JP2510630B2 - Alumina-based fluidized catalyst manufacturing method - Google Patents
Alumina-based fluidized catalyst manufacturing methodInfo
- Publication number
- JP2510630B2 JP2510630B2 JP62288830A JP28883087A JP2510630B2 JP 2510630 B2 JP2510630 B2 JP 2510630B2 JP 62288830 A JP62288830 A JP 62288830A JP 28883087 A JP28883087 A JP 28883087A JP 2510630 B2 JP2510630 B2 JP 2510630B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- fluidized catalyst
- slurry
- metal
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明はアルミナ担体に金属成分を担持してなる流動
触媒の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a method for producing a fluidized catalyst in which a metal component is supported on an alumina carrier.
〈発明が解決しようとする問題点〉 流動床反応は気固の接触効率が良いため反応率が高
く、又発熱あるいは吸熱を伴う反応におけるは熱の除
去、供給が容易である等の利点を有しており数多くの反
応に用いられている。<Problems to be Solved by the Invention> The fluidized bed reaction has a high reaction rate because of good gas-solid contact efficiency, and has advantages such as easy removal and supply of heat in reactions involving exotherm or endotherm. It is used in many reactions.
流動床反応における触媒粒子は粒子相互および装置の
器壁との衝突により微粉化されると、触媒層の圧損増
大、粒度分布のかたよりによる流動性の悪化、触媒の飛
散等を招くので特に耐摩耗性に優れていることが要求さ
れる。When the catalyst particles in the fluidized bed reaction are pulverized due to collision between the particles and the vessel wall of the equipment, the pressure loss of the catalyst layer increases, the fluidity deteriorates due to the particle size distribution, and the catalyst scatters. It is required to have excellent properties.
〈問題点を解決する為の手段〉 本発明者等はかかる問題点を克服するべく鋭意検討し
た結果、本発明に到着した。しかしてその目的は、耐摩
耗性に優れたアルミナ担体と金属成分から成る流動触媒
及びその製造方法を提供することにあり、かかる本発明
の目的は、担体成分であるアルミナと金属成分を含有す
るスラリーを噴霧乾燥し、焼成して流動触媒を製造する
方法において、噴務乾燥に先立ち該スラリーを湿式で平
均粒径0.35μｍ以下になるまで微粉砕することによって
容易に達成される。<Means for Solving Problems> The present inventors arrived at the present invention as a result of extensive studies to overcome such problems. Therefore, an object of the present invention is to provide a fluidized catalyst comprising an alumina carrier having excellent wear resistance and a metal component, and a method for producing the same, and an object of the present invention is to provide a carrier component containing alumina and a metal component. In a method of producing a fluidized catalyst by spray-drying a slurry and calcining it, it is easily achieved by finely pulverizing the slurry by a wet method until the average particle size becomes 0.35 μm or less, prior to spray drying.
以下本発明を更に詳細に説明すると、担体成分である
アルミナはγ−アルミナが好ましいが市販のものでも擬
ベーマイトゲルを焼成して得たものでもよい。Explaining the present invention in more detail below, γ-alumina is preferable as alumina as the carrier component, but it may be commercially available or obtained by firing pseudo-boehmite gel.
本発明において、このアルミナ担体に担持される金属
成分は、場合に応じて広い種類のものを包含し、通常酸
化物として担持される。In the present invention, the metal component supported on the alumina carrier includes a wide variety of metals depending on the case, and is usually supported as an oxide.
そして担持の方法としては、例えばγ−アルミナを水
と混合して５〜60wt％好ましくは10〜40wt％の水性スラ
リーとした後、金属成分であるコバルト、鉄、ニッケ
ル、マンガン、ルテニウム等の原料化合物と混合する。
金属成分の原料化合物は可溶性のものであれば何でもよ
いが、経済性及び取扱いが容易等のため硫酸塩が好まし
く一般には水溶液として用いられる。Then, as a supporting method, for example, γ-alumina is mixed with water to form an aqueous slurry of 5 to 60 wt%, preferably 10 to 40 wt%, and then a raw material of metal components such as cobalt, iron, nickel, manganese, and ruthenium. Mix with compound.
