline aluminosilicate having a silica to alumina molar ratio (Si/AA) of 20 or more as a catalyst when producing virol by catalytically reacting furan and ammonia in the presence of water vapor. The present invention relates to a method for producing pyrrole, characterized in that it is used as -5=.
本発明に用いるペンタシル型結晶性アルミノシリケート
は、たとえば、ジャーナル・オブ・フィジカルケミスト
リー (J ournal of P hysical
Chemistry、 Vol、 85. P22
38)に記載されているように、S i Oa とAj
Oイからなる三次元網状構造物を構成しており、構造内
の三面体は、酸素原子の架橋により交叉結合されており
、アルミニウムおよびシリコンの全原子対酸素の比は1
:2となっている。また、5R環10個で形成する10
員環の細孔を有するものとされている。The pentasil type crystalline aluminosilicate used in the present invention is described, for example, in the Journal of Physical Chemistry.
Chemistry, Vol. 85. P22
38), S i Oa and Aj
It constitutes a three-dimensional network structure consisting of Oi, and the trihedrons in the structure are cross-linked by bridges of oxygen atoms, and the ratio of all atoms of aluminum and silicon to oxygen is 1.
:2. In addition, 10 formed by 10 5R rings
It is said to have ring-membered pores.
ペンタシル型結晶性アルミノシリケートは公知の製造法
で調整できる。例えば、シリカ供給物質、アルミナ供給
物質、アルカリ金属イオン供給物質、水およびカチオン
性有機窒素化合物を含む反応混合物を100〜250°
Cの温度に加熱して、結晶が生成するのに充分な時間反
応させることにより得られる。詳しくはモービル・オイ
ル・コーポレーション社が開発したZSM−5(米国特
許第3702886号)やZSM−11(米国特許第3
709979号)等が使用できる。Pentasil type crystalline aluminosilicate can be prepared by a known production method. For example, a reaction mixture containing a silica feed material, an alumina feed material, an alkali metal ion feed material, water and a cationic organic nitrogen compound is heated at 100-250°C.
It is obtained by heating to a temperature of C and reacting for a sufficient time to form crystals. For details, see ZSM-5 (U.S. Patent No. 3702886) and ZSM-11 (U.S. Patent No. 3) developed by Mobil Oil Corporation.
709979) etc. can be used.
本発明で使用するペンタシル型結晶性アルミノシリケー
トのアルミナに対するシリカモル比(Si/AI)は選
択性の点において20以上が好ましく、その上限は特に
規定するものではないが、1000以下、好ましくは2
00以下である。1000以上になると触媒の活性が低
下し、単位触媒量当たりの生産性が悪くなり好ましくな
い。The silica to alumina molar ratio (Si/AI) of the pentasil-type crystalline aluminosilicate used in the present invention is preferably 20 or more in terms of selectivity, and the upper limit is not particularly specified, but it is 1000 or less, preferably 20.
00 or less. When it exceeds 1000, the activity of the catalyst decreases and the productivity per unit amount of catalyst deteriorates, which is not preferable.
ペンタシル型結晶性アルミノシリケートは、アルミニウ
ムを含有する四面体の電子価が結晶内にカチオンを含有
することで平衡が保たれるとされており、これらカチオ
ンは、公知のイオン交換技術を用いてカチオン交換する
ことができる。本発明に供するに当たり、プロトン、M
g、 Ca、 Sr等のアルカリ土類金属、La 、C
e等の希土類金属、Pd等の貴金属でイオン交換したも
のを用いることができる。In pentasil-type crystalline aluminosilicate, it is said that the electron valence of the aluminum-containing tetrahedron is balanced by the inclusion of cations within the crystal, and these cations can be exchanged with cations using known ion exchange technology. Can be exchanged. In providing the present invention, protons, M
Alkaline earth metals such as g, Ca, Sr, La, C
Those ion-exchanged with rare earth metals such as e or noble metals such as Pd can be used.
本発明を実施するに際し、アンモニア/フラン(モル比
)は2〜15モル、好ましくは4〜10モルを選ぶこと
ができる。When carrying out the present invention, the ammonia/furan (molar ratio) can be selected from 2 to 15 mol, preferably from 4 to 10 mol.
また、H2O7フラン(モル比)も2〜15モル、好ま
しくは4〜10モルを選ぶことが出来る。Further, the H2O7 furan (mole ratio) can also be selected from 2 to 15 moles, preferably from 4 to 10 moles.
さらに、反応温度は375〜550°Cを選ふことかで
きる。さらに好ましくは400〜500°Cを選ふこと
かできる。Furthermore, the reaction temperature can be selected from 375 to 550°C. More preferably, a temperature of 400 to 500°C can be selected.
さらにまた、反応圧力は特に限定するものではなく、減
圧、加圧下いずれも選ぶことができる。Furthermore, the reaction pressure is not particularly limited, and either reduced pressure or increased pressure can be selected.
