JP6905380B2 - Method for manufacturing zeolite extruded product - Google Patents
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- JP6905380B2 JP6905380B2 JP2017078249A JP2017078249A JP6905380B2 JP 6905380 B2 JP6905380 B2 JP 6905380B2 JP 2017078249 A JP2017078249 A JP 2017078249A JP 2017078249 A JP2017078249 A JP 2017078249A JP 6905380 B2 JP6905380 B2 JP 6905380B2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 129
- 239000010457 zeolite Substances 0.000 title claims description 129
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 124
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 235000012438 extruded product Nutrition 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 238000001125 extrusion Methods 0.000 claims description 76
- 150000007524 organic acids Chemical class 0.000 claims description 60
- 239000004927 clay Substances 0.000 claims description 53
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 238000000465 moulding Methods 0.000 claims description 36
- 239000000314 lubricant Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 23
- 239000004014 plasticizer Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 12
- 239000005642 Oleic acid Substances 0.000 description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 206010058109 Hangnail Diseases 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 102000007641 Trefoil Factors Human genes 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000007605 air drying 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Press-Shaping Or Shaping Using Conveyers (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
本発明は、圧縮強度に優れたゼオライト押出成型体の製造方法に関する。 The present invention relates to a method for producing a zeolite extruded body having excellent compressive strength.
ゼオライトは、結晶性の多孔質アルミノシリケートおよび結晶性のメタロケイ酸塩の総称である。また、ゼオライトと同様の構造を持つ物質はゼオライト類似物質と呼ばれている。国際ゼオライト学会は、ゼオライトおよびゼオライト類似物質について「開かれた三次元ネットワークを形成する組成ＡＢn（ｎ≒２）の化合物で、Ａが４本、Ｂが２本の結合を持ち、骨格密度が２０．５以下の物質」と定義している（非特許文献１）。 Zeolites is a general term for crystalline porous aluminosilicates and crystalline metallosilicates. A substance having a structure similar to that of zeolite is called a zeolite-like substance. The International Zeolite Society has stated that zeolites and zeolite-like substances are " compounds of composition AB n (n≈2) that form an open three-dimensional network, with four bonds of A and two bonds of B, and a skeletal density. It is defined as "a substance of 20.5 or less" (Non-Patent Document 1).
ゼオライトおよびゼオライト類似物質（以下、ゼオライトおよびゼオライト類似物質を総称してゼオライトという。）は、その結晶構造に由来する特殊な細孔を有しており、この細孔を利用して様々な用途で使用されている。例えば、前記細孔に化合物が吸着することを利用して、脱水剤、脱臭剤などの用途で広く使用されている。また、前記細孔構造を分子篩として利用して、ガスの分離膜にも使用されている。更に、ゼオライトが有する固体酸性と前記分子篩機能を利用して、種々の触媒反応に使用されている。 Zeolites and zeolite-like substances (hereinafter, zeolite and zeolite-like substances are collectively referred to as zeolite) have special pores derived from their crystal structure, and these pores can be used in various applications. in use. For example, it is widely used in applications such as dehydrating agents and deodorants by utilizing the adsorption of compounds in the pores. Further, the pore structure is used as a molecular sieve and is also used as a gas separation membrane. Furthermore, it is used in various catalytic reactions by utilizing the solid acidity of zeolite and the molecular sieving function.
ゼオライトは、その用途に適した形状に成型されて使用される。例えば、吸着剤や触媒用としては押出成型や打錠成型等によって円柱状に成型される。特に、押出成型は打錠成型と比較して生産速度が速いので、生産コストが安くなる傾向がある。このため、前記用途において使用されるゼオライトは、押出成型で成型されたものが一般的である。 Zeolites are used after being molded into a shape suitable for the intended use. For example, for an adsorbent or a catalyst, it is formed into a columnar shape by extrusion molding, tableting molding or the like. In particular, extrusion molding has a higher production speed than tableting molding, so that the production cost tends to be lower. Therefore, the zeolite used in the above application is generally one that is molded by extrusion molding.
押出成型は、可塑化した原料を押出機でダイから押出し、所定の形状・寸法を付与する連続的な成型法である。ゼオライトを押出成型する場合、プラスチック等のように加熱等によって可塑化することは困難であるため、バインダーや溶媒と混合して捏和物にして可塑性を付与する。このような可塑性を付与した捏和物を押出機で押出して成型体にし、それを乾燥・焼成して、バインダーや溶媒等の成分を除去している。 Extrusion molding is a continuous molding method in which a plasticized raw material is extruded from a die with an extruder to give a predetermined shape and dimensions. When zeolite is extruded, it is difficult to plasticize it by heating or the like like plastic, so it is mixed with a binder or a solvent to make a kneaded product to impart plasticity. A kneaded product having such plasticity is extruded by an extruder to form a molded product, which is dried and fired to remove components such as a binder and a solvent.
このように、押出成型によって得られた成型体は、乾燥や焼成によりバインダーや溶媒が除去される際に空隙が生成するので、強度が低下することが多い。そこで、乾燥や焼成により除去されない無機バインダーを用いてゼオライトを押出成型する方法が種々提案されている。例えば、特許文献１には、ゼオライトの１種である結晶性シリコアルミノリン酸とアルミナ（バインダー）を押出成型して、ペレット状の成型体を得る方法が開示されている。また、特許文献２には、ゼオライト粉末、可塑剤及びシラノール基含有ポリシロキサンを含有する反応混合物を押出成型して、ハニカム状の成型体を得る方法が開示されている。しかし、これらの方法で得られる成型体は、より過酷な環境下で使用することを想定すると、十分な強度を有するとは云えない。 As described above, the molded product obtained by extrusion molding often has a low strength because voids are formed when the binder and the solvent are removed by drying or firing. Therefore, various methods have been proposed in which zeolite is extruded using an inorganic binder that is not removed by drying or calcination. For example, Patent Document 1 discloses a method of obtaining a pellet-shaped molded product by extrusion-molding crystalline silicoaluminophosphate, which is a kind of zeolite, and alumina (binder). Further, Patent Document 2 discloses a method for obtaining a honeycomb-shaped molded product by extrusion-molding a reaction mixture containing a zeolite powder, a plasticizer and a silanol group-containing polysiloxane. However, the molded products obtained by these methods cannot be said to have sufficient strength, assuming that they are used in a harsher environment.
本発明は、「従来のゼオライト押出成型体はその強度が低い」という課題を解決したものであり、特に圧縮強度に優れたゼオライト押出成型体を製造する方法を提供する。 The present invention solves the problem that "the strength of a conventional zeolite extruded body is low", and provides a method for producing a zeolite extruded body particularly excellent in compressive strength.