The raw material compound of the metal component may be any soluble compound, but a sulfate salt is preferable and generally used as an aqueous solution because of its economical efficiency and easy handling.
金属成分の担持量は触媒の使用目的により決定され
る。The amount of the metal component supported depends on the purpose of use of the catalyst.
次に上記の金属成分を含有するアルミナスラリーにア
ルカリ含有溶液を添加し、金属成分を難溶性の水酸化物
として担体上に析出させる。硝酸根及びアルカリ金属は
過又は傾溶により更に必要ならば洗浄により除去す
る。Next, an alkali-containing solution is added to the above-mentioned alumina slurry containing the metal component to deposit the metal component as a sparingly soluble hydroxide on the carrier. Nitrate and alkali metal are removed by over-dissolving or decanting, and if necessary by washing.
得られた過ケーキを水と混合し再度５〜60wt％好ま
しくは10〜30wt％の水性スラリーとした後湿式でスラリ
ー粒子の平均粒径が0.35μｍ以下になるまで微粉砕す
る。The obtained overcake is mixed with water again to make an aqueous slurry of 5 to 60 wt%, preferably 10 to 30 wt%, and then finely pulverized by a wet method until the average particle diameter of the slurry particles becomes 0.35 μm or less.
粉砕の方式は特に限定されないが微粉砕の程度が不充
分だと耐摩耗性の優れた触媒が得られず、驚くべきこと
に平均粒径がわずかに0.1μｍ大きくなっただけで極度
に耐摩耗強度が低下する。The method of pulverization is not particularly limited, but if the degree of fine pulverization is insufficient, a catalyst with excellent wear resistance cannot be obtained, and surprisingly, it is extremely wear resistant even if the average particle size increases slightly by 0.1 μm. Strength is reduced.
次に微粉砕されたスラリーを噴霧乾燥し、次いで適度
な温度で空気雰囲気下焼成して耐摩耗性の優れた流動触
媒を得る。Next, the finely pulverized slurry is spray-dried and then calcined at an appropriate temperature in an air atmosphere to obtain a fluidized catalyst having excellent wear resistance.
以下実施例により本発明を具体的に説明するが本発明
はその要旨をこえない限り以下の実施例に限定されるも
のではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお、耐摩耗強度は流動接触分解触媒の試験法として
知られる“Test Method of Synthetic Cracking Cataly
sts"アメリカンサイアナミッド社6/31 4m-1/57記載の方
法に準じ行った下記の式より求めた摩耗損失の値で示し
た。The abrasion resistance is known as "Test Method of Synthetic Cracking Cataly"
sts "American Cyanamid Co., Ltd. 6/31 4m-1 / 57 The value of wear loss obtained by the following formula was performed according to the method described.
但し、A:0〜５時間に飛散もしくは摩耗損失した触媒
の重量 B:5〜20時間に摩耗損失した触媒の重量 C:試験に供した触媒の重量 実施例−１ 擬ベーマイトゲルを焼成して得た微粒状γ−アルミナ
3.0kgを水7.0kg中に添加し、ついで硝酸ルテニウム含有
溶液74g（Ru＝4.4g）硝酸マンガン水溶液2.41kg（Mn＝
0.37kg）、硝酸コバルト水溶液4.36kg（Co＝0.88kg）を
撹拌下添加した。 However, A: Weight of catalyst that was scattered or lost due to wear for 0 to 5 hours B: Weight of catalyst that was lost due to wear for 5 to 20 hours C: Weight of catalyst used for the test Example-1 Fine-grained γ-alumina obtained
3.0 kg was added to 7.0 kg of water, and then ruthenium nitrate-containing solution 74 g (Ru = 4.4 g) manganese nitrate aqueous solution 2.41 kg (Mn =
0.37 kg) and 4.36 kg of cobalt nitrate aqueous solution (Co = 0.88 kg) were added with stirring.
次に10wt％水酸化ナトリウム水溶液をスラリーpHが1
0.2になるまで添加し、各金属の水酸化物沈澱をγ−ア
ルミナ上に析出させ、過洗浄後再び水を添加し26.1kg
のスラリーとした。Next, add a 10 wt% sodium hydroxide aqueous solution to a slurry pH of 1
Add to 0.2 to precipitate the hydroxide precipitate of each metal on γ-alumina, after overwashing add water again to 26.1 kg.
