JP2006321700A - Method of manufacturing zeolite and zeolite manufactured by using the method - Google Patents
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- 239000010457 zeolite Substances 0.000 title claims abstract description 67
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 66
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 28
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- 235000013405 beer Nutrition 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 36
- 239000011734 sodium Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000005909 Kieselgur Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- -1 aluminum aluminate Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 26
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 239000010802 sludge Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000002956 ash Substances 0.000 description 4
- 239000010883 coal ash Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、ゼオライトの製造方法に関し、廃材、特に、ビール製造の濾過工程で用いられた廃ケイソウ土を用いてゼオライトを製造する方法と該方法により製造されたゼオライトに関する。 The present invention relates to a method for producing zeolite, and more particularly, to a method for producing zeolite using waste materials, particularly waste diatomaceous earth used in a filtration process of beer production, and a zeolite produced by the method.
最近、産業用として製造される純度の高い合成ゼオライトに代わり、副産物の再利用に配慮し、石炭灰、製紙スラッジ焼却灰、活性汚泥焼却灰等の副産物を原料としたゼオライトの製造方法が提案されている。こうした提案は、例えば、石炭灰等の副産物を、単なる廃棄物として爾後処理を行うのではなく、再利用（リサイクル）を行うための一手段としてなされたものであり、ゼオライトの生成と同時に副産物の再利用としての役目も果たしている。
ところで、前述した石炭灰、製紙スラッジ焼却灰、活性汚泥焼却灰等と同様に、ビール製造工程において濾過材として用いられるケイソウ土の爾後処理が問題となっている。この種の廃ケイソウ土の廃棄処理は、主に、埋め立て又は農業資材としての利用に止まっていた。 By the way, as in the case of coal ash, paper sludge incineration ash, activated sludge incineration ash, and the like described above, diatomaceous earth post-treatment used as a filtering material in a beer production process has become a problem. This type of waste diatomaceous earth has mainly been used as landfill or agricultural material.
本発明者は、ビール濾過工程における廃材の処理に際し、特に、そのケイソウ土に、ゼオライトの合成に必要なシリカ成分が多量に含まれていることに着目し、これを原材料としてゼオライトの合成が可能となるのではないかと推測した。 The present inventor pays attention to the fact that the diatomaceous earth contains a large amount of silica components necessary for the synthesis of zeolite in the processing of waste materials in the beer filtration process, and it is possible to synthesize zeolite using this as a raw material. I guessed it would be.
そこで、濾過工程で用いた廃ケイソウ土を使用してゼオライトを製造することを試みた。この際、廃ケイソウ土は、ビール製造における濾過工程で用いられ、麦芽、ホップ等の残渣が溜まっており、これらがゼオライトの製造において、不都合なものであるとして、洗浄除去することが必要であるとの考えから、アルカリ洗浄工程を入れていたが、その際、有効なケイソウ土そのものも比較的多量に喪失してしまうという問題が生じた。
その結果、ゼオライトへの変換効率が低下すると共に、アルカリ洗浄によって流出した有機物、ケイソウ土を含む廃液の二次処理を行わなくてはならないという問題が生じる。Therefore, an attempt was made to produce zeolite using the waste diatomaceous earth used in the filtration step. At this time, the waste diatomaceous earth is used in a filtration process in beer production, and residues such as malt and hops are accumulated, and it is necessary to wash and remove them because they are inconvenient in the production of zeolite. In view of this, an alkali washing process was included, but at that time, there was a problem that a relatively large amount of effective diatomaceous earth itself was lost.
As a result, the conversion efficiency to zeolite is reduced, and there arises a problem that a secondary treatment of waste liquid containing organic matter and diatomaceous earth that has flowed out by alkali washing must be performed.
