JPS60238149A - Preparation of porous inorganic oxide - Google Patents
Preparation of porous inorganic oxideInfo
- Publication number
- JPS60238149A JPS60238149A JP59092794A JP9279484A JPS60238149A JP S60238149 A JPS60238149 A JP S60238149A JP 59092794 A JP59092794 A JP 59092794A JP 9279484 A JP9279484 A JP 9279484A JP S60238149 A JPS60238149 A JP S60238149A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- gel
- particle
- inorg
- binder
- 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
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000011148 porous material Substances 0.000 claims abstract description 45
- 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 36
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 229940100445 wheat starch Drugs 0.000 claims abstract description 3
- 239000000499 gel Substances 0.000 claims description 14
- 229920002261 Corn starch Polymers 0.000 claims description 13
- 239000008120 corn starch Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010418 carrageenan Nutrition 0.000 claims description 3
- 229920001525 carrageenan Polymers 0.000 claims description 3
- 239000000679 carrageenan Substances 0.000 claims description 3
- 229940113118 carrageenan Drugs 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 229920000057 Mannan Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000001035 drying Methods 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 description 15
- 229940099112 cornstarch Drugs 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- -1 naphtha Substances 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は多孔性無機酸化物の製造方法に関し、詳しくは
大粒子と小粒子からなるとともに大細孔を有するもので
あって、重質炭化水素の水素化触媒や担体などとして用
いた場合に、炭素分や金属分が析出しても活性の低下が
小さく、極めて好適に利用できる多孔性無機酸化物の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a porous inorganic oxide, and more specifically, it is composed of large particles and small particles and has large pores, and the present invention relates to a method for producing a porous inorganic oxide, which is composed of large particles and small particles and has large pores. The present invention relates to a method for producing porous inorganic oxides that can be used very suitably, with little reduction in activity even when carbon or metal components are precipitated.
近年、世界的に原油が重質化する傾向にあると同時に、
石油の需要構造が変化し、軽質油が不足し、一方で重質
油が余る傾向を示している。そのため重質油を分層して
ナフサ、灯油、軽油などの軽質油に転化する技術が多数
開発されてきている。In recent years, there has been a global trend toward heavier crude oil, and at the same time,
The demand structure for oil is changing, with light oil in short supply and heavy oil in surplus. For this reason, many technologies have been developed to separate heavy oil into light oils such as naphtha, kerosene, and diesel oil.
そのうち水素化分解、水素化精製などの水素化処理の技
術は良質の軽質油が得られるため、非常に有望視されて
いる。またこの重質油の水素化処理にあたっては、ゼオ
ライト触媒を用いることが広く行なわれている。Among these, hydroprocessing technologies such as hydrocracking and hydrorefining are considered very promising because they yield high-quality light oil. Furthermore, in the hydrogenation treatment of heavy oil, zeolite catalysts are widely used.
しかしながら、従来使用されているゼオライト触媒では
、水素化処理において生成するアスファルテン、金属な
どが沈析して触媒の活性点を塞ぎ、短期間に触媒活性が
低下してしまうという問題があった。However, conventionally used zeolite catalysts have a problem in that asphaltenes, metals, etc. produced during hydrotreating precipitate and block the active sites of the catalyst, resulting in a decrease in catalytic activity in a short period of time.
そのため、ゼオライトに１０００λ以上の大細孔を生成
させたものを使用することが提案されている。しかし、
このような大細孔を有するぞオライドであっても、アル
ミナゾルなどのようなバインダーを用いて成形して得ら
れるものは、ゼオライトの大細孔がアルミナなどのバイ
ンダー粒子により塞がれるため、充分な触媒活性は得ら
れず触媒寿命も短いものであった。Therefore, it has been proposed to use zeolite with large pores of 1000λ or more. but,
Even if a zeolite has such large pores, it cannot be molded using a binder such as alumina sol, since the large pores of the zeolite are blocked by binder particles such as alumina. No significant catalytic activity was obtained and the catalyst life was short.