Of the slurry.
次にこのスラリーを湿式粉砕機にてスラリー平均粒径
0.35μｍまで微粉砕した。Next, this slurry is processed by a wet pulverizer to obtain an average particle size of the slurry.
Finely pulverized to 0.35 μm.
次いで微粉砕されたスラリーを回転円盤式噴霧乾燥機
にて噴霧乾燥し得られた乾燥物を空気雰囲気下500℃で3
0分焼成して触媒を調製した。Then, the finely pulverized slurry was spray-dried with a rotary disk type spray dryer, and the dried product was dried at 500 ° C in an air atmosphere at 3 ° C.
The catalyst was prepared by calcining for 0 minutes.
実施例−２ スラリー平均粒径を0.28μｍまで微粉砕した外は実施
例−１と全く同様にして触媒を調製した。Example-2 A catalyst was prepared in exactly the same manner as in Example-1 except that the average particle size of the slurry was finely pulverized to 0.28 μm.
比較例−１、２ スラリー平均粒径を0.45μｍ、0.55μｍとした外は実
施例−１と全く同様にして触媒を調製した。Comparative Examples-1 and 2 A catalyst was prepared in exactly the same manner as in Example-1, except that the average particle diameter of the slurry was 0.45 µm and 0.55 µm.
実施例−１、２及び比較例−１、２で得られた触媒の
耐摩耗強度を（表−１）に示す。The abrasion resistance strengths of the catalysts obtained in Examples-1 and 2 and Comparative Examples-1 and 2 are shown in (Table-1).
〈発明の効果〉 本発明により耐摩耗性に優れた、アルミナ担体に金属
元素を担持して成る流動触媒を製造することができる。 <Effects of the Invention> According to the present invention, it is possible to produce a fluidized catalyst which is excellent in wear resistance and which is obtained by supporting a metal element on an alumina carrier.
フロントページの続き (56)参考文献 特開 昭57−45344（ＪＰ，Ａ) 特公 昭43−9645（ＪＰ，Ｂ１) 特公 昭45−39616（ＪＰ，Ｂ１) 特公 昭32−10164（ＪＰ，Ｂ１)Continuation of the front page (56) Reference JP-A-57-45344 (JP, A) JP-B 43-9645 (JP, B1) JP-B 45-39616 (JP, B1) JP-B 32-10164 (JP) , B1)
Claims (2)
するスラリーを噴霧乾燥し、焼成して流動触媒を製造す
る方法において、噴霧乾燥に先立ち該スラリーを湿式で
平均粒径0.35μｍ以下になるまで微粉砕することを特徴
とする耐摩耗性に優れた流動触媒の製造方法。1. A method for producing a fluidized catalyst by spray-drying a slurry containing alumina as a carrier component and a metal component and firing the slurry to obtain a fluidized catalyst having a mean particle size of 0.35 μm or less prior to spray-drying. A method for producing a fluidized catalyst having excellent wear resistance, characterized by finely pulverizing to
あり、金属成分中の金属元素が鉄族金属及びマンガンあ
るいは鉄族金属、マンガンおよび白金族金族金属である
特許請求の範囲第１項記載の方法。2. The support component alumina is γ-alumina, and the metal element in the metal component is an iron group metal and manganese or an iron group metal, manganese and a platinum group gold group metal. The method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288830A JP2510630B2 (en) | 1987-11-16 | 1987-11-16 | Alumina-based fluidized catalyst manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288830A JP2510630B2 (en) | 1987-11-16 | 1987-11-16 | Alumina-based fluidized catalyst manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01130737A JPH01130737A (en) | 1989-05-23 |
| JP2510630B2 true JP2510630B2 (en) | 1996-06-26 |
Family
ID=17735295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288830A Expired - Fee Related JP2510630B2 (en) | 1987-11-16 | 1987-11-16 | Alumina-based fluidized catalyst manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2510630B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5745344A (en) * | 1981-07-23 | 1982-03-15 | Kyushu Refract Co Ltd | Catalyst for fluidized bed catalytic gasification of heavy duty oil |
-
1987
- 1987-11-16 JP JP62288830A patent/JP2510630B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01130737A (en) | 1989-05-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |