JPH03288544A - Adsorbent for vapor of alcohol fuel - Google Patents
Adsorbent for vapor of alcohol fuelInfo
- Publication number
- JPH03288544A JPH03288544A JP2089558A JP8955890A JPH03288544A JP H03288544 A JPH03288544 A JP H03288544A JP 2089558 A JP2089558 A JP 2089558A JP 8955890 A JP8955890 A JP 8955890A JP H03288544 A JPH03288544 A JP H03288544A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- adsorbent
- alcohol
- adsorption
- vapor
- 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.)
- Granted
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003463 adsorbent Substances 0.000 title claims abstract description 41
- 239000000446 fuel Substances 0.000 title claims abstract description 29
- 239000010457 zeolite Substances 0.000 claims abstract description 73
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 62
- 239000013078 crystal Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052680 mordenite Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 38
- 239000011148 porous material Substances 0.000 description 26
- 238000003795 desorption Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012013 faujasite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal cations Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
- F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
- F02M25/0854—Details of the absorption canister
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルコールを燃料とする車両のキャニスタ−
なとに使用するアルコール炉材蒸気用吸着剤に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a canister for a vehicle that uses alcohol as fuel.
This article relates to an adsorbent for alcohol furnace material vapor used in water.
近年、黒煙や窒素酸化物の排出が少ないメタノール、エ
タノールなどのアルコールをガソリンに混合した燃料で
走る車が注目されている。In recent years, cars that run on fuel mixed with gasoline and alcohols such as methanol and ethanol have been attracting attention, as they emit less black smoke and nitrogen oxides.
ガソリン燃料用キャニスタ−吸着剤としては破砕または
造粒した活性炭が広範に使用されている。しかし、活性
炭はアルコールの捕集効率か低く、アルコール燃料蒸気
用吸着剤としては適当てはない。Crushed or granulated activated carbon is widely used as a gasoline fuel canister adsorbent. However, activated carbon has a low alcohol trapping efficiency and is not suitable as an adsorbent for alcohol fuel vapor.
二つの吸着剤層を設けた蒸発燃料吸着装置か特開昭５９
−２２６．２６３号に提案されている。ここでは、極性
成分を吸着する材料からなる第二の吸着剤層を設けるこ
とが記載されている。第二の吸着剤層に適した材料とし
てゼオライトも有効であるとしている。しかしながら、
この目的に対して最適なゼオライトの種類や特性につい
ては何等説明がなされていない。−船釣に、汎用ゼオラ
イトは極性分子である水やアルコールに対して低濃度域
まで強い吸着力を示す。そのため水分またはアルコール
等の極性分子を含んだ燃料蒸気と接触させると、極性分
子はゼオライトに強力に捕捉される。キャニスタ−の場
合、吸着剤に吸着された蒸発燃料の脱着は外気を吸着剤
床に導入することによって、即ち燃料蒸気の分圧差によ
って吸脱着が行われる。しかし、−旦汎用ゼオライドに
強力に吸着された極性分子は吸着剤床に外気を導入した
程度の分圧差では脱着されない。このためアルコール蒸
気用吸着剤として使用した場合の有効な吸着量は小さい
。An evaporated fuel adsorption device with two adsorbent layers or JP-A-59
-226.263. Here, it is described that a second adsorbent layer made of a material that adsorbs polar components is provided. Zeolite is also said to be an effective material for the second adsorbent layer. however,
No explanation is given as to the type or characteristics of the zeolite that is most suitable for this purpose. -For boat fishing, general-purpose zeolite exhibits strong adsorption power for water and alcohol, which are polar molecules, even at low concentrations. Therefore, when brought into contact with fuel vapor containing water or polar molecules such as alcohol, the polar molecules are strongly captured by the zeolite. In the case of a canister, the vaporized fuel adsorbed on the adsorbent is desorbed by introducing outside air into the adsorbent bed, that is, by the partial pressure difference of the fuel vapor. However, the polar molecules strongly adsorbed on the general-purpose zeolide cannot be desorbed by a partial pressure difference as large as the introduction of outside air into the adsorbent bed. Therefore, when used as an adsorbent for alcohol vapor, the effective amount of adsorption is small.