そこで、本発明者らは上記問題点を解決し、重質油の水
素化処理などに好適な触媒あるいは担体を開発するべく
、鋭意研究した。その結果、特定の大きさのゼオライト
にバインダーとともに水膨潤性ゲル状物質を混合し、乾
燥、焼成することＫよって、重質炭化水素の水素化処理
をはじめ各種の反応の触媒あるいはその触媒担体として
好適な多孔性の無機酸化物が得られることを見い出し、
この知見に基づいて本発明を完成した。Therefore, the present inventors conducted extensive research in order to solve the above problems and develop a catalyst or carrier suitable for hydrotreating heavy oil. As a result, zeolite of a specific size is mixed with a water-swellable gel material along with a binder, dried, and calcined.Therefore, it can be used as a catalyst or catalyst support for various reactions, including the hydrogenation of heavy hydrocarbons. It was discovered that a suitable porous inorganic oxide could be obtained,
The present invention was completed based on this knowledge.
すなわち、本発明は大粒子と小粒子からなるとともに大
細孔を有する多孔性無機酸化物を製造するにあたり、大
粒子ゼオライトに小粒子形成性無機結合剤および水膨潤
性ゲル状物質を混合することを特徴とする多孔性無機酸
化物の製造方法を提供するものである。That is, in producing a porous inorganic oxide consisting of large particles and small particles and having large pores, the present invention involves mixing large particle zeolite with a small particle forming inorganic binder and a water-swellable gel material. The present invention provides a method for producing a porous inorganic oxide characterized by the following.
本発明において用いられる大粒子ゼオライトとしては各
種の天然あるいは合成ゼオライトをあげることができる
。例えば、アンモニウムＹ型（ＮＨ４Ｙ型）ゼオライト
、これを焼成して得られるプロオライド、金属プロトン
Ｙ ｉｌｌ （ＭＨＹ型）ゼオライト、金属スチーム処
理Ｙ型（ＭｓＨｙ型）ゼオライトなどが挙げられる。こ
こでゼオライト中に含まれている金属としては、２価あ
るいは３価の金属。As the large particle zeolite used in the present invention, various natural or synthetic zeolites can be mentioned. Examples include ammonium Y type (NH4Y type) zeolite, proolide obtained by firing this, metal proton Y ill (MHY type) zeolite, and metal steam-treated Y type (MsHy type) zeolite. Here, the metals contained in zeolite are divalent or trivalent metals.
具体的にはマグネシウム、カルシウム、セリウム。Specifically, magnesium, calcium, and cerium.
アルミニウム、鉄、ニッケル、コバルト、銅などがある
。These include aluminum, iron, nickel, cobalt, and copper.
本発明の大粒子ゼオライトの粒径は、小粒子形成性無機
結合剤から形成される小粒子との比較においてより大き
いものであれば良く、特に制限はないが、大粒子ゼオラ
イトの粒径（４）と小粒子形成性無機結合剤から形成さ
れる粒子の粒径（９）の比が通常はん４≧２、好ましく
は１００以上である。The particle size of the large-particle zeolite of the present invention is not particularly limited as long as it is larger than the small particles formed from the small-particle-forming inorganic binder, but the particle size of the large-particle zeolite (4 ) and the particle size (9) of the particles formed from the small particle-forming inorganic binder is usually 4≧2, preferably 100 or more.
また大粒子ゼオライトの粒径そのものの大きさについて
は通常１〜１０μ、好ましくは２〜５μ程度のものが用
いられる。このような粒径の大粒子ゼオライトを用いる
と、粒子間空隙が８００〜２０００Ｘとなり、また、こ
れに５０〜２ｏｏＸ程度の粒径の小粒子形成性無機結合
剤を組合せると所望の大きさの粒子空隙が形成されるこ
ととなる。Further, the particle size of the large-particle zeolite itself is usually about 1 to 10 microns, preferably about 2 to 5 microns. If large particle zeolite with such a particle size is used, the interparticle voids will be 800 to 2000X, and if this is combined with a small particle forming inorganic binder with a particle size of about 50 to 200X, the desired size can be obtained. Particle voids will be formed.
本発明は上記の如き大粒子ゼオライトに、小粒子形成性
無機結合剤および水膨潤性ゲル状物質を混合する。ここ
で小粒子形成性無機結合剤としては、触媒中において小
粒子を形成する無機物の結合剤であれば良く、特に制限
はないが、例えばベーヴノＬ Ａ’ ｎノ マｎ７ぐ−
Ｊ−ｓｌ −！、マｎ−コニｄ脅 ごノリカゲル、シリ
カ・アルミナゲル、シリカゾルなどを挙げることができ
る。この小粒子形成性無機結合剤は粒径等に％に制限は
ないが他の成分と混練して、得られる多孔性無機酸化物
中で小粒子として存在するもので、大粒子ゼオライトと
の粒径比が前記の如きものであればよい。In the present invention, a small particle-forming inorganic binder and a water-swellable gel material are mixed with the above-mentioned large particle zeolite. Here, the small particle-forming inorganic binder is not particularly limited as long as it is an inorganic binder that forms small particles in the catalyst.