本発明の製造方法は、下記工程(１)〜(４)、
(１)ゼオライト、シリカ、可塑剤、および溶媒を混合して粘土を調製し、
(２)前記粘土に酸強度が低い有機酸を添加して成型用組成物を調製し、
(３)押出成型機の内部に滑剤をコートした後に前記成型用組成物を押出成型し、
(４)得られた押出成型体を４００〜１０００℃の温度で焼成する、
を有し、該粘土中のゼオライト含有量が粘土重量の２０〜６０質量であり、該粘土中のシリカ含有量が粘土重量の１〜３０質量％であり、該粘土に添加される酸強度が低い有機酸の添加量がゼオライトとシリカに含まれるＳｉ合計量のモル数に対して０.００１〜０.０１モルの範囲にあることを特徴とし、この構成によって従来の前記課題を解決したゼオライト押出成型体の製造方法である。
The production method of the present invention comprises the following steps (1) to (4),
(1) Clay is prepared by mixing zeolite, silica, plasticizer, and solvent.
(2) An organic acid having a low acid strength is added to the clay to prepare a molding composition.
(3) After coating the inside of the extrusion molding machine with a lubricant, the molding composition is extrusion-molded.
(4) The obtained extruded product is fired at a temperature of 400 to 1000 ° C.
The zeolite content in the clay is 20 to 60% by mass of the clay weight, the silica content in the clay is 1 to 30% by mass of the clay weight, and the acid strength added to the clay is The low amount of organic acid added is in the range of 0.001 to 0.01 mol with respect to the total number of moles of Si contained in the zeolite and silica, and this configuration solves the above-mentioned conventional problems. This is a method for manufacturing an extruded body.
本発明の製造方法は、前記成型用組成物中においてゼオライトおよびシリカの表面を酸強度が低い有機酸（以下、単に有機酸と云うことがある）で溶解した後に焼成することで、溶解したゼオライトとシリカの表面が互いに融着し、圧縮強度の高いゼオライト押出成型体を得ることができる。また、押出成形機の内部に滑剤をコートしてから押出成型することにより、生産性が劇的に向上する。さらに、好ましくは滑剤として有機酸を用いれば、押出成形の際に成型体の表面が有機酸に触れて成型体表面の溶解が進み、これが焼成されることで、粉化しにくい（耐摩耗性に優れた）ゼオライト押出成型体が得られる。 In the production method of the present invention, the surfaces of zeolite and silica in the molding composition are dissolved with an organic acid having a low acid strength (hereinafter, may be simply referred to as an organic acid) and then fired to dissolve the zeolite. And the surfaces of silica are fused to each other, and a zeolite extruded body having high compressive strength can be obtained. In addition, productivity is dramatically improved by coating the inside of the extrusion molding machine with a lubricant and then extrusion molding. Further, preferably, when an organic acid is used as a lubricant, the surface of the molded body comes into contact with the organic acid during extrusion molding to promote dissolution of the surface of the molded body, which is fired to prevent pulverization (wear resistance). An excellent) zeolite extrusion is obtained.
本発明の製造方法によれば、圧縮強度の高いゼオライト押出成型体が得られる。更に、滑剤を押出成型機の内部にコートすることによって、ゼオライト押出成型体の生産速度が劇的に向上する。さらに、滑剤として有機酸を用いることによって、耐摩耗性に優れたゼオライト押出成型体を得ることができる。 According to the production method of the present invention, a zeolite extruded product having high compressive strength can be obtained. Further, by coating the lubricant inside the extrusion molding machine, the production rate of the zeolite extrusion molding is dramatically improved. Further, by using an organic acid as a lubricant, a zeolite extruded body having excellent wear resistance can be obtained.
以下、本発明を実施形態に基づいて具体的に説明する。
〔本発明の製造方法〕
本発明の製造方法はゼオライト押出成型体の製造方法に関する。本発明の製造方法は、下記(１)〜(４)の工程を有し、該粘土中のゼオライト含有量が粘土重量の２０〜６０質量であり、該粘土中のシリカ含有量が粘土重量の１〜３０質量％であり、該粘土に添加される酸強度が低い有機酸の添加量がゼオライトとシリカに含まれるＳｉ合計量のモル数に対して０.００１〜０.０１モルの範囲にすることによって、ゼオライト押出成型体の生産速度を速めるとともに、得られるゼオライト押出成型体の強度を高める。
(１)ゼオライト、シリカ、可塑剤、および溶媒を混合して粘土を調製し、
(２)前記粘土に酸強度が低い有機酸を添加して成型用組成物を調製し、
(３)押出成型機の内部に滑剤をコートした後に前記成型用組成物を押出成型し、
(４)得られた押出成型体を４００〜１０００℃の温度で焼成する。
Hereinafter, the present invention will be specifically described based on the embodiments.
[Manufacturing method of the present invention]
The production method of the present invention relates to a method for producing an extruded zeolite product. The production method of the present invention has the following steps (1) to (4), the zeolite content in the clay is 20 to 60 mass by weight of the clay, and the silica content in the clay is the weight of the clay. The amount of organic acid added to the clay, which is 1 to 30% by mass and has a low acid strength, is in the range of 0.001 to 0.01 mol with respect to the total number of moles of Si contained in zeolite and silica. by, with increase the production rate of the zeolite extrudate body, increasing the strength of the resulting zeolite extruded molded body.
(1) Clay is prepared by mixing zeolite, silica, plasticizer, and solvent.
(2) An organic acid having a low acid strength is added to the clay to prepare a molding composition.
(3) After coating the inside of the extrusion molding machine with a lubricant, the molding composition is extrusion-molded.
(4) The obtained extruded product is fired at a temperature of 400 to 1000 ° C.
本発明の製造方法によって得られるゼオライト押出成型体の強度が向上する理由は、必ずしも明確ではないが、下記(Ａ)〜(Ｂ)のメカニズムによるものと推察される。
（Ａ）ゼオライトとシリカが有機酸で溶解され、成型用組成物中にＳｉが溶出する。
（Ｂ）その後、４００〜１０００℃で焼成されることにより、ゼオライトとシリカの表面が溶出したＳｉを介して融着する。
The reason why the strength of the zeolite extruded product obtained by the production method of the present invention is improved is not necessarily clear, but it is presumed to be due to the following mechanisms (A) to (B).
(A) Zeolite and silica are dissolved with an organic acid, and Si is eluted in the molding composition.
(B) After that, by firing at 400 to 1000 ° C., the surfaces of zeolite and silica are fused via the eluted Si.
