JPH06343862A - Production of solid base catalyst - Google Patents
Production of solid base catalystInfo
- Publication number
- JPH06343862A JPH06343862A JP5138469A JP13846993A JPH06343862A JP H06343862 A JPH06343862 A JP H06343862A JP 5138469 A JP5138469 A JP 5138469A JP 13846993 A JP13846993 A JP 13846993A JP H06343862 A JPH06343862 A JP H06343862A
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- sodium
- catalyst
- solid base
- base catalyst
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007787 solid Substances 0.000 title abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 19
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 7
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 e.g. Chemical compound 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 150000003388 sodium compounds Chemical group 0.000 claims description 8
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000011324 bead Substances 0.000 abstract description 7
- 239000011521 glass Substances 0.000 abstract description 6
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000006317 isomerization reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、化学工業で使用される
固体塩基触媒の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a solid base catalyst used in the chemical industry.
【０００２】[0002]
【従来の技術】従来、炭化水素化合物の異性化、エステ
ル化、重合等に固体の塩基触媒を使用することが知られ
ている。例えば、講談社発行、田部浩三、野依良治著
「超強酸・超強塩基」１１５〜１２５頁（１９８０年）
には、各種の超強塩基触媒が記載されており、同書１２
２頁には、Ｎａ−ＭｇＯ系触媒の調製方法として、Ｍｇ
（ＮＯ3 ）2 の加水分解によって得たＭｇ（ＯＨ）2 を
アルゴン中、５５０℃で焼成したＭｇＯに金属ナトリウ
ムを接触させ５５０℃で加熱して０．４〜１．７ｗｔ％
のＮａを含むＭｇＯが得られたことが記載されている。2. Description of the Related Art Conventionally, it has been known to use a solid base catalyst for isomerization, esterification, polymerization and the like of hydrocarbon compounds. For example, Kozosha, Kozo Tabe, Ryoji Noyori, "Superacids / bases", pp. 115-125 (1980).
Describes various super strong base catalysts.
On page 2, as a method for preparing a Na-MgO-based catalyst, Mg
Mg (OH) 2 obtained by hydrolysis of (NO 3 ) 2 in argon was heated to 550 ° C., and metallic sodium was brought into contact with MgO to heat at 550 ° C. to 0.4-1.7 wt%.
It is described that MgO containing Na was obtained.
【０００３】[0003]
【発明が解決しようとする課題】ところで、このような
固体塩基触媒の形態は粉末である。そして、反応性を高
めるため比表面積を大きくしようとして粉末を細かく粉
砕している。このようにして、反応物質と触媒の活性点
との接触割合を高め反応効率を高めている。The solid base catalyst has a powder form. Then, in order to increase the reactivity, the powder is finely pulverized in order to increase the specific surface area. In this way, the contact ratio between the reactive substance and the active site of the catalyst is increased to enhance the reaction efficiency.
【０００４】しかし反面、粉末を細かくすればするほ
ど、反応終了後、触媒を反応物から分離するのが困難に
なる。微粉末の触媒の分離法としては、沈降法や濾過法
があるが、沈降法では時間がかかり、また濾過法でも目
の細かいフイルターを使用するので時間がかかる。特
に、反応溶液の粘度が高いと益々時間がかかり工業生産
には適さないという問題点がある。本発明の目的は、上
記の問題点を解決するものであり、比表面積が大きいた
め触媒としての効率がよく、かつ、反応に使用した後の
触媒の分離が容易である固体塩基触媒の製造方法を提供
することにある。On the other hand, however, the finer the powder, the more difficult it is to separate the catalyst from the reaction product after the reaction is completed. As a method for separating the fine powder catalyst, there are a sedimentation method and a filtration method. However, the sedimentation method takes time, and the filtration method also requires time because a fine filter is used. In particular, if the viscosity of the reaction solution is high, it takes more time and is not suitable for industrial production. The object of the present invention is to solve the above problems, the efficiency of the catalyst as a large specific surface area is large, and a method for producing a solid base catalyst which is easy to separate the catalyst after use in the reaction. To provide.