J-sl-! Examples include silica gel, silica/alumina gel, and silica sol. This small particle-forming inorganic binder is present as small particles in the porous inorganic oxide obtained by kneading it with other ingredients, although there is no limit to the particle size or the like. It is sufficient if the diameter ratio is as described above.
次に本発明においては、さらに水膨潤性ゲル状物質を加
えることが必要である。この水膨潤性ゲル状物質とは、
水により膨潤するものでありかつ、加熱時にゲル状を保
つものであれば良く、特に制限はない。具体的には、コ
ーンスターチ、馬鈴薯でんぷん、サツマイモでんぷん、
小麦でんぷん。Next, in the present invention, it is necessary to further add a water-swellable gel material. What is this water-swellable gel-like substance?
There are no particular limitations as long as it swells with water and maintains a gel-like state when heated. Specifically, corn starch, potato starch, sweet potato starch,
wheat starch.
に−カラジーナン、マンナン、アルギン酸塩などが挙げ
られ、特にコーンスターチまたはに一力２ジーナンが好
適である。Examples include carrageenan, mannan, alginates, etc., and cornstarch or dianine is particularly preferred.
本発明において、大粒子ゼオライト、小粒子形成性無機
結合剤および水膨潤性ゲル状物質の配合割合は特に制限
はなく、小粒子形成性無機結合剤がバインダーとして充
分に機能しうる量であるとともに−＊膨粘性ゲル状物書
六二す詩竿ギナラスＬの大細孔を閉塞するに充分な量で
あればよ（・。具体的には、大粒子ゼオライ）１００重
量部に対して、小粒子形成性無機結合剤を９０〜１０１
景部、好ましくは７０〜４０重量部とし、水膨潤性ゲル
状物質を０．５〜１５重量部、好ましくは１〜１０重量
部とする。In the present invention, there is no particular restriction on the blending ratio of large-particle zeolite, small-particle-forming inorganic binder, and water-swellable gelatinous material, and the amount of the small-particle-forming inorganic binder can sufficiently function as a binder. - *If the amount is sufficient to block the large pores of the swelling viscous gel-like material 62 Sushi Rod Guinaras L (・Specifically, large particle zeolite) Particle-forming inorganic binder from 90 to 101
The amount of water-swellable gel material is preferably 0.5-15 parts by weight, preferably 1-10 parts by weight.
またこれらの各成分を混合するにあたっては、混合順序
、操作における制限はな（、様々な手法によって行なえ
ばよい。例えば、水性媒体中で大粒子ゼオライトに他の
成分を同時に、あるいは順次加えて混合するなどによっ
て行なう。さらに具体的には、各成分をニーダ−等の混
合機を用いて混合後、成形可能な状態まで約１００℃程
度で１時間前後捏和し、その後室温まで冷却し、さらに
１．５時間程度捏和を行なうなどによればよい。In addition, when mixing these components, there are no restrictions on the mixing order or operation (it can be done by various methods. For example, mixing large particle zeolite in an aqueous medium by adding other components simultaneously or sequentially) More specifically, each component is mixed using a mixer such as a kneader, kneaded at about 100°C for about an hour until it can be molded, then cooled to room temperature, and then kneaded. The mixture may be kneaded for about 1.5 hours.
このようにして得られた混合物を通常の方法にしたがっ
て、成形、乾燥、焼成等を行なうことにより、本発明の
多孔性無機酸化物を得ることができる。The porous inorganic oxide of the present invention can be obtained by subjecting the mixture thus obtained to molding, drying, sintering, etc. according to conventional methods.
ここで乾燥条件は原料により異なり一義的に決定されな
いが十分乾燥されるまで行なえば良いが通常８０〜１５
０℃、好ましくは９０〜１２０℃で１〜１０時間、好ま
しくは３〜５時間行なえば良い。また、焼成条件も、特
に制限はないが、通常４００〜７００℃、好ましくは４
５０〜６００℃で１〜１０時間、好ましくは３〜５時間
行なう。Here, the drying conditions vary depending on the raw material and cannot be determined uniquely, but it is sufficient to carry out the drying process until it is sufficiently dried, but it is usually 80 to 15
It may be carried out at 0°C, preferably 90 to 120°C, for 1 to 10 hours, preferably 3 to 5 hours. The firing conditions are also not particularly limited, but are usually 400 to 700°C, preferably 400°C to 700°C.
It is carried out at 50 to 600°C for 1 to 10 hours, preferably 3 to 5 hours.
本発明においては、水膨潤性ゲル状物質を加えることに
より、これが水性媒体中で膨潤し大粒子ゼオライトの粒
子空隙中に入りこんで、粒子空隙を塞ぎその結果、小粒
子形成性無機結合剤が混合中に大粒子ゼオライトの粒子
空隙に入りこむのを防ぐことができる。しかも、その後
に乾燥、焼成を行なえば、大粒子ゼオライトの粒子空隙
中の水膨潤性ゲル状物質は燃焼見て完全に消失し、また
この粒子空隙アルミナゾル、ベーマイトゲル等の無機結
合剤により閉塞されることもないため、数多くの大細孔
が存在する無機酸化物が得られることとなる。In the present invention, by adding a water-swellable gel-like substance, it swells in an aqueous medium and enters the particle voids of large-particle zeolite, closing the particle voids and as a result, the small-particle-forming inorganic binder is mixed. This can prevent particles from entering the voids of large zeolite particles. Moreover, if drying and calcination are performed afterwards, the water-swellable gel-like substance in the pores of large-particle zeolite particles will completely disappear upon combustion, and the pores will be blocked by inorganic binders such as alumina sol and boehmite gel. Therefore, an inorganic oxide containing many large pores can be obtained.
このようにして得られる多孔性無機酸化物は、粒径１μ
〜５μ程度の大粒子ゼオライトおよび粒径５０〜３００
λ程度の小粒子形成性無機結合剤の小粒子からなり、多
くの大細孔を有しているものである。ここで大細孔とは
通常１０００Ｘ以上の大きさの細孔を言（・、本発明の
多孔性無機酸化物の大細孔は、その細孔分布、細孔容積
については製造の際の条件等により異なるが、１００〜
２００１の細孔と１０００，１以上の細孔の２モード型
の細孔分布を有し、細孔容積は５００〜１０００スが０
．１５ ＣＣ／ｆ１以上、１０００＾以上が０．１ｃｃ
今以上であって、全体として０．５ ｃｃ／ｇ程度の値
である。The porous inorganic oxide thus obtained has a particle size of 1 μm.
~ Large particle zeolite of about 5μ and particle size 50-300
It consists of small particles of a small particle-forming inorganic binder of about λ, and has many large pores. Here, large pores usually refer to pores with a size of 1000X or more (・The large pores of the porous inorganic oxide of the present invention are determined by the conditions during production regarding its pore distribution and pore volume. etc., but it varies from 100 to
It has a bimodal pore distribution of 2001 pores and 1000.1 or more pores, and the pore volume is 500 to 1000 s.
．． 15 CC/f1 or more, 1000^ or more is 0.1cc
This is higher than the current value, and the total value is about 0.5 cc/g.
以上の如く多孔性無機酸化物は、そのまま触媒あるいは
触媒担体として用いることができ、また、種々の金属、
特に、水素化活性金属例えば■Ｂ族または■族金属など
を含浸法、共沈法などの方法で担持すれば極めて良好な
炭化水素転化用触媒として利用することができる。本発
明の多孔性無機酸化物を用いた触媒は大細孔を有してい
るため、重質炭化水素の水素化反応において炭素や不純
物金属を析出しても、活性の低下が小さく、触媒寿命も
長いものである。As mentioned above, porous inorganic oxides can be used as catalysts or catalyst carriers as they are, and can be used as catalysts or catalyst carriers.
In particular, if a hydrogenation-active metal, such as a Group 1B or Group 2 metal, is supported by a method such as an impregnation method or a coprecipitation method, it can be used as an extremely good catalyst for hydrocarbon conversion. Since the catalyst using the porous inorganic oxide of the present invention has large pores, even if carbon or impurity metals are precipitated in the hydrogenation reaction of heavy hydrocarbons, the activity will be small and the catalyst will have a long life. It is also long.
よって、本発明は石油産業や一般の化学工業において極
めて有用である。Therefore, the present invention is extremely useful in the petroleum industry and general chemical industry.
実施例１ 市販のナトリウムＹ型ゼオライト（８ｉ０７ＡＪ、Ｏ。Example 1 Commercially available sodium Y-type zeolite (8i07AJ, O.
＝４．６（モル比））を塩化アンモニウム水溶液でイオ
ン交換し、酸化ナトリウム含量帆５重景％のアンモニウ
ムＹ型（ＮＨａＹ型）ゼオライトを得た。=4.6 (molar ratio)) was ion-exchanged with an aqueous ammonium chloride solution to obtain ammonium Y type (NHaY type) zeolite with a sodium oxide content of 5%.
なお、平均粒径は３μであった。Note that the average particle size was 3μ.
このようにして得られたＮ′Ｈ４Ｙ型ゼオライト６０重
量％、ベーマイトゲル４０重量％およびコーンスターチ
をゼオライトおよびベーマイトゲルの合計乾燥重量の５
重量％を混合し、１００℃で６０分混線を行なった。得
られたものを直径１ｕの円柱状に押出し成形した後に１
２０℃にて３時間乾燥した。このものの細孔分布および
細孔容積を水銀圧入法にて測定した。結果を第１表に示
す。60% by weight of the N'H4Y type zeolite, 40% by weight of boehmite gel and cornstarch were added to 5% of the total dry weight of the zeolite and boehmite gel.
% by weight were mixed and mixed at 100° C. for 60 minutes. The obtained product was extruded into a cylindrical shape with a diameter of 1U, and then
It was dried at 20°C for 3 hours. The pore distribution and pore volume of this material were measured by mercury intrusion method. The results are shown in Table 1.
次いで、得られたものを５５０℃で３時間焼成し、多孔
性無機酸化物を得た。このものの細孔分布および細孔容
積の測定結果を第１表に示す。Next, the obtained product was fired at 550° C. for 3 hours to obtain a porous inorganic oxide. Table 1 shows the measurement results of the pore distribution and pore volume of this product.
実施例２
実施例１において、コーンスターチに代工て馬鈴薯でん
ぷんを用いたこと以外′は実施例１と同様の操作を行な
った。細孔分布および細孔容積の結果を第１表に示す。Example 2 The same operations as in Example 1 were carried out except that potato starch was used as a substitute for cornstarch. The results of pore distribution and pore volume are shown in Table 1.
実施例３
実施例１において、コーンスターチニ代工てに一カラジ
ーナンを用いたこと以外は実施例１と同様の操作を行な
った。細孔分布および細孔容積の結果を第１表に示す。Example 3 The same operations as in Example 1 were carried out except that one carrageenan was used as a substitute for corn starch. The results of pore distribution and pore volume are shown in Table 1.
実施例４
実施例１において、コーンスターチの使用量をゼオライ
トおよびベーマイトゲルの合計乾燥重量の２重量％とじ
たこと以外は実施例１と同様の操作を行なった。細孔分
布および細孔容積の結果を第１表に示す。Example 4 The same operation as in Example 1 was performed except that the amount of corn starch used was 2% by weight of the total dry weight of zeolite and boehmite gel. The results of pore distribution and pore volume are shown in Table 1.
実施例５
実施例１において、コーンスターチの使用量をゼオライ
トおよびベーマイトゲルの合計乾燥重量の１０重月％と
したこと以外は、実施例１と同様の操作を行なった。細
孔分布および細孔容積の結果を第１表に示す。Example 5 The same operation as in Example 1 was performed except that the amount of corn starch used was 10% of the total dry weight of zeolite and boehmite gel. The results of pore distribution and pore volume are shown in Table 1.
比較例１
実施例１において、コーンスターチの代わりに可溶性デ
ンプンを使用したこと以外は実施例１と同様の操作を行
なった。細孔分布および細孔容積の結果を第１表に示す
。Comparative Example 1 The same operation as in Example 1 was performed except that soluble starch was used instead of cornstarch. The results of pore distribution and pore volume are shown in Table 1.
比較例２
実施例１において、コーンスターチの代わりにゼラチン
を使用したこと以外は、実施例１と同様の操作を行なっ
た。細孔分布および細孔容積の結果を第１表に示す。Comparative Example 2 The same operation as in Example 1 was performed except that gelatin was used instead of cornstarch. The results of pore distribution and pore volume are shown in Table 1.
比較例３
実施例１においてコーンスターチの代わりにブドウ糖を
用（・たこと以外は実施例１と同様の操作を行なった。Comparative Example 3 The same operation as in Example 1 was performed except that glucose was used instead of cornstarch.