このように、従来から知られている吸着剤を単に組み合
わせただけではアルコール燃料蒸気の吸脱着に対して満
足できる性能は得られず、これまでアルコール燃料を対
象とした好適な吸着剤がなかった。As described above, it is not possible to obtain satisfactory performance for adsorption and desorption of alcohol fuel vapor by simply combining conventionally known adsorbents, and until now there has been no suitable adsorbent for alcohol fuel. .
本発明は、アルコールを含む燃料蒸気の捕集に対して優
れた吸着性能を示すゼオライト系吸着剤を提供するもの
である。The present invention provides a zeolite-based adsorbent that exhibits excellent adsorption performance for collecting fuel vapor containing alcohol.
〔課題を解決するための手段および作用〕ゼオライト結
晶の基本構造はＳｉＯ４とその置換体のＡｌＯ４のそれ
ぞれの四面体で、それらがお互いに頂点の酸素原子を共
有し、３次元方向に発達した結晶構造を形成している。[Means and actions for solving the problem] The basic structure of a zeolite crystal is a tetrahedron of SiO4 and its substitute AlO4, which share the oxygen atom at the apex with each other, resulting in a three-dimensionally developed crystal. forming a structure.
その結果、ゼオライト結晶は他の鉱物に見られないよう
な非常に大きな空洞や孔路を有している。As a result, zeolite crystals have extremely large cavities and pores not found in other minerals.
これらの細孔の人口径はゼオライトによってことなるが
、通常３〜９オングストロームであり種々の分子を細孔
内部に捕捉することができる。Although the population diameter of these pores varies depending on the zeolite, it is usually 3 to 9 angstroms, and various molecules can be trapped inside the pores.
また、結晶内部にはＡ Ｉ Ｏａの負電荷を補うために
陽イオンが存在している。この陽イオンによって形成さ
れた静電場の影響により極性分子や分極性分子を選択的
に吸着する。汎用の吸着剤として一般的に使用されてい
るＡ型ゼオライト、ｘ型ゼオライト、Ｙ型ゼオライト等
のＳｉ／Ａｌモル比は１〜２５と低く、これらのゼオラ
イトに吸着されたアルコールは静電場の影響によって強
力にゼオライト細孔内に捕捉され、分圧を下げただけで
はアルコールが脱離せず十分な有効吸着量がとれない。Furthermore, cations exist inside the crystal to compensate for the negative charge of A I Oa. Polar molecules and polarizable molecules are selectively adsorbed under the influence of the electrostatic field formed by these cations. The Si/Al molar ratio of A-type zeolite, The alcohol is strongly trapped in the zeolite pores, and simply lowering the partial pressure will not desorb the alcohol, making it impossible to obtain a sufficient effective amount of adsorption.
この様な理由から、Ｓｉ／Ａｌ比が１〜２．５である汎
用ゼオライトはアルコール蒸気用の吸着剤として適当で
はない。For these reasons, general-purpose zeolites with a Si/Al ratio of 1 to 2.5 are not suitable as adsorbents for alcohol vapors.
しかしなから、３〜９オングストロームの細孔を有する
ゼオライト結晶の特異な細孔構造は低沸点成分の吸着、
特にアルコールや低級炭化水素成分の吸着に対して、ゼ
オライトの細孔径と吸着される分子の大きさがほぼ回し
であるために大変魅力的である。However, the unique pore structure of zeolite crystals, which have pores of 3 to 9 angstroms, allows for the adsorption of low-boiling components.
In particular, zeolite is very attractive for the adsorption of alcohols and lower hydrocarbon components because the pore diameter and the size of the adsorbed molecules are almost the same.