触媒の使用量は、調製した触媒の活性を測定することに
より、通常の手法で求めることができる。The amount of catalyst to be used can be determined by a conventional method by measuring the activity of the prepared catalyst.
W/F CW−触媒重量(g) 、F :フラン流量(
moj2/Hr))で100〜600を選ぶことができ
るが、特に限定するものではない。W/F CW-catalyst weight (g), F: Furan flow rate (
moj2/Hr)) can be selected from 100 to 600, but is not particularly limited.
(実施例) 次に、本発明を実施例によりさらに詳しく説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
触媒調製I
Qブランドケイ酸ナトリウム水溶液(SiOz −29
,9重量%)150gに10%水酸化テトラプロピルア
ンモニウム水溶液180gを加え、さらに硫酸アルミニ
ウムCAI。(504)3・18H20)25gと水4
00gを加え、10分間撹拌した。Catalyst Preparation I Q brand sodium silicate aqueous solution (SiOz-29
, 9% by weight) was added with 180 g of a 10% tetrapropylammonium hydroxide aqueous solution, and further aluminum sulfate CAI. (504)3・18H20) 25g and water 4
00g was added and stirred for 10 minutes.
その後、その溶液を強撹拌しながら、10%硫酸を滴下
してpH]、0〜10.5に調整して均質なゲルを得た
。このゲルを撹拌機付1pオートクレーブに入れ、15
0°Cで30時間強撹拌した。室温に放冷した後、得ら
れた生成物を充分なイオン交換水で洗浄し、次いで、1
N硝酸水溶液中に室温で4時間浸漬濾過を4回繰り返し
、プロトンタイプにした。120“Cで乾燥した後、圧
縮成型し、さらに8〜14メソシユに破砕して触媒に供
した。Thereafter, while stirring the solution strongly, 10% sulfuric acid was added dropwise to adjust the pH to 0 to 10.5 to obtain a homogeneous gel. Place this gel in a 1P autoclave equipped with a stirrer,
The mixture was vigorously stirred at 0°C for 30 hours. After cooling to room temperature, the obtained product was washed with sufficient ion-exchanged water, and then 1
Filtration by immersion in an aqueous N nitric acid solution at room temperature for 4 hours was repeated four times to obtain a proton type. After drying at 120"C, it was compression molded and further crushed into 8 to 14 mesh pieces and used as a catalyst.
得られた触媒は、X線回折によりSM−5と同定された
。また、蛍光X線分析により求めたアルミナに対するシ
リカモル比(Si/Aで)は27であった。The obtained catalyst was identified as SM-5 by X-ray diffraction. Further, the molar ratio of silica to alumina (Si/A) determined by X-ray fluorescence analysis was 27.
触媒調製2
触媒調製1で調整した触媒をカチオン交換することによ
り、Mg−Mg−11Zs 、Ce−Ce−11ZS
、Pd−IIZSM−5をJ周整した。Catalyst Preparation 2 By cation-exchanging the catalyst prepared in Catalyst Preparation 1, Mg-Mg-11Zs, Ce-Ce-11ZS
, Pd-IIZSM-5 was J-sized.
カチオン交換はINの各金属塩[MgC1□、Ce(N
O:l) 3、PdC]□〕水溶液を触媒量の10倍量
を用い、80°Cで3〜4時間カチオン交換を行った。Cation exchange is performed for each metal salt of IN [MgC1□, Ce(N
O:l) 3, PdC]□] Using an aqueous solution 10 times the amount of the catalyst, cation exchange was performed at 80°C for 3 to 4 hours.
交換反応は4回繰り返した後、水洗、乾燥を行い、50
0 ’Cで3時間焼成した。ゲ−りを粉砕し、プレス、
成型後、8〜14メソシユに破砕して触媒に供した。After repeating the exchange reaction 4 times, washing with water and drying was performed.
Calcined at 0'C for 3 hours. Grind and press the Geeri.
After molding, it was crushed into 8 to 14 mesh pieces and used as a catalyst.
触媒調製3
511!ビーカー中で室温で撹拌することにより、下記
の組成を有する溶液Aおよび溶液Bを調整した。Catalyst Preparation 3 511! Solution A and solution B having the following compositions were prepared by stirring in a beaker at room temperature.
溶液A
Qブランド珪酸ナトリウム 1000 g水
1400 g溶液B
硫酸アルミニラ1、 32 g塩化すトリ
ウム 320g臭化テトラプDピルア
ンモニウム 135 g濃
硫酸 92 g
水 1900
g内容積10βの高速撹拌式ホモゲナイザー中で、溶液
Aおよび溶液Bを室温で混合して反応混合物(ゲル)を
調整した。Solution A Q brand sodium silicate 1000 g water
1400 g Solution B Aluminum sulfate 1, 32 g Thorium chloride 320 g Tetrap D pylammonium bromide 135 g Concentrated sulfuric acid 92 g Water 1900
A reaction mixture (gel) was prepared by mixing solution A and solution B at room temperature in a high-speed stirring homogenizer with an internal volume of 10β.
」二記混合物を内容積7βのオートクレーブに仕込め、
気相部を窒素ガス置換した後、オートクレーブを閉じ、
反応温度が140°Cとなるまで、回転数8Qrpmで
撹拌を行いつつ加熱した。次に、回転数を600rpm
とし、反応温度140°Cで36時間反応させた。室温
に放冷して得られた生成物を、触媒調製1と同様に処理
し触媒に供した。”Pour the mixture mentioned above into an autoclave with an internal volume of 7β,
After replacing the gas phase with nitrogen gas, close the autoclave and
The mixture was heated with stirring at a rotational speed of 8 Qrpm until the reaction temperature reached 140°C. Next, increase the rotation speed to 600 rpm.
The mixture was reacted for 36 hours at a reaction temperature of 140°C. The product obtained by cooling to room temperature was treated in the same manner as in Catalyst Preparation 1 and used as a catalyst.
得られた触媒はX線回折によりZSM−5と同定された
。また、蛍光X線分析により求めたアルミナに対するシ
リカモル比(Si/Aβ)は47であった。The obtained catalyst was identified as ZSM-5 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/Aβ) determined by X-ray fluorescence analysis was 47.
触媒調製4
触媒調製1と同様にして触媒を調整した。ただし、1で
オートクレーブに仕込む反応液は、次のとおり言周整し
た。Catalyst Preparation 4 A catalyst was prepared in the same manner as Catalyst Preparation 1. However, the reaction solution to be charged into the autoclave in step 1 was arranged as follows.
Qブランドケイ酸ナトリウム水溶液150gに硫酸アル
ミニウム5gと水400gを加え、さらに塩化トリエチ
ルアンモニウム50gを加え、10−10 =
分間撹拌した後、10%硫酸でpH11〜11.5に調
整した。5 g of aluminum sulfate and 400 g of water were added to 150 g of Q brand sodium silicate aqueous solution, and further 50 g of triethylammonium chloride was added. After stirring for 10-10 = minutes, the pH was adjusted to 11 to 11.5 with 10% sulfuric acid.
触媒調製1と同様にしてプロトン型にし、触媒に供した
。It was made into a proton form in the same manner as in Catalyst Preparation 1 and used as a catalyst.
得られた触媒は、X線回折によりZSM−5と同定され
た。また、蛍光X線分析により求めたアルミナに対する
シリカモル比(Si/A j! )は90であった。The obtained catalyst was identified as ZSM-5 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/A j!) determined by X-ray fluorescence analysis was 90.
触媒調製5
Qブランドケイ酸ナトリウム水溶液150gに硫酸アル
ミニウム10gと水400gを加え、さらにオクタメチ
レンジアミン30gを加え、10分間撹拌した。その後
、その溶液を強撹拌しながら、10%硫酸を滴下してp
H11〜11.5に調整して均質なゲルを保った。この
ゲルを撹拌機付1βオートクレーブに入れ、180°C
で100時間撹拌した。室温に放冷した後、得られた生
成物を充分なイオン交換水で洗浄し、触媒調製1と同様
にして破砕したプロトンタイプの触媒を得た。Catalyst Preparation 5 10 g of aluminum sulfate and 400 g of water were added to 150 g of Q brand sodium silicate aqueous solution, and further 30 g of octamethylene diamine was added, followed by stirring for 10 minutes. Then, while stirring the solution strongly, 10% sulfuric acid was added dropwise to p
A homogeneous gel was maintained by adjusting H11 to 11.5. This gel was placed in a 1β autoclave equipped with a stirrer and heated to 180°C.
The mixture was stirred for 100 hours. After cooling to room temperature, the obtained product was washed with sufficient ion-exchanged water, and a crushed proton type catalyst was obtained in the same manner as in Catalyst Preparation 1.
得られた触媒は、X線回折によりZSM−11と同定さ
れた。また、蛍光X線分析により求めたアルミナに対す
るシリカモル比(Si/Aβ)は50であった。The obtained catalyst was identified as ZSM-11 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/Aβ) determined by X-ray fluorescence analysis was 50.