細孔分布および細孔分布の結果を第１表に示す。The results of pore distribution and pore distribution are shown in Table 1.
比較例４
実施例１においてコーンスターチを使用しなかったこと
以外は実施例１と同様の操作を行なった。Comparative Example 4 The same operation as in Example 1 was performed except that cornstarch was not used in Example 1.
細孔分布および細孔分布の結果を第１表に示す。The results of pore distribution and pore distribution are shown in Table 1.
比較例５
アルミナおよびこのアルミナの乾燥重量に対して５重量
％のコーンスターチを混合し、１００℃で６０分混練を
行なった。得られたものを直径１朋の円柱状に押出し成
形した後に、１２０℃にて３時間乾燥した。このものの
細孔分布および細孔容積を測定した。結果を第１表に示
す。Comparative Example 5 Alumina and 5% by weight of corn starch based on the dry weight of the alumina were mixed and kneaded at 100° C. for 60 minutes. The obtained product was extruded into a cylindrical shape with a diameter of 1 mm, and then dried at 120° C. for 3 hours. The pore distribution and pore volume of this material were measured. The results are shown in Table 1.
手続ネ甫正書（自発）
昭和６０年５月２日
特許庁長官 志賀 学 殿
■、事件の表示
特願昭５９−９２７９４
２、発明の名称
多孔性無機酸化物の製造方法
３、補正をする者
事件との関係 特許出願人
重質油対策技術研究組合
４、代理人
〒１０４
東京都中央区京橋１丁目１番１０号
西勘ビル５階
（７４０７）弁理士 久保１）藤 部
電話（２７５）０７２１番
５、補正の対象
明細書の発明の詳細な説明の憫
６、補正の内容
（１）明細書箱９頁３行目のｒｌｏ００Å以上」を「５
００Å以上」に訂正する。Proceedings (self-motivated) May 2, 1985 Mr. Manabu Shiga, Director General of the Japan Patent Office ■, Indication of Case Patent Application No. 59-92794 2. Title of Invention Process for Producing Porous Inorganic Oxide 3. Amendments to be made Patent applicant: Heavy Oil Countermeasures Technology Research Association 4, Agent: 5F Nishikan Building, 1-10 Kyobashi, Chuo-ku, Tokyo (7407) 104 Patent Attorney Kubo 1) Fujibe Telephone (275) ) 0721 No. 5, Detailed explanation of the invention in the specification subject to amendment 6, Contents of amendment (1) "rlo00Å or more" on page 9, line 3 of the specification box to "5"
00Å or more”.
（２）同第９頁７行目のｒｉｏｏｏÅ以上」を「５００
Å以上」に訂正する。(2) On page 9, line 7, ``more than rioooÅ'' is changed to ``500
Corrected to ``more than Å''.
（３）同第９頁８〜９行目の「５００〜１０００人」を
「５００Å以上」に訂正する。(3) On page 9, lines 8-9, "500 to 1000 people" is corrected to "500 Å or more."
（４） 同第９頁９〜１０行目の「、１０００Å以上が
０．１ ｃｃ／ ｇ以上」を削除する。(4) Delete "1000 Å or more is 0.1 cc/g or more" on page 9, lines 9-10.
（５）同第１４頁の第１表を別紙の如く訂正する。(5) Table 1 on page 14 of the same page is corrected as shown in the attached sheet.