本発明者らは、各種ゼオライトを直接合成法または合成
ゼオライトに修飾処理を施す方法によって調製し、アル
コール燃料蒸気の捕集に対して有利な吸脱着特性をゼオ
ライトに発現させるへく鋭意検討を重ねた。その結果、
結晶骨格におけるＳｉ／Ａｌモル比１０以上のゼオライ
トがアルコール燃料蒸気に対して優れた吸脱着特性を示
し、キャニスタ−用吸着剤などとして有用であることを
見いだした。The present inventors prepared various zeolites by a direct synthesis method or a method of modifying synthetic zeolites, and made extensive studies to develop zeolites with adsorption and desorption properties that are advantageous for collecting alcohol fuel vapor. Ta. the result,
It has been found that zeolite with a Si/Al molar ratio of 10 or more in the crystal skeleton exhibits excellent adsorption/desorption properties for alcohol fuel vapor and is useful as an adsorbent for canisters.
ゼオライトのＳｊ／ＡＡのモル比が１０未満の場合は、
アルコールに対する吸着力が強すぎ吸着はするものの脱
離か困難となる。また、Ｓｉ／Ａｌのモル比が５００を
こえるとアルコールの吸着量が減少する傾向にあり、好
ましくはＳｉ／Ａｌのモル比１０〜５００のゼオライト
がアルコール蒸気用の吸着剤として適当である。When the molar ratio of Sj/AA of zeolite is less than 10,
The adsorption power for alcohol is so strong that although it can be adsorbed, it is difficult to remove it. Moreover, when the Si/Al molar ratio exceeds 500, the amount of alcohol adsorbed tends to decrease, and zeolite with a Si/Al molar ratio of 10 to 500 is preferably suitable as an adsorbent for alcohol vapor.
アルコールの吸脱着特性はＳｉ／’Ａ７！比率以外にも
ゼオライトの種類によっても変化する。Alcohol adsorption/desorption properties are Si/'A7! In addition to the ratio, it also changes depending on the type of zeolite.
アルコールや低級炭化水素（自動車用のアルコール燃料
は、通常ガソリンとアルコールとの混合物である）の吸
着か可能なゼオライトの細孔はその入口か酸素８． ＋
０．１２．員環によって形成されたものに限られ、チャ
バサイト、オフレタイト モルデナイト フォージャサ
イト、Ｌ。The pores of the zeolite, which are capable of adsorbing alcohol and lower hydrocarbons (alcoholic fuel for automobiles is usually a mixture of gasoline and alcohol), are either at their entrance or at the entrance to oxygen. +
0.12. Limited to those formed by member rings: chabasite, offretite, mordenite, faujasite, L.
Ω、ＺＳＭ−５，ＺＳＭ−ＩＩ型なとの結晶構造をもつ
ものかアルコールの吸着に適している。Ω, ZSM-5, and ZSM-II types are suitable for adsorption of alcohol.
また、ゼオライトの静的な飽和吸着量は結晶の空孔体積
（ゼオライト結晶１ ｍｌ中の空孔の体積）によってき
まる。ゼオライトの空孔体積は０、１５〜０．５ｍｌ／
′ｍｌであり、特に空孔体積が０．２５以上のフォージ
ャサイト、チャバサイト、オフレタイト、 Ｔ、
Ｌ、 Ω、フィリプサイト、メソライト、モルデナイ
ト型等の結晶構造をもつゼオライドはアルコール飽和吸
着量も高い。Further, the static saturated adsorption amount of zeolite is determined by the pore volume of the crystal (volume of pores in 1 ml of zeolite crystal). The pore volume of zeolite is 0.15~0.5ml/
'ml, especially faujasite, chabasite, offretite, with a pore volume of 0.25 or more, T,
Zeolides with crystal structures such as L, Ω, philipsite, mesolite, and mordenite have a high alcohol saturation adsorption amount.