実施例1
触媒調製1で調整した触媒(以下、023M−5と記す
)10gを内径20φの石英製反応管に充填し、常圧流
通法で実験を行った。触媒層を窒素気流下で外部の加熱
炉により昇温し、所定の温度(400’c)に到達して
からアンモニア及び水を所定量流し、30分処理を行っ
てから原料フランを導入し、反応を開始させた。アンモ
ニアはマスフロルメーターにより75 Nml/min
に、フラン及び水を定量ポンプによりそれぞれ1.7
g/Hr 、3.4 g/Hrに制御し導入した。Example 1 10 g of the catalyst prepared in Catalyst Preparation 1 (hereinafter referred to as 023M-5) was filled into a quartz reaction tube with an inner diameter of 20φ, and an experiment was conducted using a normal pressure flow method. The temperature of the catalyst layer is raised in an external heating furnace under a nitrogen stream, and after reaching a predetermined temperature (400'c), a predetermined amount of ammonia and water are poured into the catalyst layer, and after processing for 30 minutes, raw material furan is introduced. The reaction was started. Ammonia was measured at 75 Nml/min using a mass fluorometer.
1.7% each of furan and water using a metering pump.
g/Hr, 3.4 g/Hr.
反応管出口には、ドライアイス−エタノールで冷却した
l・ランプおよび水を入れた吸収層を直列に通し、反応
生成物を捕集した。反応生成物はOV−1をカラムとし
たキャピラリーカラムを用いて定量した。At the outlet of the reaction tube, a L lamp cooled with dry ice-ethanol and an absorption layer containing water were passed in series to collect the reaction product. The reaction product was quantified using a capillary column using OV-1 as a column.
反応成績は反応開始して3時間以」二経過した後、20
分反応生成物を捕集し、捕集した生成物の重量より求め
た。反応成績は次の計算式による。結果を表2に示す。The reaction results were measured at 20% after 3 hours had passed since the start of the reaction.
The reaction product was collected and determined from the weight of the collected product. The reaction results are calculated using the following formula. The results are shown in Table 2.
生産性−生成したピロール(g/Hr)/触媒量(χ)
実施例2〜3
実施例1と同様にして反応を行った。ただし、反応温度
を425°C(実施例2)及び450°C(実施例3)
とした。結果を表2に示す。Productivity - pyrrole produced (g/Hr)/catalyst amount (χ)
Examples 2-3 Reactions were carried out in the same manner as in Example 1. However, the reaction temperature was 425°C (Example 2) and 450°C (Example 3).
And so. The results are shown in Table 2.
実施例4〜6
触媒として触媒調製2で調整したカチオン交換触媒を1
0g充填し、反応温度400°Cで反応を行う以外は、
実施例1と同様に反応を行った。結果を表2に示す。Examples 4 to 6 The cation exchange catalyst prepared in Catalyst Preparation 2 was used as a catalyst.
Except for charging 0g and carrying out the reaction at a reaction temperature of 400°C,
The reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.
実施例7〜8
触媒として触媒調製3および4で調整したアルミナに対
するシリカモル比47および90の触媒を用いる以外は
、実施例4と同様に反応を行った。Examples 7 to 8 The reaction was carried out in the same manner as in Example 4, except that the catalysts prepared in Catalyst Preparations 3 and 4 with silica to alumina molar ratios of 47 and 90 were used as catalysts.
結果を表2に示す。The results are shown in Table 2.
実施例9
触媒として触媒調製5で調整したH2SM−11を用い
る以外は、実施例4と同様に反応を行った。Example 9 A reaction was carried out in the same manner as in Example 4, except that H2SM-11 prepared in Catalyst Preparation 5 was used as a catalyst.
結果を表2に示す。The results are shown in Table 2.
以下余白Margin below
Claims (1)
せてピロールを製造するに際し、アルミナに対するシリ
カモル比(Si/Al)が20以上であるペンタシル型
結晶性アルミノシリケートを触媒として用いることを特
徴とするピロールの製造法A pyrrole characterized in that a pentasil-type crystalline aluminosilicate having a silica to alumina molar ratio (Si/Al) of 20 or more is used as a catalyst when producing pyrrole by catalytically reacting furan and ammonia in the presence of water vapor. manufacturing method
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63131313A JPH01301658A (en) | 1988-05-31 | 1988-05-31 | Production of pyrrole |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63131313A JPH01301658A (en) | 1988-05-31 | 1988-05-31 | Production of pyrrole |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01301658A true JPH01301658A (en) | 1989-12-05 |
Family
ID=15055035
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63131313A Pending JPH01301658A (en) | 1988-05-31 | 1988-05-31 | Production of pyrrole |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01301658A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002193930A (en) * | 2000-12-27 | 2002-07-10 | Koei Chem Co Ltd | Production method of pyrroles |
CN106831527A (en) * | 2017-02-07 | 2017-06-13 | 铜仁学院 | Pyrroles and preparation method thereof |
-
1988
- 1988-05-31 JP JP63131313A patent/JPH01301658A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002193930A (en) * | 2000-12-27 | 2002-07-10 | Koei Chem Co Ltd | Production method of pyrroles |
CN106831527A (en) * | 2017-02-07 | 2017-06-13 | 铜仁学院 | Pyrroles and preparation method thereof |
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