（以上）(that's all)
Claims (1)
多孔性無機酸化物を製造するＫあたり、大粒子ゼオライ
トに小粒子形成性無機結合剤および水膨潤性ゲル状物質
を混合することを特徴とする多孔性無機酸化物の製造方
法。 （２〕 大粒子ゼオライトの粒径が、０６１〜１０μで
ある特許請求の範囲第１項記載の製造方法。 （３） 小粒子形成性無機結合剤が、アルミナゾル。 アルミナゲル、シリカゲル、シリカ・アルミナゲル、シ
リカゾルあるいはベーマイトゲルである特許請求の範囲
第１項記載の製造方法。 （４）水膨潤性ゲル状物質が、コーンスターチ。 馬鈴薯でんぷん、サツマイモでんぷん、小麦でんぷん、
九−カラジーナン、マンナンあるいはアルギン酔憔で本
る縣詐饋重の節■笛１頂貫Ｐ載の加岳方法。[Claims] (1) Per K for producing a porous inorganic oxide consisting of large particles and small particles and having large pores, a large particle zeolite is combined with a small particle forming inorganic binder and a water-swellable gel-like material. A method for producing a porous inorganic oxide, the method comprising mixing substances. (2) The manufacturing method according to claim 1, wherein the large particle zeolite has a particle size of 0.61 to 10 μm. (3) The small particle forming inorganic binder is alumina sol. Alumina gel, silica gel, silica-alumina The manufacturing method according to claim 1, which is a gel, silica sol, or boehmite gel. (4) The water-swellable gel-like substance is corn starch. Potato starch, sweet potato starch, wheat starch,
9 - Carrageenan, mannan or algin A method of playing the prefecture fraud and heavy play with drunkenness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59092794A JPS60238149A (en) | 1984-05-11 | 1984-05-11 | Preparation of porous inorganic oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59092794A JPS60238149A (en) | 1984-05-11 | 1984-05-11 | Preparation of porous inorganic oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60238149A true JPS60238149A (en) | 1985-11-27 |
| JPH0456666B2 JPH0456666B2 (en) | 1992-09-09 |
Family
ID=14064330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59092794A Granted JPS60238149A (en) | 1984-05-11 | 1984-05-11 | Preparation of porous inorganic oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60238149A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030003632A (en) * | 2001-07-02 | 2003-01-10 | 주식회사 나노 | Fabricating Method for Catalyst Supporter using Inorganic Binder Sol |
| CN1309471C (en) * | 2001-04-13 | 2007-04-11 | 格雷斯公司 | Zeolite based catalyst of ultra-high kinetic conversion activity |
| JP2010179267A (en) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | Support, and method of producing the same |
| WO2012133327A1 (en) * | 2011-03-31 | 2012-10-04 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for producing hydrogenation catalyst |
| JP2012533427A (en) * | 2009-07-20 | 2012-12-27 | ユーオーピー エルエルシー | Binderless zeolite adsorbent, method for producing binderless zeolite adsorbent, and method for adsorption separation of para-xylene from mixed xylene using binderless zeolite adsorbent |
| CN111086997A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing mesoporous high-crystallinity Y-type molecular sieve by template method |
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| JP2010179268A (en) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | Plant for producing support |
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-
1984
- 1984-05-11 JP JP59092794A patent/JPS60238149A/en active Granted
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309471C (en) * | 2001-04-13 | 2007-04-11 | 格雷斯公司 | Zeolite based catalyst of ultra-high kinetic conversion activity |
| KR20030003632A (en) * | 2001-07-02 | 2003-01-10 | 주식회사 나노 | Fabricating Method for Catalyst Supporter using Inorganic Binder Sol |
| JP2010179267A (en) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | Support, and method of producing the same |
| JP2012533427A (en) * | 2009-07-20 | 2012-12-27 | ユーオーピー エルエルシー | Binderless zeolite adsorbent, method for producing binderless zeolite adsorbent, and method for adsorption separation of para-xylene from mixed xylene using binderless zeolite adsorbent |
| US8859448B2 (en) | 2009-07-20 | 2014-10-14 | Uop Llc | Binderless zeolitic adsorbents, methods for producing binderless zeolitic adsorbents, and processes for adsorptive separation of para-xylene from mixed xylenes using the binderless zeolitic adsorbents |
| WO2012133327A1 (en) * | 2011-03-31 | 2012-10-04 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for producing hydrogenation catalyst |
| JP2012213715A (en) * | 2011-03-31 | 2012-11-08 | Japan Oil Gas & Metals National Corp | Method for producing hydrogenation catalyst |
| AP3769A (en) * | 2011-03-31 | 2016-08-31 | Nippon Steel & Sumikin Eng Co | Method for producing hydrogenation catalyst |
| EA025233B1 (en) * | 2011-03-31 | 2016-12-30 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Method for producing hydrogenation catalyst |
| AU2012233965B2 (en) * | 2011-03-31 | 2017-03-02 | Cosmo Oil Co., Ltd. | Method for producing hydrogenation catalyst |
| US9839904B2 (en) | 2011-03-31 | 2017-12-12 | Japan Oil, Gas And Metals National Corporation | Method for producing hydrogenation catalyst |
| CN111086997A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing mesoporous high-crystallinity Y-type molecular sieve by template method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0456666B2 (en) | 1992-09-09 |
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