【０００５】[0005]
【課題を解決するための手段】本発明で使用される粒子
は、粒径０．０２〜１０ｍｍとされる。粒径が大きくな
ると、反応溶液中に十分分散し難くなり反応効率が悪く
なり、小さくなると分離性が低下する。粒子の形状は、
特に限定されるものではなく、例えば、ボール、ビー
ズ、バルーン等の球状；板状；針状等が挙げられる。粒
子の材質は、反応溶液や処理液で変質せず、触媒製造過
程での熱処理に耐えるものであれば、特に限定されるも
のではなく、例えば、アルミナ、ジルコニア、チタニア
等のセラミックス；ガラス等が挙げられる。The particles used in the present invention have a particle size of 0.02 to 10 mm. When the particle size is large, it becomes difficult to sufficiently disperse it in the reaction solution and the reaction efficiency is poor, and when it is small, the separability is deteriorated. The shape of the particles is
It is not particularly limited, and examples thereof include spherical shapes such as balls, beads, and balloons; plate shapes; needle shapes. The material of the particles is not particularly limited as long as it does not deteriorate in the reaction solution or the treatment solution and can withstand the heat treatment in the catalyst manufacturing process. For example, ceramics such as alumina, zirconia, titania; Can be mentioned.
【０００６】本発明で使用されるマグネシウム化合物
（ａ）は、一般式Ｍｇ（ＯＲ）2 で表されるマグネシウ
ムジアルコキシド、硝酸マグネシウムおよび塩化マグネ
シウムからなる群から選ばれる少なくとも１種である。
Ｒは炭素数１〜５のアルキル基を表すが、炭素数が大き
くなると溶液の安定性が低下して取扱が困難になるの
で、炭素は１〜５に限定される。Ｒの例としては、メチ
ル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル
基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチ
ル基等が挙げられる。一般式Ｍｇ（ＯＲ）2 で表される
化合物としては、例えば、マグネシウムジメトキシド、
マグネシウムジエトキシド等が挙げられる。The magnesium compound (a) used in the present invention is at least one selected from the group consisting of magnesium dialkoxide represented by the general formula Mg (OR) 2 , magnesium nitrate and magnesium chloride.
R represents an alkyl group having 1 to 5 carbon atoms, but the carbon number is limited to 1 to 5 because the stability of the solution decreases and the handling becomes difficult when the carbon number becomes large. Examples of R include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the compound represented by the general formula Mg (OR) 2 include magnesium dimethoxide,
Examples thereof include magnesium diethoxide.
【０００７】本発明で使用されるナトリウム化合物
（ｂ）は、一般式ＮａＯＲ1 で表されるナトリウムアル
コキシド、硝酸ナトリウムおよび塩化ナトリウムからな
る群から選ばれる少なくとも１種である。Ｒ1 は炭素数
１〜５のアルキル基を表すが、炭素数が大きくなると溶
液の安定性が低下して取扱が困難になるので、炭素は１
〜５に限定される。Ｒ1 の例としては、メチル基、エチ
ル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチ
ル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げ
られる。一般式ＮａＯＲ1 で表される化合物としては、
例えば、ナトリウムメトキシド、ナトリウムエトキシド
等が挙げられる。The sodium compound (b) used in the present invention is at least one selected from the group consisting of sodium alkoxide represented by the general formula NaOR 1 , sodium nitrate and sodium chloride. R 1 represents an alkyl group having 1 to 5 carbon atoms. However, if the carbon number becomes large, the stability of the solution decreases and the handling becomes difficult.
Limited to ~ 5. Examples of R 1 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. As the compound represented by the general formula NaOR 1 ,
For example, sodium methoxide, sodium ethoxide and the like can be mentioned.
【０００８】本発明の固体塩基触媒の製造方法は、粒径
０．０２〜１０ｍｍの粒子表面に、上記のマグネシウム
化合物（ａ）およびナトリウム化合物（ｂ）を含有する
溶液を塗布し、次いで乾燥し、さらに焼成する工程から
なる。In the method for producing a solid base catalyst of the present invention, a solution containing the above magnesium compound (a) and sodium compound (b) is applied to the surface of particles having a particle size of 0.02 to 10 mm, and then dried. And the step of further firing.
【０００９】上記溶液の溶媒としては、水または有機溶
媒が好ましい。有機溶媒としては、上記マグネシウム化
合物（ａ）およびナトリウム化合物（ｂ）を溶解するも
のであれば特に限定されるものではなく、例えば、メチ
ルアルコール、エチルアルコール、イソプロピルアルコ
ール等のアルコール類が挙げられる。The solvent for the above solution is preferably water or an organic solvent. The organic solvent is not particularly limited as long as it dissolves the magnesium compound (a) and the sodium compound (b), and examples thereof include alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol.
【００１０】前記溶液中のマグネシウム化合物（ａ）と
ナトリウム化合物（ｂ）のモル比は、マグネシウム化合
物（ａ）１モルに対して、ナトリウム化合物（ｂ）が
０．１モル以下が好ましい。ナトリウム化合物（ｂ）が
多くなると、触媒としての効率が低下し易くなる。The molar ratio of the magnesium compound (a) to the sodium compound (b) in the solution is preferably 0.1 mol or less of the sodium compound (b) with respect to 1 mol of the magnesium compound (a). If the amount of the sodium compound (b) increases, the efficiency as a catalyst tends to decrease.