これらのＳｉ／Ａｌモル比１０以上のゼオライトはＳｉ
／Ａｌモル比１０％未満のものとは異なり水よりもアル
コールや低級炭化水素を選択的に吸着する。即ち、Ｓｉ
／ＡＡ’モル比１０以上のゼオライトにあらかじめ水分
を吸着させ、アルコール蒸気の吸脱着試験を繰り返すと
、最初の数回は非常に高い有効吸着量が観測される。さ
らにアルコールの吸脱着試験を繰り返すと、水分を含ま
ない状態のゼオライトと同じ有効吸着量を示す。初期の
高い有効吸着量は、あらかじめ吸着させておいた水とア
ルコールが置換し、吸着層の温度上昇が抑制された為に
起こる特異な現象と考えられる。しかし、この特異な現
象も長続きはせずゼオライト細孔中の水分子がアルコー
ルと置換した後は、正常な有効吸着量を示すようになる
。この様に、Ｓｉ／ＡＡ’モル比１０以上のゼオライト
は多量の水分に吸着剤がさらされた場合ですら、その吸
着性能の低下は認められない。These zeolites with a Si/Al molar ratio of 10 or more are Si
/Al molar ratio of less than 10%, it selectively adsorbs alcohol and lower hydrocarbons rather than water. That is, Si
When water is adsorbed in advance on zeolite with a /AA' molar ratio of 10 or more and the alcohol vapor adsorption/desorption test is repeated, a very high effective adsorption amount is observed the first few times. Further repeated alcohol adsorption and desorption tests show that the zeolite has the same effective adsorption amount as zeolite without water. The initial high effective adsorption amount is considered to be a unique phenomenon that occurs because the alcohol replaces the water that was adsorbed in advance, and the temperature rise in the adsorption layer is suppressed. However, this unique phenomenon does not last long, and after the water molecules in the zeolite pores are replaced with alcohol, the amount of adsorption returns to normal. In this way, the adsorption performance of zeolite with a Si/AA' molar ratio of 10 or more is not observed even when the adsorbent is exposed to a large amount of water.
Ｓｉ／Ａｌモル比１０以上のゼオライトの調製方法とし
ては天然ゼオライト或は合成ゼオライトを出発原料とし
脱アルミニウム処理によって調製する方法、或はシリカ
源、アルミナ源、アルカリ源を混合し結晶化する直接合
成法またはさらに有機鉱化剤を添加して合成する方法等
がある。Methods for preparing zeolite with a Si/Al molar ratio of 10 or more include a method using natural zeolite or synthetic zeolite as a starting material and preparation by dealumination treatment, or direct synthesis in which a silica source, an alumina source, and an alkali source are mixed and crystallized. method, or a method of synthesis by further adding an organic mineralizing agent.
脱アルミニウム処理によって調製されたＳｉ／’ Ａ
１モル比１０以上のゼオライトとしては、脱アルミニウ
ムモルデナイト（Ｎ、 Ｙ、 Ｃｈｅｎ、 １． Ｐｔ
＋ｙＣｈｅｍ、 ８０ （］）、 ６０〜６４（１
９７６）） 、超安定化Ｙ型ゼオライト（特開昭５４−
１２２．７００号； ５ｔｕｄｉｅｓ ＋ｎ５ｕｒｆａ
ｃｅ ５ｉｅｎｃｅ ａｎｄ Ｃａｔａ１７ｓｉｓ、
Ｖｏｌｕｍｅ ５，２０３〜２１０ （１９８０））
、超安定化り型ゼオライト（特開昭６０−０５０．３１
２号）等が知られている。Si/'A prepared by dealumination process
Zeolites with a molar ratio of 10 or more include dealuminated mordenite (N, Y, Chen, 1.Pt
+yChem, 80 (]), 60-64 (1
976)), ultra-stabilized Y-type zeolite (Japanese Patent Application Laid-open No. 1983-
No. 122.700; 5tudies +n5urfa
ce 5ience and Cata17sis,
Volume 5, 203-210 (1980))
, ultra-stabilized zeolite (JP-A-60-050.31
No. 2) etc. are known.
直接合成によって調製されたＳｉ／Ａｌモル比１０以上
のゼオライトとしてはモルデナイト（Ｒ，Ｍ、 Ｂａ「
「ｅ「、 １． Ｃｂｅｍ、 Ｓｏｃ、 、 １９４８
．２１５８） 、Ｚ ５Ｍ−５（特開昭４６−１０．０
６４号） 、ＺＳＭ−ＩＩ（特開昭５３−２３．２８０
号）等が知られている。Zeolites with a Si/Al molar ratio of 10 or more prepared by direct synthesis include mordenite (R, M, Ba'
"e", 1. Cbem, Soc, , 1948
．． 2158), Z 5M-5 (Japanese Patent Application Laid-Open No. 1973-10.0
64), ZSM-II (Unexamined Japanese Patent Publication No. 53-23.280
No.) etc. are known.
アルコール燃料蒸気用吸着剤として、これらゼオライト
のいずれも好適に使用できる。また、ゼオライトのＳｉ
／Ａｌ比率は修飾処理条件または直接合成条件によって
自由に制御することか可能であり、アルコール燃料蒸気
の吸脱着に最適な吸着剤を提供することか可能である。Any of these zeolites can be suitably used as an adsorbent for alcohol fuel vapor. In addition, Si of zeolite
/Al ratio can be freely controlled by modified processing conditions or direct synthesis conditions, and it is possible to provide an adsorbent optimal for adsorption and desorption of alcohol fuel vapor.
アルコール燃料の吸脱着に最適な結晶骨格のＳｉ／Ａｌ
比率はゼオライトの結晶構造によって異なる。フォージ
ャサイト型ゼオライトの場合メタノールやエタノールの
吸脱着に最適なＳｉ／ＡＡモル比は２０〜１００の範囲
内に見いだされるのに対して、モルデナイト型ゼオライ
トの場合、その最適なＳｉ／Ａｌモル比は５０〜２００
の範囲内に見いだされ、さらにＺＳＭ−５の場合は１０
０〜５００の範囲内に見いたされる。Si/Al with crystalline skeleton ideal for adsorption/desorption of alcohol fuel
The ratio varies depending on the crystal structure of the zeolite. In the case of faujasite-type zeolite, the optimum Si/AA molar ratio for adsorption and desorption of methanol and ethanol is found within the range of 20 to 100, whereas in the case of mordenite-type zeolite, the optimum Si/Al molar ratio is found to be within the range of 20 to 100. is 50-200
and in the case of ZSM-5, 10
Found within the range of 0-500.
フォージャサイト型のゼオライトでは細孔の入口径は８
オングストロームであるが、結晶内の空孔の大きさは約
１３オングストロームである。In faujasite type zeolite, the pore entrance diameter is 8
angstrom, but the size of the pores within the crystal is approximately 13 angstroms.
一方、モルデナイトやＺＳＭ−５の場合は細孔の入口径
と結晶内の空孔の大きさは等しく、それぞれ７オングス
トローム、６オングストロームである。この様に、アル
コールの吸脱着特性はゼオライト結晶の空孔径とゼオラ
イト骨格の極性のバランスによってきまる。即ち、ゼオ
ライトの空孔径かアルコール分子の大きさとほぼ等しい
場合には結晶骨格かはとんと極性をもたなくてもアルコ
ールを十分捕捉でき、しかも吸着されたアルコールは分
圧差のみてち容易に脱離することかできる。しかし、フ
ォージャサイトのように空孔径かメタノール分子やエタ
ノル分子の大きさの２倍以上もあるような場合には、ゼ
オライト結晶自体にある程度極性をもたせないとアルコ
ールに対する吸着力が小さくなる。しかし、Ｓｉ／ＡＡ
比率を低く設定しすぎると、吸着したアルコールの脱離
が困難となり、有効吸着量か小さくなる。On the other hand, in the case of mordenite and ZSM-5, the entrance diameter of the pores and the size of the pores in the crystal are equal, and are 7 angstroms and 6 angstroms, respectively. In this way, the adsorption and desorption properties of alcohol are determined by the balance between the pore size of the zeolite crystal and the polarity of the zeolite skeleton. In other words, when the pore size of the zeolite is approximately equal to the size of the alcohol molecule, the crystal skeleton can sufficiently capture alcohol even if it is not extremely polar, and the adsorbed alcohol can be easily desorbed due to the difference in partial pressure. I can do something. However, in cases such as faujasite, where the pore size is more than twice the size of methanol molecules or ethanol molecules, the adsorption power for alcohol will be reduced unless the zeolite crystal itself has some degree of polarity. However, Si/AA
If the ratio is set too low, it will be difficult to desorb the adsorbed alcohol, and the effective adsorption amount will be small.