更に、本発明の製造方法は、押出成型機の内部に滑剤をコートした後に成型用組成物を押出成型することによって、ゼオライト押出成型体の生産性が劇的に向上することも特徴の一つである。押出成型の技術分野において、滑剤は成型用組成物中に加えることが一般的であるが、本発明の製造方法では、押出成型機の内部に滑剤を予めコートする。ここで、押出成型機の内部とは、押出成型機を用いて押出成型する際に成型用組成物が接触する可能性がある全ての場所を指し、その一部分にでも滑剤を予めコートしておけば、本発明の効果を得ることができる。押出成型機内部の全部に滑剤を予めコートしておけば、本発明の効果を最大限得ることができるが、押出成型機内部の一部に滑剤を予めコートしても良い。特に押出成型する際に最も負荷のかかるダイ（金型）の内側に滑剤をコートしておくことによって、生産性が劇的に向上する（例えば、実施例１、比較例１等）。なお、この特長は、ゼオライトの成型のみならず、一般的な無機化合物の成型にも応用することができる。更に、滑剤として有機酸を用いることによって、耐摩耗性に優れたゼオライト押出成型体を得ることができる。これは、任意の形状に押し出された成型用組成物（押出成形体）の表面に有機酸がコートされ、その表面で前述の有機酸の効果が発揮されたためと考えられる。 Further, one of the features of the manufacturing method of the present invention is that the productivity of the zeolite extrusion molded product is dramatically improved by coating the inside of the extrusion molding machine with a lubricant and then extrusion molding the molding composition. Is. In the technical field of extrusion molding, the lubricant is generally added to the composition for molding, but in the production method of the present invention, the lubricant is pre-coated inside the extrusion molding machine. Here, the inside of the extrusion molding machine refers to all places where the molding composition may come into contact during extrusion molding using the extrusion molding machine, and even a part thereof should be coated with a lubricant in advance. For example, the effect of the present invention can be obtained. The effect of the present invention can be maximized if the entire inside of the extrusion molding machine is coated with the lubricant in advance, but a part of the inside of the extrusion molding machine may be coated with the lubricant in advance. In particular, by coating the inside of the die (mold), which is most loaded during extrusion molding, with a lubricant, productivity is dramatically improved (for example, Example 1, Comparative Example 1, etc.). This feature can be applied not only to the molding of zeolite but also to the molding of general inorganic compounds. Further, by using an organic acid as a lubricant, a zeolite extruded body having excellent wear resistance can be obtained. It is considered that this is because the surface of the molding composition (extruded molded product) extruded into an arbitrary shape is coated with an organic acid, and the effect of the above-mentioned organic acid is exhibited on the surface.
本発明の製造方法では、まず、ゼオライト、シリカ、可塑剤、および溶媒を混合して、粘土を調製する。本発明の製造方法において、ゼオライトは、従来公知のゼオライトを使用することができる。例えば、ＦＡＵ、ＭＦＩ、ＭＯＲ、ＣＨＡ構造等を有する従来公知のゼオライトを使用することができる（これらの構造は、Ｘ線回折測定により判別できる）。より具体的には、Ｙ型ゼオライト、ＺＳＭ−５、シリカライト、ＭＣＭ−４１、ＳＳＺ−１３等を使用することができる。 In the production method of the present invention, first, zeolite, silica, a plasticizer, and a solvent are mixed to prepare clay. In the production method of the present invention, a conventionally known zeolite can be used as the zeolite. For example, conventionally known zeolites having FAU, MFI, MOR, CHA structures and the like can be used (these structures can be discriminated by X-ray diffraction measurement). More specifically, Y-type zeolite, ZSM-5, silica light, MCM-41, SSZ-13 and the like can be used.
本発明の製造方法においては、ゼオライトの表面を有機酸で溶解してＳｉを溶出させるので、ゼオライトはＳｉを含むことが好ましく、そのＳｉの含有量はＳｉＯ２換算で、７０〜１００質量％の範囲にあることが好ましい。更に、そのＳｉの含有量は、９０〜１００質量％の範囲にあることが特に好ましい。そのＳｉの含有量が高くなるにつれ、ゼオライトの表面に露出するＳｉの量が増加するので、ゼオライトの表面からＳｉが溶出しやすくなり、最終的にゼオライト押出成型体の強度が向上する。また、ゼオライト中のＳｉの含有量が高くなると、ゼオライトが疎水性になる。ゼオライトが疎水性であれば、有機酸となじみやすくなり、有機酸を添加する効果がより顕著に表れるので、好ましい。 In the production method of the present invention, since the surface of the zeolite is dissolved with an organic acid to elute Si, the zeolite preferably contains Si, and the content of Si is 70 to 100% by mass in terms of SiO 2. It is preferably in the range. Further, the Si content is particularly preferably in the range of 90 to 100% by mass. As the content of Si increases, the amount of Si exposed on the surface of the zeolite increases, so that Si is easily eluted from the surface of the zeolite, and finally the strength of the zeolite extruded body is improved. Further, when the content of Si in the zeolite is high, the zeolite becomes hydrophobic. If the zeolite is hydrophobic, it becomes more compatible with the organic acid, and the effect of adding the organic acid becomes more remarkable, which is preferable.
粘土中に含まれるゼオライトは、粘土の重量に対して２０〜６０質量％含まれることが好ましく、３０〜６０質量％含まれることがより好ましく、４０〜６０質量％含まれることが特に好ましい。ゼオライトの特長を生かした用途に使用する場合、ゼオライトの含有量が高い方が、その効果も高くなるので、好ましい。 The zeolite contained in the clay is preferably contained in an amount of 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass with respect to the weight of the clay. When used for applications that take advantage of the features of zeolite, the higher the zeolite content, the higher the effect, which is preferable.
粘土中に含まれるシリカは、従来公知のシリカを使用することができる。例えば、シリカゾル、ヒュームドシリカ等を使用することができる。本発明の製造方法において、シリカの粒子径（ＲＳｉＯ２）は、ゼオライトの粒子径（ＲＺＥＯ）より小さいことが好ましく、ゼオライトの粒子径の１／１０以下がより好ましく、ゼオライトの粒子径の１／１００以下〜１／１０００以上であることが特に好ましい。シリカの粒子径がこの範囲にあると、ゼオライト粒子間の空隙にシリカが入り込み、これらの粒子が密に接触して接触面積が大きくなるので、ゼオライト押出成形体の圧縮強度が向上する。なお、本発明における粒子径は、レーザー回折式や動的散乱法を用いた粒度分布測定により得られる粒度分布（体積換算）から求めた平均粒子径を指す。シリカゾルを用いる場合は、シアーズ法により算出した平均粒子径を指す。 As the silica contained in the clay, conventionally known silica can be used. For example, silica sol, fumed silica and the like can be used. In the production method of the present invention, the silica particle size (R SiO2 ) is preferably smaller than the zeolite particle size (R ZEO ), more preferably 1/10 or less of the zeolite particle size, and 1 of the zeolite particle size. It is particularly preferably / 100 or less to 1/1000 or more. When the particle size of silica is in this range, silica enters the voids between the zeolite particles, and these particles come into close contact with each other to increase the contact area, so that the compressive strength of the zeolite extruded product is improved. The particle size in the present invention refers to an average particle size obtained from a particle size distribution (volume conversion) obtained by particle size distribution measurement using a laser diffraction method or a dynamic scattering method. When silica sol is used, it refers to the average particle size calculated by the Sears method.
粘土中に含まれるシリカは、粘土の重量に対して１〜３０質量％含まれることが好ましく、５〜２５質量％含まれることがより好ましく、１０〜２５質量％含まれることが特に好ましい。シリカの含有量が増えるとゼオライト押出成型体の圧縮強度は増加するが、ゼオライト押出成型体中のゼオライトの含有量が相対的に低下するので、ゼオライトの特長を生かした用途に使用する場合、その効果が低くなることがある。従って、粘土中のゼオライトの含有量とシリカの含有量はおのおの前記範囲内が好ましく、ゼオライトとシリカの各含有量が前記範囲内であれば、圧縮強度が高く、かつゼオライトによる効果も優れたゼオライト押出成型体を得ることができる。なお、本発明の製造方法では、シリカの含有量が前記範囲内で少ない数質量％であっても、ゼオライトから溶出したＳｉがゼオライトとシリカの表面を融着するので、圧縮強度に優れたゼオライト押出成型体を得ることができる。従って、本発明の製造方法によれば、ゼオライト含有量が高く、圧縮強度に優れたゼオライト押出成型体を得ることができる。 The silica contained in the clay is preferably contained in an amount of 1 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 25% by mass with respect to the weight of the clay. As the silica content increases, the compressive strength of the zeolite extruded body increases, but the zeolite content in the zeolite extruded body decreases relatively. The effect may be reduced. Therefore, the content of zeolite and the content of silica in clay are preferably within the above ranges, and when the contents of zeolite and silica are within the above ranges, zeolite having high compressive strength and excellent effect by zeolite. An extrusion molded product can be obtained. In the production method of the present invention, even if the silica content is as small as several mass% within the above range, Si eluted from the zeolite fuses the zeolite and the surface of the silica, so that the zeolite has excellent compressive strength. An extrusion molded product can be obtained. Therefore, according to the production method of the present invention, it is possible to obtain a zeolite extruded product having a high zeolite content and excellent compressive strength.
粘土中に含まれる可塑剤は、粉末に可塑性を付与できるものであり、かつ有機酸と接触しても変質しないものであれば良く、従来公知のものを使用することができる。例えば、メチルセルロース等のセルロース類、澱粉、ポリビニルアルコール等を使用することができる。より具体的には、ポリエチレングリコール、ポリビニルアルコール、メチルセルロース等を使用することができる。これらの可塑剤は、１種類でもよく、２種以上を混合して使用してもよい。 The plasticizer contained in the clay may be any as long as it can impart plasticity to the powder and does not deteriorate even when it comes into contact with an organic acid, and conventionally known plasticizers can be used. For example, celluloses such as methyl cellulose, starch, polyvinyl alcohol and the like can be used. More specifically, polyethylene glycol, polyvinyl alcohol, methyl cellulose and the like can be used. These plasticizers may be used alone or in admixture of two or more.
粘土中に含まれる可塑性の量は、粘土に可塑性が付与される量であれば良い。具体的には、例えば、粘土の重量に対して０.１〜１０質量％が好ましく、０.１〜７質量％がより好ましく、０.１〜５質量％が特に好ましい。可塑剤の含有量が前記範囲より多いと、焼成した際にゼオライト押出成型体中に空隙が生じやすくなり、その結果ゼオライト押出成型体の圧縮強度が低下するので好ましくない。 The amount of plasticity contained in the clay may be an amount that imparts plasticity to the clay. Specifically, for example, 0.1 to 10% by mass is preferable, 0.1 to 7% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable with respect to the weight of clay. If the content of the plasticizer is more than the above range, voids are likely to be generated in the zeolite extruded body at the time of firing, and as a result, the compressive strength of the zeolite extruded body is lowered, which is not preferable.
粘土中に含まれる溶媒は、可塑剤を分散させることができるものであれば良く、従来公知のものを使用することができる。例えば、水、有機溶媒等を使用することができる。より具体的には、水、エタノール、ポリエチレングリコール等を使用することができる。これらの溶媒は、１種類でもよく、２種以上を混合して用いてもよい。但し、２種以上を混合して使用する場合は、溶媒が分離しないように極性が近いものを選ぶことが好ましい。 The solvent contained in the clay may be any solvent as long as it can disperse the plasticizer, and conventionally known solvents can be used. For example, water, an organic solvent and the like can be used. More specifically, water, ethanol, polyethylene glycol and the like can be used. These solvents may be used alone or in admixture of two or more. However, when two or more kinds are mixed and used, it is preferable to select one having a similar polarity so that the solvent does not separate.
粘土中に含まれる溶媒の量は、可塑剤を分散させる量であれば良い。具体的には、例えば、粘土の重量に対して２０〜５０質量％が好ましく、２５〜４５質量％がより好ましく、３０〜４０質量％が特に好ましい。溶媒の含有量が前記範囲より多いと、焼成した際にゼオライト押出成型体中に空隙が生じやすくなり、その結果ゼオライト押出成型体の圧縮強度が低下するので、好ましくない。 The amount of the solvent contained in the clay may be an amount that disperses the plasticizer. Specifically, for example, 20 to 50% by mass is preferable, 25 to 45% by mass is more preferable, and 30 to 40% by mass is particularly preferable with respect to the weight of clay. If the content of the solvent is more than the above range, voids are likely to be generated in the zeolite extruded body at the time of firing, and as a result, the compressive strength of the zeolite extruded body is lowered, which is not preferable.
本発明の製造方法において、前記粘土は、例えば、ニーダー、ハイスピードミキサー、ミックスマラー等の従来公知の混合器を用いて調製することができる。具体的には、混合機中でゼオライト、シリカ、溶媒および可塑剤を混合する。この時、可塑剤は、事前に溶媒に溶解した状態で混合してもよい。混合が進むにつれて粘土が熱を持ち、その熱によって溶媒が蒸発することがあるので、このような場合は、溶媒を適時追加するか密閉して混合することが好ましい。粘土の処理量にもよるが、少なくとも１時間以上混合することで、各成分が分散した良質な粘土が得られる。 In the production method of the present invention, the clay can be prepared using, for example, a conventionally known mixer such as a kneader, a high-speed mixer, or a mix maller. Specifically, zeolite, silica, solvent and plasticizer are mixed in a mixer. At this time, the plasticizer may be mixed in a state of being previously dissolved in a solvent. As the mixing progresses, the clay becomes hot, and the heat may evaporate the solvent. In such a case, it is preferable to add the solvent in a timely manner or to mix the clay in a sealed manner. Although it depends on the amount of clay to be treated, mixing for at least 1 hour or more gives a high-quality clay in which each component is dispersed.
本発明の製造方法において、粘土を調製した後に有機酸を加えてさらに混合し、成型用組成物を調製する。粘土に有機酸を添加することによって、粘土に含まれるゼオライトとシリカの表面が溶解され、互いに融着するので、最終的に得られるゼオライト押出成型体の圧縮強度が向上する。有機酸に代えて無機酸等を添加すると、ゼオライトが過剰に溶解されてしまい、ゼオライト構造を維持できなくなるので好ましくない。従って、有機酸は弱酸であることが好ましく、特に、オレイン酸、リノール酸、乳酸、酪酸など、有機酸の中でも酸強度が低い有機酸を用いることが好ましい。酢酸やギ酸を有機酸として用いることもできるが、結晶性の低いゼオライトを用いる場合、酸によってゼオライト構造が破壊され、ゼオライト構造を維持できなくなる場合がある。 In the production method of the present invention, after preparing clay, an organic acid is added and further mixed to prepare a molding composition. By adding an organic acid to the clay, the surfaces of the zeolite and silica contained in the clay are dissolved and fused to each other, so that the compressive strength of the finally obtained zeolite extrusion molded product is improved. If an inorganic acid or the like is added instead of the organic acid, the zeolite is excessively dissolved and the zeolite structure cannot be maintained, which is not preferable. Therefore, the organic acid is preferably a weak acid, and in particular, it is preferable to use an organic acid having a low acid strength among organic acids such as oleic acid, linoleic acid, lactic acid, and butyric acid. Acetic acid and formic acid can be used as the organic acid, but when zeolite having low crystallinity is used, the zeolite structure may be destroyed by the acid and the zeolite structure may not be maintained.
成型用組成物中に含まれる有機酸の量は、成型用組成物に含まれるＳｉ（ゼオライト中に含まれるＳｉとシリカ中に含まれるＳｉの総量）のモル数に対して、０.００１〜０.０１モル％が好ましく、０.００１〜０.００８モル％がより好ましく、０.００１〜０.００６モル％が特に好ましい。有機酸の含有量が前記範囲より多いと、焼成した際にゼオライト押出成型体中に空隙が生じやすくなり、その結果ゼオライト押出成型体の圧縮強度が低下するので、好ましくない。有機酸の添加量が前記範囲より少ないと、ゼオライトとシリカの表面が十分に溶解されないためか、ゼオライト押出成型体の圧縮強度が低下する傾向がある。 The amount of organic acid contained in the molding composition is 0.001 to 0.001 to the number of moles of Si contained in the molding composition (total amount of Si contained in zeolite and Si contained in silica). 0.01 mol% is preferable, 0.001 to 0.008 mol% is more preferable, and 0.001 to 0.006 mol% is particularly preferable. If the content of the organic acid is more than the above range, voids are likely to be generated in the zeolite extruded body at the time of firing, and as a result, the compressive strength of the zeolite extruded body is lowered, which is not preferable. If the amount of the organic acid added is less than the above range, the compressive strength of the zeolite extruded product tends to decrease, probably because the surfaces of the zeolite and silica are not sufficiently dissolved.
なお、従来、オレイン酸やリノール酸を滑剤として使用することがあるが、本発明の製造方法においては、オレイン酸やリノール酸などの有機酸をゼオライトやシリカの表面を溶解するために用いる。有機酸の含有量が前記範囲では滑剤としての機能はあまり得られない。そこで、本発明の製造方法においては、滑剤を押出成型機内部にコートすることによって、押出成型機内部への成型用組成物の付着を防止する。 Conventionally, oleic acid or linoleic acid may be used as a lubricant, but in the production method of the present invention, an organic acid such as oleic acid or linoleic acid is used to dissolve the surface of zeolite or silica. When the content of the organic acid is in the above range, the function as a lubricant is not so much obtained. Therefore, in the production method of the present invention, the lubricant is coated on the inside of the extrusion molding machine to prevent the molding composition from adhering to the inside of the extrusion molding machine.
本発明の製造方法において、前記成型用組成物は、粘土を調製した混合器を引き続き使用して調製することができる。有機酸と粘土の混合は、有機酸の含有量にもよるが、３０〜５０℃の温度で行うことが好ましい。温度が低すぎる場合、粘土の可塑性が低下して押出成型する際の抵抗が増すので好ましくない。また、有機酸によるゼオライトとシリカの表面の溶解が進まず、最終的に得られるゼオライト押出成型体の圧縮強度が低下することがある。一方、温度が高すぎても、溶媒が蒸発しやすくなり、成型用組成物の内部で局所的に有機酸の濃度が高くなることがある。このような状態になると、有機酸によるゼオライトの溶解が過剰に進み、ゼオライトの結晶性が低下することがある。ゼオライトの結晶性が低下すると、ゼオライトの特長を生かした用途に使用する場合、その効果が低くなることがあるので、好ましくない。 In the production method of the present invention, the molding composition can be continuously prepared using a mixer in which clay is prepared. The mixing of the organic acid and the clay is preferably carried out at a temperature of 30 to 50 ° C., although it depends on the content of the organic acid. If the temperature is too low, the plasticity of the clay will decrease and the resistance during extrusion will increase, which is not preferable. In addition, the dissolution of the surfaces of zeolite and silica by the organic acid does not proceed, and the compressive strength of the finally obtained zeolite extrusion molded product may decrease. On the other hand, if the temperature is too high, the solvent tends to evaporate, and the concentration of the organic acid may locally increase inside the molding composition. In such a state, the dissolution of the zeolite by the organic acid proceeds excessively, and the crystallinity of the zeolite may decrease. When the crystallinity of zeolite is lowered, its effect may be lowered when it is used for an application utilizing the characteristics of zeolite, which is not preferable.
有機酸と粘土の混合は、有機酸の含有量にもよるが、粘土中に有機酸が均一に分散する程度まで行うことが好ましい。有機酸と粘土の分散が不十分な場合、有機酸に接触できないゼオライトやシリカが局所的に発生するので、本発明の効果が十分に得られなくなる。 The mixing of the organic acid and the clay depends on the content of the organic acid, but it is preferable to mix the organic acid to the extent that the organic acid is uniformly dispersed in the clay. If the dispersion of the organic acid and the clay is insufficient, zeolite or silica that cannot come into contact with the organic acid is locally generated, so that the effect of the present invention cannot be sufficiently obtained.
本発明の製造方法は、成型用組成物を押出成型機を用いて押出成型する。この押出成型は、押出成型機の内部に滑剤をコートした後に行う。滑剤は、常温で押出成型機内にコートでき、成型用組成物が壁面に付着するのを抑制する効果があるものであれば、従来公知の滑剤を使用することができる。滑剤は、常温で液体であるものが好ましく、例えば、不飽和脂肪酸類、グリセリン等を使用することができる。これらの滑剤を押出成形機内部にコートすると、押出成型機内部の摩擦抵抗が低下するためか、効率よく成型用組成物を押し出すことができる。コートする方法は、霧吹きや刷毛塗りなど制限されない。 In the production method of the present invention, the composition for molding is extruded using an extrusion molding machine. This extrusion molding is performed after coating the inside of the extrusion molding machine with a lubricant. As the lubricant, a conventionally known lubricant can be used as long as it can be coated in the extrusion molding machine at room temperature and has an effect of suppressing the molding composition from adhering to the wall surface. The lubricant is preferably liquid at room temperature, and for example, unsaturated fatty acids, glycerin and the like can be used. When these lubricants are coated on the inside of the extrusion molding machine, the composition for molding can be efficiently extruded probably because the frictional resistance inside the extrusion molding machine is reduced. The method of coating is not limited to spraying or brushing.
本発明の製造方法では、滑剤として有機酸を用いることができる。有機酸としては、前述のオレイン酸、リノール酸などの酸強度が低く、常温で液体である有機酸が好ましい。常温で固体の有機酸を用いる場合は、前述の滑剤（グリセリン等）に溶解させて用いることができる。押出成型機内部にコートされた有機酸は、滑剤の作用と共に、押出成形体の表面のゼオライトやシリカを溶解する作用を有する。押出成形機の内部を有機酸でコートした後に押し出された押出成形体は、その表面が有機酸でコートされ、これが焼成されることによって、焼成体表面の密度が高くなり、耐摩耗性に優れたゼオライト押出成型体が得られる。 In the production method of the present invention, an organic acid can be used as a lubricant. As the organic acid, an organic acid having a low acid strength such as the above-mentioned oleic acid and linoleic acid and which is liquid at room temperature is preferable. When an organic acid solid at room temperature is used, it can be used by dissolving it in the above-mentioned lubricant (glycerin or the like). The organic acid coated inside the extrusion molding machine has the action of a lubricant and the action of dissolving zeolite and silica on the surface of the extrusion molding body. The surface of the extruded body extruded after coating the inside of the extrusion molding machine with an organic acid is coated with an organic acid, and when this is fired, the density of the surface of the fired body becomes high and the abrasion resistance is excellent. A zeolite extrusion molded product is obtained.
本発明の製造方法において、押出成型機は、従来公知のものを使用することができる。例えば、ディスクペレッター、スクリュー式押出成型機等の押出成型機を用いて行うことができる。これらの押出成型機には、穴が開いたダイがセットされている。成型用組成物を押出成型機からダイを通して押し出すことで、様々な形状の押出成型体が得られる。押出成型体は、ハニカム状、柱状といった押出成型で得られる一般的な形状を取ることができる。本発明の製造方法においては、押出成型体の形状は、柱状であることが好ましく、例えば、円柱状、三つ葉状、四葉状、マカロニ状等であることがより好ましい。特に、三つ葉状、四葉状といった形状が複雑でダイとの接触面積が大きい形状の押出成型体を調製する際に、本発明は有効に作用する。 In the production method of the present invention, a conventionally known extrusion molding machine can be used. For example, it can be carried out by using an extrusion molding machine such as a disc pelleter or a screw type extrusion molding machine. These extruders are set with dies with holes. By extruding the molding composition from an extruder through a die, extrusions of various shapes can be obtained. The extruded body can take a general shape obtained by extrusion molding such as honeycomb shape and columnar shape. In the production method of the present invention, the shape of the extruded body is preferably columnar, and more preferably columnar, trefoil, four-leaf, macaroni, or the like. In particular, the present invention works effectively when preparing an extruded body having a complicated shape such as a three-leaf shape or a four-leaf shape and a large contact area with a die.
本発明の製造方法において、押出成型機で押し出された押出成型体は、４００〜１０００℃で焼成される。押出成型体を上記温度範囲で焼成することよって、押出成型体から溶媒や可塑剤などが除去されるとともに、ゼオライトとシリカが有機酸で溶出したＳｉを介して融着し、ネットワークを形成する。これにより、最終的に得られるゼオライト押出成型体の圧縮強度が向上する。 In the production method of the present invention, the extruded body extruded by the extrusion molding machine is fired at 400 to 1000 ° C. By firing the extruded product in the above temperature range, solvents, plasticizers, and the like are removed from the extruded product, and zeolite and silica are fused via Si eluted with an organic acid to form a network. As a result, the compressive strength of the finally obtained zeolite extruded product is improved.
本発明の製造方法において、前述の押出成型体は、必要によって乾燥した後に押出成型を行ってもよい。押出成型直後の押出成型体は、溶媒、可塑剤等が含まれた状態であり、その表面がわずかに濡れているので、押出成型体が互いに引っ付きやすい。押出成型体が互いに引っ付いた状態で焼成すると、接着面がそのまま固化してしまい、割れかけの原因となる。そこで、押出成型体を焼成する前に乾燥して溶媒等を除去することで、押出成型体が互いに引っ付き難くなり、これを焼成しても割れかけが起こりにくくなる。 In the production method of the present invention, the above-mentioned extruded product may be extruded after being dried, if necessary. Immediately after extrusion molding, the extruded body contains a solvent, a plasticizer, and the like, and the surface thereof is slightly wet, so that the extruded bodies tend to stick to each other. If the extruded bodies are fired while they are attracted to each other, the adhesive surface will solidify as it is, causing cracking. Therefore, by drying the extruded body before firing to remove the solvent and the like, the extruded bodies are less likely to stick to each other, and even if the extruded body is fired, cracking is less likely to occur.
本発明の製造方法において、押出成型体の乾燥方法は、従来公知の方法を使用することができる。例えば、風乾、減圧乾燥、加熱乾燥等の方法を使用することができる。押出成型体の乾燥温度は２０〜１５０℃が好ましい。この温度範囲でゆっくりと押出成型体を乾燥することで、押出成型体内部に空隙ができ難くなり、その結果、最終的に得られるゼオライト押出成型体の圧縮強度が向上する。 In the production method of the present invention, a conventionally known method can be used as the method for drying the extruded product. For example, methods such as air drying, vacuum drying, and heat drying can be used. The drying temperature of the extruded product is preferably 20 to 150 ° C. By slowly drying the extruded body in this temperature range, it becomes difficult for voids to be formed inside the extruded body, and as a result, the compressive strength of the finally obtained zeolite extruded body is improved.
本発明の製造方法において、押出成型体の焼成方法は、従来公知の方法を使用することができる。例えば、マッフル炉、環状炉、トンネル炉、キルン等を使用して焼成することができる。焼成温度は、４００〜１０００℃が好ましく、５００〜７００℃がより好ましい。焼成温度が前記範囲より高すぎると、ゼオライト構造が壊れやすくなり、ゼオライトの結晶性が低下する可能性がある。焼成温度が前記範囲より低すぎても、ゼオライトとシリカの表面が有機酸により溶出したＳｉを介して融着し難くなり、その結果得られるゼオライト押出成型体の圧縮強度が低下する。 In the production method of the present invention, a conventionally known method can be used as the method for firing the extruded product. For example, firing can be performed using a muffle furnace, a ring furnace, a tunnel furnace, a kiln, or the like. The firing temperature is preferably 400 to 1000 ° C, more preferably 500 to 700 ° C. If the calcination temperature is too high above the above range, the zeolite structure is fragile and the crystallinity of the zeolite may decrease. Even if the firing temperature is lower than the above range, the surfaces of the zeolite and silica are difficult to fuse with each other via Si eluted by the organic acid, and the compressive strength of the resulting zeolite extruded body is lowered.
また、押出成型体の仕込量にもよるが、前記温度範囲で少なくとも１時間以上焼成することが好ましく、３〜１２時間焼成することが特に好ましい。押出成型体を十分な時間焼成することで、ゼオライトとシリカの表面が有機酸により溶出したＳｉを介して融着しやすくなり、最終的に得られるゼオライト押出成型体の圧縮強度が向上する。 Further, although it depends on the amount of the extruded product charged, it is preferable to bake at least 1 hour or more in the above temperature range, and it is particularly preferable to bake for 3 to 12 hours. By firing the extruded body for a sufficient time, the surfaces of the zeolite and silica are easily fused via Si eluted by the organic acid, and the compressive strength of the finally obtained zeolite extruded body is improved.
さらに、前記焼成温度に到達するまでの昇温速度は、２００℃／hr以下が好ましく、１００℃／hr以下がより好ましい。昇温速度が高すぎると、押出成型体中に含まれる有機物が急激に酸化され多量のＣＯ２が急激に発生するので、押出成型体の内圧が上がり、割れかけの原因となるので好ましくない。 Further, the rate of temperature rise until the firing temperature is reached is preferably 200 ° C./hr or less, more preferably 100 ° C./hr or less. If the rate of temperature rise is too high, the organic matter contained in the extruded body is rapidly oxidized and a large amount of CO 2 is rapidly generated, which increases the internal pressure of the extruded body and causes cracking, which is not preferable.
本発明の実施例を比較例と共に以下に示す。なお、本発明はこれらの実施例に限定されない。実施例において、圧縮強度は以下のように測定した。実施例において、各成分の含有量は仕込量から算出した値である。なお、各成分を従来公知の方法で定量してもよい。例えば、シリカの含有量であれば、ＩＣＰ発光分光分析や蛍光Ｘ線分析等で測定することができる。
＜圧壊強度測定＞
ゼオライト押出成型体の側面に圧力がかかるように、ゼオライト押出成形体を木屋式硬度計（藤原製作所社製：043019-A）の試料台にセットして加圧し、試料が圧壊したときの圧力を圧壊強度とした。表１に示す測定値はこの測定を１０回して得られた値の平均値である（単位：Ｎ）。
Examples of the present invention are shown below together with comparative examples. The present invention is not limited to these examples. In the examples, the compressive strength was measured as follows. In the examples, the content of each component is a value calculated from the charged amount. In addition, each component may be quantified by a conventionally known method. For example, the silica content can be measured by ICP emission spectroscopic analysis, fluorescent X-ray analysis, or the like.
<Measurement of crush strength>
Set the zeolite extruded body on the sample stand of a Kiya type hardness tester (manufactured by Fujiwara Seisakusho Co., Ltd .: 043019-A) and pressurize it so that pressure is applied to the side surface of the zeolite extruded body. The crushing strength was used. The measured values shown in Table 1 are the average values of the values obtained by repeating this measurement 10 times (unit: N).
〔実施例１〕
Ｙ型ゼオライト（ＪＧＣ Ｃ＆Ｃ社製品：Ｓｉ含有量７５質量％（ＳｉＯ２換算）、粒子径７μｍ）１１２５ｇ(ドライ換算)に可塑剤のポリビニルアルコール(酢ビポバール製ＪＰ−１８)を３０ｇ添加し、ニーダーで５分混合した。その後、シリカゾル(ＪＧＣ Ｃ＆Ｃ社製品：カタロイドＳ−２０ＬＥ、Ｓｉ含有量２０質量％（ＳｉＯ２換算）、粒子径１８ｎｍ) １８７５ｇを少しずつニーダーに入れながら、シリカゾルを全て添加した後、室温まで冷却した。更に、メチルセルロース(信越化学製品：チローゼMH6009P4)を３０ｇ添加し、１時間混練（混合）して粘土を得た。この時、粘土中の溶媒の含有量は３８.７質量％であった。
この粘土に、有機酸（オレイン酸：関東化学製品）を１５ｇ添加し、５分混合して成型用組成物を調製した。
次に、押出成型する前に滑剤としてオレイン酸を、ダイと押出成型機内部に吹き付けた後、前記成形用組成物を押出して押出成形体を調製した。得られた押出成形体の形状は２mmの円柱状であった。この押出成型性を以下の基準で評価した。結果を表１に示す。
良好：◎(成型が良好で、成型能力が高い。押出時間１５分以内)
普通：○(成型が良好で、成型能力が中程度。押出時間１５〜３０分)
不十分：△(成型できるが、成型能力が低い。押出時間３０分以上)
不良：×(成型できない)
得られた押出成形体を１２０℃の乾燥機で１２時間乾燥し、ついでマッフル焼成炉で６００℃、３時間焼成して、ゼオライト押出成形体を得た。得られたゼオライト押出成形体は、その表面にささくれ等はなく、粉化も少なかった。
このゼオライト押出成形体について、木屋式硬度計を使用して圧壊強度を測定した。結果を表１に示す。
[Example 1]
Y-type zeolite (JGC C & C product: Si content 75% by mass (SiO 2 equivalent), particle size 7 μm) 1125 g (dry equivalent), 30 g of plasticizer polyvinyl alcohol (JP-18 made by Vam & Poval vinegar) was added, and kneader Was mixed for 5 minutes. Then, while adding 1875 g of silica sol (JGC C & C product: Cataloid S-20LE, Si content 20% by mass (SiO 2 equivalent), particle size 18 nm) little by little to the kneader, all the silica sol was added and then cooled to room temperature. .. Further, 30 g of methyl cellulose (Shin-Etsu Chemical product: Tyrose MH6009P4) was added and kneaded (mixed) for 1 hour to obtain clay. At this time, the content of the solvent in the clay was 38.7% by mass.
To this clay, 15 g of an organic acid (oleic acid: Kanto Chemical Co., Inc.) was added and mixed for 5 minutes to prepare a molding composition.
Next, oleic acid was sprayed as a lubricant into the die and the inside of the extrusion molding machine before extrusion molding, and then the molding composition was extruded to prepare an extrusion molded product. The shape of the obtained extruded body was a 2 mm columnar shape. This extrusion moldability was evaluated according to the following criteria. The results are shown in Table 1.
Good: ◎ (Good molding, high molding capacity. Extrusion time within 15 minutes)
Normal: ○ (Good molding, medium molding capacity. Extrusion time 15 to 30 minutes)
Insufficient: △ (Can be molded, but the molding capacity is low. Extrusion time is 30 minutes or more)
Defective: × (cannot be molded)
The obtained extruded product was dried in a dryer at 120 ° C. for 12 hours, and then calcined in a muffle furnace at 600 ° C. for 3 hours to obtain a zeolite extruded product. The obtained zeolite extruded product had no hangnail on its surface and had little pulverization.
The crush strength of this zeolite extruded body was measured using a Kiya-type hardness tester. The results are shown in Table 1.
〔実施例２〕
押出成型する前に、滑材としてオレイン酸を押出成形機内部に吹き付けたこと以外は、実施例１と同様にしてゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 2]
A zeolite extrusion molded product was obtained in the same manner as in Example 1 except that oleic acid was sprayed into the extrusion molding machine as a lubricant before extrusion molding. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例３〕
押出成型する前に、滑材としてオレイン酸をダイに吹き付けたこと以外は、実施例１と同様にしてゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 3]
A zeolite extrusion molded product was obtained in the same manner as in Example 1 except that oleic acid was sprayed onto the die as a lubricant before extrusion molding. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例４〕
焼成温度を４５０℃とした以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 4]
A zeolite extruded product was obtained in the same manner as in Example 1 except that the firing temperature was 450 ° C. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例５〕
焼成温度を８００℃とした以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 5]
A zeolite extruded body was obtained in the same manner as in Example 1 except that the firing temperature was set to 800 ° C. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例６〕
有機酸として、オレイン酸の代わりに乳酸を６ｇ添加したこと以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 6]
A zeolite extruded product was obtained in the same manner as in Example 1 except that 6 g of lactic acid was added instead of oleic acid as the organic acid. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例７〕
ゼオライトとして、ＺＳＭ−５型ゼオライト（ＪＧＣ Ｃ＆Ｃ社製品：Ｓｉ含有量９５質量％（ＳｉＯ２換算）、粒子径３μｍ）１１２５ｇ(ドライ換算)を用いた以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 7]
Zeolite in the same manner as in Example 1 except that ZSM-5 type zeolite (JGC C & C product: Si content 95% by mass (SiO 2 equivalent), particle size 3 μm) 1125 g (dry equivalent) was used as the zeolite. An extruded body was obtained. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例８〕
滑剤としてグリセリンを、ダイと押出成型機内部に吹き付けた以外は、実施例６と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 8]
A zeolite extrusion molded product was obtained in the same manner as in Example 6 except that glycerin was sprayed into the die and the inside of the extrusion molding machine as a lubricant. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例９〕
有機酸として、オレイン酸を３０ｇ添加したこと以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 9]
A zeolite extruded product was obtained in the same manner as in Example 1 except that 30 g of oleic acid was added as the organic acid. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔実施例１０〕
有機酸として、オレイン酸を６ｇ添加したこと以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。
[Example 10]
A zeolite extruded product was obtained in the same manner as in Example 1 except that 6 g of oleic acid was added as the organic acid. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1.
〔比較例１〕
有機酸および滑剤を使用しなかったこと以外は、実施例１と同様にして、成型用組成物を押出成形機に投入したが、押出成形機が詰まり押出成形体を得ることができなかった。
[Comparative Example 1]
The molding composition was put into the extrusion molding machine in the same manner as in Example 1 except that no organic acid and lubricant were used, but the extrusion molding machine was clogged and an extrusion molded product could not be obtained.
〔比較例２〕
滑剤を使用しなかったこと以外は、実施例１と同様にして、成型用組成物を押出成形機に投入したが、押出成形機が詰まり押出成形体を得ることができなかった。
[Comparative Example 2]
The molding composition was put into the extrusion molding machine in the same manner as in Example 1 except that no lubricant was used, but the extrusion molding machine was clogged and an extrusion molded product could not be obtained.
〔比較例３〕
有機酸を使用しなかったこと以外は、実施例１と同様にして、ゼオライト押出成形体を得た。また、実施例１と同様の方法で強度を測定した。結果を表１に示す。滑剤としてオレイン酸をダイと押出成型機内部に吹き付けた後に押出成形を行ったので、成型体表面はささくれ等が無く、粉化も少ないが、押出成型前の粘土に有機酸を添加していないので、成型体の圧縮強度が低い。
[Comparative Example 3]
A zeolite extruded product was obtained in the same manner as in Example 1 except that no organic acid was used. Moreover, the strength was measured by the same method as in Example 1. The results are shown in Table 1. Since oleic acid was sprayed into the die and the inside of the extrusion molding machine as a lubricant and then extrusion molding was performed, the surface of the molded body was not rubbed and powdered less, but no organic acid was added to the clay before extrusion molding. Therefore, the compressive strength of the molded product is low.
Claims (2)
(１)ゼオライト、シリカ、可塑剤、および溶媒を混合して粘土を調製し、
(２)前記粘土に酸強度が低い有機酸を添加して成型用組成物を調製し、
(３)押出成型機の内部に滑剤をコートした後に前記成型用組成物を押出成型し、
(４)得られた押出成型体を４００〜１０００℃の温度で焼成する、
を有するゼオライト成型体の製造方法であって、
前記粘土中のゼオライト含有量が粘土重量の２０〜６０質量であり、
前記粘土中のシリカ含有量が粘土重量の１〜３０質量％であり、
前記粘土に添加される酸強度が低い有機酸の添加量がゼオライトとシリカに含まれるＳｉ合計量のモル数に対して０.００１〜０.０１モルの範囲にある、
ことを特徴とするゼオライト押出成型体の製造方法。 The following steps (1) to (4),
(1) Clay is prepared by mixing zeolite, silica, plasticizer, and solvent.
(2) An organic acid having a low acid strength is added to the clay to prepare a molding composition.
(3) After coating the inside of the extrusion molding machine with a lubricant, the molding composition is extrusion-molded.
(4) The obtained extruded product is fired at a temperature of 400 to 1000 ° C.
It is a manufacturing method of a zeolite molded body having
The zeolite content in the clay is 20 to 60 mass by weight of the clay.
The silica content in the clay is 1 to 30% by mass based on the weight of the clay.
The amount of the organic acid having a low acid strength added to the clay is in the range of 0.001 to 0.01 mol with respect to the total number of moles of Si contained in the zeolite and silica.
A method for producing an extruded zeolite product.
The method for producing a zeolite extrusion molded product according to claim 1, wherein an organic acid is used as a lubricant to be coated inside the extrusion molding machine.
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