【００１１】前記溶液の塗布方法は、既知の任意の方法
が可能であるが、例えば、前記の粒子を溶液中に浸漬し
た後、フイルターで粒子を濾別して粒子表面に溶液を塗
布する方法；粒子に溶液をスプレーで粉霧する方法等が
挙げられる。The method of applying the solution may be any known method, for example, a method of immersing the particles in the solution, filtering the particles with a filter, and applying the solution to the surface of the particles; A method of atomizing the solution with a spray can be mentioned.
【００１２】前記の乾燥の方法は特に限定されないが、
例えば、室温放置で乾燥する方法；公知の装置を使用し
て加熱乾燥する方法が挙げられる。The method of drying is not particularly limited,
For example, a method of drying at room temperature; a method of heating and drying using a known device can be mentioned.
【００１３】前記の焼成方法は特に限定されないが、例
えば、空気または窒素等のガス雰囲気中で３５０〜８０
０℃特に好ましくは３５０〜６５０℃で、２〜５時間か
けて行う方法が挙げられる。The firing method is not particularly limited, but is, for example, 350 to 80 in a gas atmosphere such as air or nitrogen.
A method of performing the treatment at 0 ° C. particularly preferably at 350 to 650 ° C. for 2 to 5 hours can be mentioned.
【００１４】[0014]
【作用】本発明で得られる固体塩基触媒は、粒子表面に
単なる溶液が塗布されている触媒と異なり、前記の特定
のマグネシウム化合物（ａ）およびナトリウム化合物
（ｂ）を含有する溶液が塗布され、乾燥され、焼成され
て得られたものであり、このようなゾル−ゲル工程を経
て触媒が担持されているので、該溶液状態のときに存在
していた溶媒やアルコキシドのアルコキシ基などが飛散
した後にできる孔が触媒層に多数存在する。従って、触
媒層は比表面積の大きい、多孔質の非晶質金属酸化物か
らなっており、このことにより、高い触媒効率が達成さ
れる。さらに、溶媒やアルコキシドのアルコキシ基を選
択することなどにより、上記の孔の径やその分布を制御
することも可能である。The solid base catalyst obtained by the present invention is different from a catalyst in which a solution is simply applied on the surface of particles, and a solution containing the specific magnesium compound (a) and sodium compound (b) is applied, It was obtained by being dried and calcined, and since the catalyst was supported through such a sol-gel process, the solvent and the alkoxy group of the alkoxide existing in the solution state were scattered. A large number of pores formed later are present in the catalyst layer. Therefore, the catalyst layer is made of a porous amorphous metal oxide having a large specific surface area, which achieves high catalyst efficiency. Further, it is possible to control the diameter and distribution of the pores by selecting the solvent or the alkoxy group of the alkoxide.
【００１５】また、本発明で得られる固体塩基触媒は、
粒径０．０２〜１０ｍｍの粒子表面に触媒成分が担持さ
れており、該粒子の径は触媒成分塗布前の粒径とほぼ同
じであるので、触媒使用後、触媒の分離が容易である。
例えば、沈降によって分離する場合には沈降速度が速
く、濾別する場合には比較的目の粗いフイルターやメッ
シュ等で効率よく分離できる。The solid base catalyst obtained in the present invention is
A catalyst component is carried on the surface of particles having a particle diameter of 0.02 to 10 mm, and the diameter of the particles is almost the same as the particle diameter before the coating of the catalyst component, so that the catalyst can be easily separated after the use of the catalyst.
For example, in the case of separation by sedimentation, the sedimentation speed is high, and in the case of filtration, separation can be efficiently performed with a relatively coarse filter or mesh.