本発明は、こうしたビール製造工程において使用された廃ケイソウ土を用いて、ゼオライト、特に、石油の接触分解に優れた触媒機能や分子篩作用を持つ純度の高いＸ型ゼオライトと、洗剤用ビルダーや気体の乾燥等に用いられているＡ型ゼオライトを効率良く製造できるゼオライトの製造方法と該方法により得られたゼオライトを提供することを目的とする The present invention uses a waste diatomaceous earth used in such a beer manufacturing process, zeolite, in particular, a high purity X-type zeolite having a catalytic function and molecular sieve action excellent in catalytic cracking of petroleum, a builder for detergent and gas It is an object of the present invention to provide a zeolite production method capable of efficiently producing A-type zeolite used for drying and the like, and a zeolite obtained by the method
本発明にかかるゼオライトの製造方法は、上記目的を達成するために、ゼオライトの製造方法であって、
ビール製造の濾過工程で用いた、有機物を含むケイソウ土を、事前処理を行わずに、そのまま水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得、
アルミン酸ナトリウム、又はアルミを含む廃棄物を水酸化ナトリウム水溶液に溶解させたアルミン酸ナトリウム水溶液を得、
これらのケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液を混合して所定時間攪拌して熟成させ、
この混合溶液を所定時間加熱処理して得られた合成物を固液分離、水洗を繰返し行い、得られたケーキを乾燥させる、
という手段を講じたものである。In order to achieve the above object, a method for producing a zeolite according to the present invention is a method for producing a zeolite,
The diatomaceous earth containing organic matter used in the filtration process of beer production was dissolved in a sodium hydroxide aqueous solution as it was without performing a pretreatment to obtain a sodium silicate aqueous solution.
Obtain a sodium aluminate aqueous solution in which waste containing aluminum aluminate or aluminum is dissolved in an aqueous sodium hydroxide solution,
These sodium silicate aqueous solution and sodium aluminate aqueous solution are mixed and aged for a predetermined time,
The composite obtained by heat-treating this mixed solution for a predetermined time is subjected to solid-liquid separation, repeated washing with water, and the resulting cake is dried.
This is a measure taken.
また、本発明にかかるゼオライトは、上記方法によって製造されたものである。 The zeolite according to the present invention is produced by the above method.
本発明によれば、ビール製造工程において発生する廃ケイソウ土をベースにし、濾過工程において含有することになったビール製造工程で発生した有機物を前処理することなく、そのままの状態で水酸化ナトリウム水溶液に溶解してケイ酸ナトリウム水溶液を得、他方、アルミン酸ナトリウム又は廃棄物アルミ材を水酸化ナトリウム水溶液に溶解させて得たアルミン酸ナトリウム水溶液とを混合させ、水熱合成させることで、原材料の洗浄喪失もなく、製造効率良く、且つ、優れた機能を有するＸ型ゼオライト、Ａ型ゼオライトを製造できるに至ったものである。 According to the present invention, based on waste diatomaceous earth generated in a beer manufacturing process, an aqueous sodium hydroxide solution is used as it is without pretreatment of organic substances generated in the beer manufacturing process that are supposed to be contained in the filtration process. To obtain a sodium silicate aqueous solution, while mixing sodium aluminate aqueous solution obtained by dissolving sodium aluminate or waste aluminum material in sodium hydroxide aqueous solution and hydrothermally synthesizing it. This has led to the production of X-type zeolite and A-type zeolite having no loss of washing, high production efficiency, and excellent functions.
本発明の実施に際しては、上記ケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液の混合溶液におけるＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝１〜４であり、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝３〜５であり、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝４０〜８０であり、上記加熱処理が少なくとも０．５時間施されるのが好ましい。In carrying out the present invention, the molar ratio of Na 2 O and SiO 2 in the mixed solution of the sodium silicate aqueous solution and the sodium aluminate aqueous solution is Na 2 O / SiO 2 = 1 to 4, and SiO 2 and Al 2 The molar ratio of O 3 is SiO 2 / Al 2 O 3 = 3 to 5, the molar ratio of H 2 O and Na 2 O is H 2 O / Na 2 O = 40 to 80, and the heating The treatment is preferably carried out for at least 0.5 hours.
この場合、図３のＸ線回折図に示されるように、Ｘ型ゼオライト由来のピークが高く表れたゼオライトが得られた。このことは、図６に示す試薬Ｘ型ゼオライトのＸ線回折図に示されるピーク特性と対することで明らかである。 In this case, as shown in the X-ray diffraction diagram of FIG. 3, a zeolite having a high peak derived from the X-type zeolite was obtained. This is clear by comparing with the peak characteristics shown in the X-ray diffraction pattern of the reagent X-type zeolite shown in FIG.
また、上記ケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液の混合溶液におけるＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝１〜４であり、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝１．５〜２．５であり、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝４０〜６０であり、上記加熱処理が少なくとも０．５時間行われるのが好ましい。
この方法によれば、図４のＸ線回折図のグラフに示すように、Ａ型ゼオライト由来のピークが高く表れたゼオライトが得られた。このことは、図７に示す試薬Ａ型ゼオライトのＸ線回折図に示されるピーク特性と対することで明らかである。Moreover, the molar ratio of Na 2 O and SiO 2 in the mixed solution of the sodium silicate aqueous solution and the sodium aluminate aqueous solution is Na 2 O / SiO 2 = 1 to 4, and the molar ratio of SiO 2 and Al 2 O 3 Is SiO 2 / Al 2 O 3 = 1.5 to 2.5, the molar ratio of H 2 O and Na 2 O is H 2 O / Na 2 O = 40 to 60, and the above heat treatment Is preferably carried out for at least 0.5 hours.