また、空孔径が１３オングストロームのゼオライトと７
オングストローム以下のものを比較した場合、静的な飽
和吸着量に対する有効吸＠量の比率は、７オングストロ
ーム以下のものが１３オングストロームのものより大き
な値を示す。In addition, zeolite with a pore size of 13 angstroms and 7
When comparing materials of 7 angstroms or less, the ratio of effective adsorption amount to static saturated adsorption amount shows a larger value for 7 angstroms or less than 13 angstroms.
このことは、メタノールの吸着特性が空孔径７オングス
トロ一ム前後で急激に変化したことによると推定される
。即ち、空孔径が８オングストロ一ム以上のゼオライト
ではメタノールやエタノールに対する吸着力が弱まり、
吸着剤床における吸着帯が長くなるため、空孔径７オン
グストローム以下のゼオライトと比べた場合、有効吸着
量が相対的に小さくなる。This is presumed to be due to the fact that the adsorption characteristics of methanol suddenly changed when the pore diameter was around 7 angstroms. In other words, in zeolites with pore diameters of 8 angstroms or more, the adsorption power for methanol and ethanol is weakened,
Due to the length of the adsorption zone in the adsorbent bed, the effective adsorption capacity is relatively small when compared to zeolites with pore diameters of 7 angstroms or less.
ゼオライトには交換性のカチオンが含まれている。アル
コール燃料蒸気を捕捉する場合、ゼオライト中のアルカ
リ金属またはアルカリ土類金属カチオンは細孔径や細孔
内の静電場に影響するため好ましくない。従って、水素
イオン型がその吸着性能が安定しており好適である。Zeolites contain exchangeable cations. When capturing alcohol fuel vapor, alkali metal or alkaline earth metal cations in the zeolite are undesirable because they affect the pore size and the electrostatic field within the pores. Therefore, the hydrogen ion type is preferred because its adsorption performance is stable.
本発明の吸着剤をキャニスタ−に使用する場合、キャニ
スタ−は自動車部品として、使用されるためその設置に
対して必要なスペースは小さければ小さいほどよい。し
たがって、ゼオライト吸着剤の充填密度は大きい方がよ
い。実用的には、０．５ｇ／ｍ１以上のものが好ましい
。When the adsorbent of the present invention is used in a canister, the canister is used as an automobile part, so the smaller the space required for its installation, the better. Therefore, the packing density of the zeolite adsorbent is preferably higher. Practically speaking, it is preferably 0.5 g/ml or more.
ゼオライト粉末をペレット、ビーズ状とするため、−船
釣にはカオリナイト或はモンノリロナイト等の粘土鉱物
やアルミナ系またはシリカ系の無機バインダーが好適に
使用される。また成形体の強度アップや粉化防止の目的
でガラス繊維等のセラミックス繊維を少量混入すること
は特に効果的である。In order to form zeolite powder into pellets or beads, clay minerals such as kaolinite or monnorillonite, or alumina-based or silica-based inorganic binders are preferably used for boat fishing. Furthermore, it is particularly effective to mix a small amount of ceramic fibers such as glass fibers for the purpose of increasing the strength of the molded body and preventing pulverization.
しかし、ゼオライト粉末にバインダーを添加したゼオラ
イト成形体の場合、アルコール燃料の吸脱着に有効なゼ
オライトは、粘土やアルミナまたはシリカ等のバインダ
ーによって希釈される。キャニスタ−用吸着剤の場合、
有効吸着量が大きいほどよい。ところで、バインダーを
使用しないで製造されたゼオライト１４！形体が特開昭
６２−７０．２２５や特開昭６２−１３８．３２θ等に
示されている。この様な、バインダー成分を含まないゼ
オライト成形体を出発原料として調製した吸着剤は有効
吸着量が大きく、アルコール燃料のキャニスタ−用吸着
剤としてとくに優れた吸脱着性能を示す。However, in the case of a zeolite molded body made by adding a binder to zeolite powder, the zeolite, which is effective in adsorbing and desorbing alcohol fuel, is diluted by the binder such as clay, alumina, or silica. In the case of adsorbent for canister,
The larger the effective adsorption amount, the better. By the way, Zeolite 14 is manufactured without using a binder! The shape is shown in JP-A-62-70.225 and JP-A-62-138.32θ. An adsorbent prepared using such a zeolite molded body containing no binder component as a starting material has a large effective adsorption amount and exhibits particularly excellent adsorption/desorption performance as an adsorbent for an alcohol fuel canister.
この発明は、以上述べたように、Ｓｉ／Ａｌモル比１０
以上であるゼオライトをアルコール燃料から発生する蒸
気捕集用吸着剤として提供するものである。これにより
、従来活性炭で困難であったアルコール燃料蒸気の捕集
がキャニスタ−などの構造に特別な工夫をすることなく
可能となった。As stated above, this invention has a Si/Al molar ratio of 10
The zeolite described above is provided as an adsorbent for collecting vapor generated from alcohol fuel. This has made it possible to collect alcohol fuel vapor, which was difficult to do with activated carbon, without making any special modifications to the structure of the canister or the like.
以下に、この発明の詳細な説明する。 The present invention will be explained in detail below.
（実施例１〜６） 表１に本発明のゼオライト系吸着剤を示す。(Examples 1 to 6) Table 1 shows the zeolite adsorbent of the present invention.
実施例１〜５のゼオライト系吸着剤は各ゼオライト１０
０重量部に対して粘土系無機バインダー２５重量部を添
加し、押出し造粒機により成形した後、６００℃で２時
間焼成することにより、直径１．５ｍｍの円柱状吸着剤
を得た。また、実施例６のゼオライト系吸着剤はバイン
ダーレスタイプの粒状ゼオライトを出発原料として調製
したものである。これら吸着剤のアルコール蒸気に対す
る吸脱着試験は、以下の方法で行った。The zeolite-based adsorbents of Examples 1 to 5 were each zeolite 10
25 parts by weight of a clay-based inorganic binder was added to 0 parts by weight, molded using an extrusion granulator, and then baked at 600° C. for 2 hours to obtain a cylindrical adsorbent with a diameter of 1.5 mm. Moreover, the zeolite-based adsorbent of Example 6 was prepared using binderless type granular zeolite as a starting material. Adsorption and desorption tests of these adsorbents for alcohol vapor were conducted in the following manner.
く吸脱着試験方法〉
吸脱着試験は図１に示す試験装置を用いて行った。 ２
５０ｍ１の内容積をもつ円筒状キャニスタ−に実施例１
〜６までの吸着剤を充填し、３０°Ｃの恒温槽にセット
する。丸底フラスコにメタノールを入れ、６０°Ｃに加
熱する。１０００ｍ１７分の空気をアルコール中に通し
、発生したメタノール蒸気をキャニスタ−に通気し、キ
ャニスタ−より排出されたメタノール量が１ｇとなった
時点て通気を止めキャニスタ−の重量を測定する。Adsorption/desorption test method> The adsorption/desorption test was conducted using the testing apparatus shown in Figure 1. 2
Example 1 in a cylindrical canister with an internal volume of 50 m1
Fill with adsorbent up to 6 and set in a constant temperature bath at 30°C. Pour methanol into a round bottom flask and heat to 60°C. Air for 1000 m and 17 minutes is passed through the alcohol, the generated methanol vapor is vented into the canister, and when the amount of methanol discharged from the canister reaches 1 g, the ventilation is stopped and the weight of the canister is measured.
次に、キャニスタ−に１２０１の空気を通し脱離を行い
再びキャニスタ−の重量を測定する。Next, air of 1201 was passed through the canister to remove it, and the weight of the canister was measured again.
メタノール吸着後のキャニスタ−重量から脱離後のキャ
ニスタ−重量を引き、吸着剤１００ ｇ当りのメタノー
ルに対する有効吸着量を求めた。The weight of the canister after desorption was subtracted from the weight of the canister after methanol adsorption to determine the effective adsorption amount of methanol per 100 g of adsorbent.