【００１６】[0016]
【実施例】以下、本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【００１７】実施例１ ５００ｍｌのフラスコにメチルアルコールを３００ｍと
り、マグネシウムジメトキシド３０ｇ、硝酸ナトリウム
１．５ｇを加え１時間攪拌した。次に、粒径１ｍｍのガ
ラスビーズを１５０ｇ加え２時間攪拌後、ガラスビーズ
を目の開きが８５０μｍのメッシュで濾別した。得られ
たガラスビーズを１００℃で２４時間乾燥した。乾燥後
のガラスビーズを５００℃で３時間焼成して固体塩基触
媒を得た。得られた固体塩基触媒の比表面積はＢＥＴ法
で測定したところ０．５４ｍ2 ／ｇであった。次に、得
られた固体塩基触媒担持ガラスビーズ６ｇを用いて、１
−ヘキセン１０ｇを異性化した。反応終了後、目の開き
が８５０μｍのメッシュで固体塩基触媒を濾別した。固
体塩基触媒は１分以内に濾別され、容易に触媒を分離で
きた。濾別後の反応液を分析した結果、異性化率は８８
％であった。Example 1 300 ml of methyl alcohol was placed in a 500 ml flask, 30 g of magnesium dimethoxide and 1.5 g of sodium nitrate were added, and the mixture was stirred for 1 hour. Next, 150 g of glass beads having a particle diameter of 1 mm was added and stirred for 2 hours, and then the glass beads were filtered off with a mesh having an opening of 850 μm. The glass beads obtained were dried at 100 ° C. for 24 hours. The dried glass beads were calcined at 500 ° C. for 3 hours to obtain a solid base catalyst. The specific surface area of the obtained solid base catalyst was 0.54 m 2 / g as measured by the BET method. Next, using 6 g of the obtained solid base catalyst-supporting glass beads, 1
10 g of hexene were isomerized. After completion of the reaction, the solid base catalyst was filtered off with a mesh having openings of 850 μm. The solid base catalyst was filtered off within 1 minute and the catalyst could be easily separated. As a result of analyzing the reaction solution after separation by filtration, the isomerization rate was 88.
%Met.
【００１８】実施例２ 実施例１と同様にして、固体塩基触媒を得た。次に、得
られた固体塩基触媒６ｇを用いて、１−ぺンテン１０ｇ
を異性化した。反応終了後、目の開きが８５０μｍのメ
ッシュで固体塩基触媒を濾別した。固体塩基触媒は１分
以内に濾別され、容易に触媒を分離できた。濾別後の反
応液を分析した結果、異性化率は８２％であった。Example 2 A solid base catalyst was obtained in the same manner as in Example 1. Then, using 6 g of the obtained solid base catalyst, 10 g of 1-pentene
Was isomerized. After completion of the reaction, the solid base catalyst was filtered off with a mesh having openings of 850 μm. The solid base catalyst was filtered off within 1 minute and the catalyst could be easily separated. As a result of analyzing the reaction solution after separation by filtration, the isomerization rate was 82%.
【００１９】実施例３ 実施例１の硝酸ナトリウムに代えてナトリウムメトキシ
ドを０．８ｇ使用した他は、実施例と同様にして固体塩
基触媒を得た。得られた固体塩基触媒の比表面積はＢＥ
Ｔ法で測定したところ１．２８ｍ2 ／ｇであった。次
に、得られた固体塩基触媒６ｇを用いて、実施例１と同
様にして１−ヘキセンを異性化した。反応終了後、目の
開きが８５０μｍのメッシュで固体塩基触媒を濾別し
た。固体塩基触媒は１分以内に濾別され、容易に触媒を
分離できた。濾別後の反応液を分析した結果、異性化率
は８９％であった。Example 3 A solid base catalyst was obtained in the same manner as in Example 1 except that 0.8 g of sodium methoxide was used instead of sodium nitrate in Example 1. The specific surface area of the obtained solid base catalyst is BE
When measured by the T method, it was 1.28 m 2 / g. Next, using 6 g of the obtained solid base catalyst, 1-hexene was isomerized in the same manner as in Example 1. After completion of the reaction, the solid base catalyst was filtered off with a mesh having openings of 850 μm. The solid base catalyst was filtered off within 1 minute and the catalyst could be easily separated. As a result of analyzing the reaction solution after separation by filtration, the isomerization rate was 89%.
【００２０】比較例 ５００ｍｌのフラスコにメチルアルコールを３００ｍと
り、マグネシウムジメトキシド３０ｇ、硝酸ナトリウム
３ｇを加え１時間攪拌した。次に、攪拌下、２８重量％
のアンモニア水を徐々に加え沈殿を生成させた。生成し
た沈殿を吸引濾過した。得られた沈殿物を１００℃で２
４時間乾燥し、さらに５００℃で３時間焼成して固体塩
基触媒を得た。次に、得られた固体塩基触媒１ｇを用い
て、１−ヘキセン１０ｇを異性化した。反応終了後、触
媒を沈降させて分離しようと試みたが、２４時間静置し
ても反応液は懸濁していた。また、同じ反応液をポアー
サイズ５μｍの濾紙を使用して吸引濾過したが濾液は懸
濁していた。また、濾過の所要時間は約４時間であっ
た。濾別後の反応液を分析した結果、異性化率は８６％
であった。Comparative Example 300 ml of methyl alcohol was placed in a 500 ml flask, 30 g of magnesium dimethoxide and 3 g of sodium nitrate were added, and the mixture was stirred for 1 hour. Then, with stirring, 28% by weight
Ammonia water was gradually added to form a precipitate. The precipitate formed was suction filtered. The precipitate obtained is heated at 100 ° C for 2
It was dried for 4 hours and then calcined at 500 ° C. for 3 hours to obtain a solid base catalyst. Next, 10 g of 1-hexene was isomerized using 1 g of the obtained solid base catalyst. At the end of the reaction, an attempt was made to settle the catalyst and separate it, but the reaction solution was still suspended after standing for 24 hours. The same reaction solution was suction filtered using a filter paper with a pore size of 5 μm, but the filtrate was suspended. The time required for filtration was about 4 hours. As a result of analyzing the reaction solution after separation by filtration, the isomerization rate is 86%.
Met.
【００２１】[0021]
【発明の効果】本発明の固体塩基触媒の製造方法は前記
した通りであり、比表面積が大きいため触媒としての効
率がよく、かつ、反応に使用した後の触媒の分離が容易
である固体塩基触媒を製造することができる。また、本
発明の製造方法によって得られたＮａ2 Ｏ−ＭｇＯ系触
媒は、異性化、炭化水素のアルキル化、重合反応等の触
媒として効果的に使用でき、特に反応系の粘度が高い場
合に有用である。The method for producing a solid base catalyst of the present invention is as described above, and the solid base has a large specific surface area and thus is efficient as a catalyst, and the catalyst can be easily separated after being used in the reaction. A catalyst can be produced. Further, the Na 2 O-MgO-based catalyst obtained by the production method of the present invention can be effectively used as a catalyst for isomerization, alkylation of hydrocarbons, polymerization reaction, etc., especially when the viscosity of the reaction system is high. It is useful.
Claims (1)
（ａ）一般式Ｍｇ（ＯＲ）2(式中、Ｒは炭素数１〜５の
アルキル基）で表されるマグネシウムジアルコキシド、
硝酸マグネシウムおよび塩化マグネシウムからなる群か
ら選ばれる少なくとも１種のマグネシウム化合物、およ
び（ｂ）一般式ＮａＯＲ1 （式中、Ｒ1 は炭素数１〜５
のアルキル基）で表されるナトリウムアルコキシド、硝
酸ナトリウムおよび塩化ナトリウムからなる群から選ば
れる少なくとも１種のナトリウム化合物を含有する溶液
を塗布し、次いで乾燥し、さらに焼成することを特徴と
する固体塩基触媒の製造方法。1. A particle surface having a particle size of 0.02 to 10 mm,
(A) A magnesium dialkoxide represented by the general formula Mg (OR) 2 (wherein R is an alkyl group having 1 to 5 carbon atoms),
At least one magnesium compound selected from the group consisting of magnesium nitrate and magnesium chloride, and (b) the general formula NaOR 1 (wherein R 1 has 1 to 5 carbon atoms).
A base containing at least one sodium compound selected from the group consisting of sodium alkoxide, sodium nitrate and sodium chloride represented by the formula (1) above, then dried and further calcined. Method for producing catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5138469A JPH06343862A (en) | 1993-06-10 | 1993-06-10 | Production of solid base catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5138469A JPH06343862A (en) | 1993-06-10 | 1993-06-10 | Production of solid base catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06343862A true JPH06343862A (en) | 1994-12-20 |
Family
ID=15222782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5138469A Pending JPH06343862A (en) | 1993-06-10 | 1993-06-10 | Production of solid base catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06343862A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999007468A1 (en) * | 1997-08-07 | 1999-02-18 | Chisso Corporation | Basic catalysts and process for producing carbonyl compound derivatives |
| JP2015039663A (en) * | 2013-08-21 | 2015-03-02 | 株式会社Ihi | Method for manufacturing catalyst |
-
1993
- 1993-06-10 JP JP5138469A patent/JPH06343862A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999007468A1 (en) * | 1997-08-07 | 1999-02-18 | Chisso Corporation | Basic catalysts and process for producing carbonyl compound derivatives |
| US6632959B2 (en) | 1997-08-07 | 2003-10-14 | Chisso Corporation | Basic catalysts and process for producing carbonyl compound derivatives |
| JP2015039663A (en) * | 2013-08-21 | 2015-03-02 | 株式会社Ihi | Method for manufacturing catalyst |
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