According to this method, as shown in the graph of the X-ray diffraction diagram of FIG. 4, a zeolite having a high peak derived from the A-type zeolite was obtained. This is clear by comparing with the peak characteristics shown in the X-ray diffraction pattern of the reagent A-type zeolite shown in FIG.
本発明の実施例１について説明すると、次の通りである。
まず、出発原料は、ビール製造工程における濾加工程で用いた有機物を含む廃ケイソウ土であり、これを４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得た。
次いで、アルミン酸ナトリウムを、４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてアルミン酸ナトリウム水溶液を得た。
それらケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液をＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝１．５、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝３．０、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝５０となるよう混合しゲルを得た。Example 1 of the present invention will be described as follows.
First, the starting material was waste diatomaceous earth containing organic substances used in the filtration process in the beer production process, and this was dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium silicate aqueous solution.
Next, sodium aluminate was dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium aluminate aqueous solution.
In these sodium silicate aqueous solution and sodium aluminate aqueous solution, the molar ratio of Na 2 O and SiO 2 is Na 2 O / SiO 2 = 1.5, and the molar ratio of SiO 2 and Al 2 O 3 is SiO 2 / Al 2. A gel was obtained by mixing so that O 3 = 3.0 and the molar ratio of H 2 O to Na 2 O was H 2 O / Na 2 O = 50.
このゲル状試料をフッ素樹脂製三角フラスコ（３００ｍｌ）に入れ、スターラーを用いて、一晩攪拌（熟成）させた。
この後、フラスコ上部を冷却管で封じ、ホットプレート上にて５時間加熱処理して合成した。尚、熟成時には、フラスコ上部をシリコン栓にて封じた。This gel sample was placed in a fluororesin Erlenmeyer flask (300 ml) and stirred (aged) overnight using a stirrer.
Thereafter, the upper part of the flask was sealed with a cooling tube, and synthesized by heat treatment on a hot plate for 5 hours. During aging, the upper part of the flask was sealed with a silicon stopper.
更に、得られた合成物を遠心分離機にかけて、遠心洗浄し、上澄液のｐＨが１０になるまで水洗を繰返し、得られたケーキを１０５℃で一晩乾燥してゼオライトの測定試料とした。
この試料のＸ線回折測定を行ったところ、図１のＸ線回折図にＸで示す如きピークが見られた。Ｐ型ゼオライトのピークも少量含まれるが、図６の試薬Ｘ型ゼオライトのＸ線回折図と対比するとわかるように、Ｘ型ゼオライトが生成されたことがわかる。Furthermore, the obtained composite was centrifuged and centrifuged, and the supernatant was repeatedly washed with water until the pH of the supernatant reached 10. The resulting cake was dried at 105 ° C. overnight to obtain a zeolite measurement sample. .
When X-ray diffraction measurement was performed on this sample, a peak as indicated by X was observed in the X-ray diffraction diagram of FIG. Although a small amount of the peak of P-type zeolite is contained, it can be seen that X-type zeolite was produced, as can be seen from comparison with the X-ray diffraction pattern of the reagent X-type zeolite in FIG.
この実施例でも、まず、出発原料は、ビール製造工程における濾加工程で用いた有機物を含む廃ケイソウ土であり、これを４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得た。
次いで、アルミン酸ナトリウムを、４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてアルミン酸ナトリウム水溶液を得た。
それらケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液をＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝２．０、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝５．０、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝５０となるよう混合し、ゲルを得た。Also in this example, first, the starting material is waste diatomaceous earth containing organic substances used in the filtration step in the beer production step, and this was dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium silicate aqueous solution. .
Next, sodium aluminate was dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium aluminate aqueous solution.
These sodium silicate aqueous solution and sodium aluminate aqueous solution had a molar ratio of Na 2 O to SiO 2 of Na 2 O / SiO 2 = 2.0, and a molar ratio of SiO 2 to Al 2 O 3 of SiO 2 / Al 2. The gel was obtained by mixing so that O 3 = 5.0 and the molar ratio of H 2 O and Na 2 O was H 2 O / Na 2 O = 50.
このゲル状試料をフッ素樹脂製三角フラスコ（３００ｍｌ）に入れ、スターラーを用いて、一晩攪拌（熟成）させた。
この後、フラスコ上部を冷却管で封じ、ホットプレート上にて５時間加熱処理して合成した。尚、熟成時には、フラスコ上部をシリコン栓にて封じた。This gel sample was placed in a fluororesin Erlenmeyer flask (300 ml) and stirred (aged) overnight using a stirrer.
Thereafter, the upper part of the flask was sealed with a cooling tube, and synthesized by heat treatment on a hot plate for 5 hours. During aging, the upper part of the flask was sealed with a silicon stopper.
更に、得られた合成物を遠心分離機にかけて、遠心洗浄し、上澄液のｐＨが１０になるまで水洗を繰り返し、得られたケーキを１０５℃で一晩乾燥してゼオライトの測定試料とした。
この試料のＸ線回折測定を行ったところ、図２のＸ線回折図にＸで示す如きピークが見られた。Ｐ型ゼオライトのピークも少量含まれるが、これを、図６に示す試薬Ｘ型ゼオライトのＸ線回折図と対比するとわかるように、試薬Ｘ型ゼオライトなみの純度のＸ型ゼオライトが生成されたことがわかる。Furthermore, the obtained composite was centrifuged and centrifuged, and the supernatant was repeatedly washed with water until the pH of the supernatant reached 10. The resulting cake was dried overnight at 105 ° C. to obtain a zeolite measurement sample. .
When X-ray diffraction measurement was performed on this sample, a peak as indicated by X was observed in the X-ray diffraction diagram of FIG. A small amount of P-type zeolite peak is also contained, but as can be seen from the X-ray diffraction pattern of the reagent X-type zeolite shown in FIG. I understand.
この実施例においても、まず、出発原料は、ビール製造工程における濾加工程で用いた有機物を含む廃ケイソウ土であり、これを４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得た。
次いで、アルミン酸ナトリウムを、４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてアルミン酸ナトリウム水溶液を得た。
それらケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液をＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝２．５、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝４．０、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝５０となるよう混合しゲルを得た。Also in this example, first, the starting material is waste diatomaceous earth containing an organic substance used in the filtration step in the beer production step, and this is dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium silicate aqueous solution. It was.
Next, sodium aluminate was dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium aluminate aqueous solution.
In these sodium silicate aqueous solution and sodium aluminate aqueous solution, the molar ratio of Na 2 O and SiO 2 is Na 2 O / SiO 2 = 2.5, and the molar ratio of SiO 2 and Al 2 O 3 is SiO 2 / Al 2. A gel was obtained by mixing so that O 3 = 4.0 and the molar ratio of H 2 O to Na 2 O was H 2 O / Na 2 O = 50.
このゲル状試料をフッ素樹脂製三角フラスコ（３００ｍｌ）に入れ、スターラーを用いて、一晩攪拌（熟成）させた。この後、フラスコ上部を冷却管で封じ、ホットプレート上にて、５時間加熱処理して合成した。尚、熟成時には、フラスコ上部をシリコン栓にて封じた。 This gel sample was placed in a fluororesin Erlenmeyer flask (300 ml) and stirred (aged) overnight using a stirrer. Thereafter, the upper part of the flask was sealed with a cooling tube, and was synthesized by heat treatment on a hot plate for 5 hours. During aging, the upper part of the flask was sealed with a silicon stopper.
更に、得られた合成物を遠心分離機にかけて、遠心洗浄し、上澄液のｐＨが１０になるまで水洗を繰り返し、得られたケーキを１０５℃で一晩乾燥してゼオライトの測定試料とした。
この試料のＸ線回折測定を行ったところ、図３のＸ線回折図にＸで示す如きピークが見られた。これを、図６に示す試薬Ｘ型ゼオライトのＸ線回折図と対比すると判るように、試薬Ｘ型ゼオライトなみの純度のＸ型ゼオライトが生成されたことがわかる。Furthermore, the obtained composite was centrifuged and centrifuged, and the supernatant was repeatedly washed with water until the pH of the supernatant reached 10. The resulting cake was dried overnight at 105 ° C. to obtain a zeolite measurement sample. .
When X-ray diffraction measurement was performed on this sample, a peak as indicated by X was observed in the X-ray diffraction diagram of FIG. As can be seen from comparison with the X-ray diffraction pattern of the reagent X-type zeolite shown in FIG. 6, it can be seen that X-type zeolite having a purity similar to that of the reagent X-type zeolite was produced.
この実施例においても、まず、出発原料は、ビール製造工程における濾加工程で用いた有機物を含む廃ケイソウ土であり、これを４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得た。
そして、この実施例では、アルミン酸ナトリウムに代えて、廃棄物アルミ材、ここではアルミ含有汚泥を用いて、４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてアルミン酸ナトリウム水溶液を得た。
それらケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液をＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝２．５、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝２．５、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝５０となるよう混合しゲルを得た。Also in this example, first, the starting material is waste diatomaceous earth containing an organic substance used in the filtration step in the beer production step, and this is dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium silicate aqueous solution. It was.
In this example, instead of sodium aluminate, a waste aluminum material, here, aluminum-containing sludge was used and dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium aluminate aqueous solution.
In these sodium silicate aqueous solution and sodium aluminate aqueous solution, the molar ratio of Na 2 O and SiO 2 is Na 2 O / SiO 2 = 2.5, and the molar ratio of SiO 2 and Al 2 O 3 is SiO 2 / Al 2. The mixture was mixed so that the molar ratio of O 3 = 2.5 and H 2 O and Na 2 O was H 2 O / Na 2 O = 50 to obtain a gel.
このゲル状試料をフッ素樹脂製三角フラスコ（３００ｍｌ）に入れ、スターラーを用いて、一晩攪拌（熟成）させた。この後、フラスコ上部を冷却管で封じ、ホットプレート上にて、この実施例では、２時間加熱処理して合成した。尚、熟成時には、フラスコ上部をシリコン栓にて封じた。 This gel sample was placed in a fluororesin Erlenmeyer flask (300 ml) and stirred (aged) overnight using a stirrer. Thereafter, the upper part of the flask was sealed with a cooling tube, and in this example, it was synthesized by heat treatment for 2 hours on a hot plate. During aging, the upper part of the flask was sealed with a silicon stopper.
更に、得られた合成物を遠心分離機にかけて、遠心洗浄し、上澄液のｐＨが１０になるまで水洗を繰り返し、得られたケーキを１０５℃で一晩乾燥してゼオライトの測定試料とした。
この試料のＸ線回折測定を行ったところ、図４のＸ線回折図にＡで示す如きピークが見られた。これを、図７に示す試薬Ａ型ゼオライトのＸ線回折図と対比すると判るように、試薬Ａ型ゼオライトなみの純度のＡ型ゼオライトが生成されたことがわかる。Furthermore, the obtained composite was centrifuged and centrifuged, and the supernatant was repeatedly washed with water until the pH of the supernatant reached 10. The resulting cake was dried overnight at 105 ° C. to obtain a zeolite measurement sample. .
When X-ray diffraction measurement was performed on this sample, a peak as indicated by A was observed in the X-ray diffraction diagram of FIG. As can be seen from comparison with the X-ray diffraction pattern of the reagent A type zeolite shown in FIG. 7, it can be seen that the A type zeolite having the purity similar to that of the reagent A type zeolite was produced.
この実施例においても、まず、出発原料は、ビール製造工程における濾加工程で用いた有機物を含む廃ケイソウ土であり、これを４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得た。
そして、この実施例では、アルミン酸ナトリウムに代えて、廃棄物アルミ材、ここではアルミ含有汚泥を用いて、４ｍｏｌ／Ｌ水酸化ナトリウム水溶液に溶解させてアルミン酸ナトリウム水溶液を得た。
それらケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液をＮａ２ＯとＳｉＯ２のモル比が、Ｎａ２Ｏ／ＳｉＯ２＝１．５、ＳｉＯ２とＡｌ２Ｏ３のモル比が、ＳｉＯ２／Ａｌ２Ｏ３＝１．５、Ｈ２ＯとＮａ２Ｏとのモル比が、Ｈ２Ｏ／Ｎａ２Ｏ＝５０となるよう混合しゲルを得た。Also in this example, first, the starting material is waste diatomaceous earth containing an organic substance used in the filtration step in the beer production step, and this is dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium silicate aqueous solution. It was.
In this example, instead of sodium aluminate, a waste aluminum material, here, aluminum-containing sludge was used and dissolved in a 4 mol / L sodium hydroxide aqueous solution to obtain a sodium aluminate aqueous solution.
In these sodium silicate aqueous solution and sodium aluminate aqueous solution, the molar ratio of Na 2 O and SiO 2 is Na 2 O / SiO 2 = 1.5, and the molar ratio of SiO 2 and Al 2 O 3 is SiO 2 / Al 2. A gel was obtained by mixing such that the molar ratio of O 3 = 1.5 and the H 2 O to Na 2 O ratio was H 2 O / Na 2 O = 50.
このゲル状試料をフッ素樹脂製三角フラスコ（３００ｍｌ）に入れ、スターラーを用いて、一晩攪拌（熟成）させた。この後、フラスコ上部を冷却管で封じ、ホットプレート上にて、２時間加熱処理して合成した。尚、熟成時には、フラスコ上部をシリコン栓にて封じた。 This gel sample was placed in a fluororesin Erlenmeyer flask (300 ml) and stirred (ripened) overnight using a stirrer. Thereafter, the upper part of the flask was sealed with a cooling tube, and was synthesized by heat treatment on a hot plate for 2 hours. During aging, the upper part of the flask was sealed with a silicon stopper.
更に、得られた合成物を遠心分離機にかけて、遠心洗浄し、上澄液のｐＨが１０になるまで水洗を繰り返し、得られたケーキを１０５℃で一晩乾燥してゼオライトの測定試料とした。
この試料のＸ線回折測定を行ったところ、図５のＸ線回折図にＡで示す如きピークが見られた。これを、図７に示す試薬Ａ型ゼオライトのＸ線回折図と対比すると判るように、Ａ型ゼオライトが生成されたことがわかる。Furthermore, the obtained composite was centrifuged and centrifuged, and the supernatant was repeatedly washed with water until the pH of the supernatant reached 10. The resulting cake was dried overnight at 105 ° C. to obtain a zeolite measurement sample. .
When X-ray diffraction measurement was performed on this sample, a peak as indicated by A was observed in the X-ray diffraction diagram of FIG. As can be seen from comparison with the X-ray diffraction pattern of the reagent A-type zeolite shown in FIG. 7, it can be seen that the A-type zeolite was produced.
本発明の活用例として、Ｘ型ゼオライト、Ａ型ゼオライト等のゼオライトを効率良く製造できるので、優れた機能を持つゼオライトを安価に提供できるところから、触媒機能、吸着機能、分子篩機能等を生かして、種々の工業分野において利用可能である。 As an application example of the present invention, zeolites such as X-type zeolite and A-type zeolite can be produced efficiently, so that zeolite having excellent functions can be provided at low cost, making use of the catalytic function, adsorption function, molecular sieve function, etc. It can be used in various industrial fields.
Claims (4)
ビール製造の濾過工程で用いられた、有機物を含む廃ケイソウ土を、事前処理を行わずに、そのまま水酸化ナトリウム水溶液に溶解させてケイ酸ナトリウム水溶液を得、
アルミン酸ナトリウム、又はアルミを含む廃棄物を水酸化ナトリウム水溶液に溶解させたアルミン酸ナトリウム水溶液を得、
これらのケイ酸ナトリウム水溶液とアルミン酸ナトリウム水溶液を混合して所定時間攪拌して熟成させ、
この混合溶液を所定時間加熱処理して得られた合成物を固液分離、水洗を繰返し行い、得られたケーキを乾燥させる、
ことを特徴とするゼオライトの製造方法。A method for producing zeolite, comprising:
The waste diatomaceous earth containing organic matter used in the filtration process of beer production was dissolved in an aqueous sodium hydroxide solution as it was without pretreatment to obtain an aqueous sodium silicate solution.
Obtain a sodium aluminate aqueous solution in which waste containing aluminum aluminate or aluminum is dissolved in an aqueous sodium hydroxide solution,
These sodium silicate aqueous solution and sodium aluminate aqueous solution are mixed and aged for a predetermined time,
The composite obtained by heat-treating this mixed solution for a predetermined time is subjected to solid-liquid separation, repeated washing with water, and the resulting cake is dried.
A method for producing zeolite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010063573A1 (en) | 2010-12-20 | 2012-06-21 | Technische Universität Dresden | Preparing a synthetic silica-rich zeolite, useful e.g. to produce drying agents and adsorbents, comprises hydrothermally crystallizing a reaction mixture containing a silicon and an aluminum source at autogenous pressure and temperature |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010063573A1 (en) | 2010-12-20 | 2012-06-21 | Technische Universität Dresden | Preparing a synthetic silica-rich zeolite, useful e.g. to produce drying agents and adsorbents, comprises hydrothermally crystallizing a reaction mixture containing a silicon and an aluminum source at autogenous pressure and temperature |
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