この操作を４回行い、２〜４回目の平均値を表１に示し
た。This operation was performed four times, and the average values of the second to fourth times are shown in Table 1.
（比較例１〜２）
比較例１．２ではそれぞれ汎用のＡ、 Ｘ型ゼオライト
の１．５圓φ粒状品を吸着剤として使用し、実施例を行
ったと同じメタノールの吸脱着試験を行った。結果を表
２に示した。(Comparative Examples 1 and 2) In Comparative Examples 1 and 2, the same methanol adsorption and desorption tests as in Examples were conducted using 1.5 mm diameter granular products of general-purpose A and X type zeolites as adsorbents. . The results are shown in Table 2.
表１および表２には、ゼオライトの構造芯、Ｓｉ／Ａｌ
比率および見かけ比重（ｇ／ｍすを併記した。Tables 1 and 2 show the structural core of zeolite, Si/Al
The ratio and apparent specific gravity (g/m) are also listed.
表１ 表Table 1 table
図１は、実施例における吸脱着試験の工程図を示す。 FIG. 1 shows a process diagram of an adsorption/desorption test in an example.
Claims (3)
オライトからなるアルコール燃料蒸気用吸着剤。(1) An adsorbent for alcohol fuel vapor made of zeolite with a Si/Al molar ratio of 10 or more in the crystal skeleton.
または用いずして成形、焼成してなるアルコール燃料蒸
気用吸着剤。(2) Using the zeolite according to claim 1 with a binder,
Alternatively, an adsorbent for alcohol fuel vapor can be formed and fired without using it.
ー用吸着剤。(3) An adsorbent for canisters using the zeolite according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089558A JP3001106B2 (en) | 1990-04-04 | 1990-04-04 | Adsorbent for alcohol fuel vapor |
| DE19914110646 DE4110646A1 (en) | 1990-04-04 | 1991-04-02 | Adsorbent for alcoholic fuel vapours - contg. zeolite of silicon-aluminium mol ratio of not less than 10, and opt. binder |
| US07/978,172 US5271914A (en) | 1990-04-04 | 1992-11-17 | Process for adsorbing the vapor of alcoholic fuels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2089558A JP3001106B2 (en) | 1990-04-04 | 1990-04-04 | Adsorbent for alcohol fuel vapor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03288544A true JPH03288544A (en) | 1991-12-18 |
| JP3001106B2 JP3001106B2 (en) | 2000-01-24 |
Family
ID=13974152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2089558A Expired - Fee Related JP3001106B2 (en) | 1990-04-04 | 1990-04-04 | Adsorbent for alcohol fuel vapor |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3001106B2 (en) |
| DE (1) | DE4110646A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010255489A (en) * | 2009-04-23 | 2010-11-11 | Sanoh Industrial Co Ltd | Method and device for heating and supplying fuel |
| JP2013119845A (en) * | 2011-12-09 | 2013-06-17 | Toyota Motor Corp | Exhaust emission control method of an internal combustion engine using alcohol mixed fuel and exhaust emission control device using the same method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4225170A1 (en) * | 1992-07-30 | 1994-02-03 | Preussag Anlagenbau | Automotive fuel storage and delivery system - removes vapours formed during storage and delivery to prevent formation of explosive mixts. |
-
1990
- 1990-04-04 JP JP2089558A patent/JP3001106B2/en not_active Expired - Fee Related
-
1991
- 1991-04-02 DE DE19914110646 patent/DE4110646A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010255489A (en) * | 2009-04-23 | 2010-11-11 | Sanoh Industrial Co Ltd | Method and device for heating and supplying fuel |
| JP2013119845A (en) * | 2011-12-09 | 2013-06-17 | Toyota Motor Corp | Exhaust emission control method of an internal combustion engine using alcohol mixed fuel and exhaust emission control device using the same method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4110646A1 (en) | 1991-10-24 |
| JP3001106B2 (en) | 2000-01-24 |
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