JPH0810627A - Impregnation of catalyst carrier - Google Patents
Impregnation of catalyst carrierInfo
- Publication number
- JPH0810627A JPH0810627A JP6170470A JP17047094A JPH0810627A JP H0810627 A JPH0810627 A JP H0810627A JP 6170470 A JP6170470 A JP 6170470A JP 17047094 A JP17047094 A JP 17047094A JP H0810627 A JPH0810627 A JP H0810627A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst carrier
- term
- carrier
- liquid
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000005470 impregnation Methods 0.000 title description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 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 5
- 239000007788 liquid Substances 0.000 claims description 53
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 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
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、触媒担体に活性金属の
Mo、Ni、Co、Mo-Ni、Mo-Co等を担持する際に用いられる
含浸方法に関するものであり、特に一次粒子のアスペク
ト比が30以下の粉体で形成される比較的脆い触媒担体の
含浸時における強度劣化を抑制する方法である。The present invention relates to a catalyst carrier containing an active metal.
Mo, Ni, Co, Mo-Ni, relates to an impregnation method used when supporting Mo-Co, etc., in particular, a relatively fragile catalyst carrier formed of powder having an aspect ratio of primary particles of 30 or less. This is a method of suppressing strength deterioration during impregnation.
【０００２】[0002]
【従来技術】触媒担体は、粉体を原料として一般的にこ
の粉体を混練、押し出し、焼成して作製される。触媒担
体はその触媒活性を上げるため細孔径が数十ｎｍ以下と
小さく、その細孔径分布がシャープであることが必要で
ある。このような触媒担体の細孔内に活性金属を担持す
るには、触媒担体を噴霧含浸、浸漬含浸などの含浸の
後、乾燥焼成を行う。噴霧含浸は、活性金属を含んだ担
持水溶液を触媒担体に噴霧することにより触媒担体に活
性金属を担持する方法であり、また浸漬含浸は、触媒担
体を活性金属を含む担持水溶液に浸漬することで触媒担
体に活性金属を担持する方法である。ところが、含浸の
際、速やかに触媒が有する細孔内部の気体と担持液の気
液置換が行われないために生ずる圧力上昇によって触媒
担体に亀裂、欠け、粉化が発生したり、機械的強度が更
に低下するという問題点がある。2. Description of the Related Art A catalyst carrier is generally produced by kneading, extruding and firing powder as a raw material. In order to enhance the catalytic activity of the catalyst carrier, it is necessary that the pore size is as small as several tens of nm or less and that the pore size distribution is sharp. In order to support the active metal in the pores of such a catalyst carrier, the catalyst carrier is impregnated by spray impregnation, immersion impregnation, etc., and then dried and calcined. Spray impregnation is a method of supporting an active metal on a catalyst carrier by spraying a supported aqueous solution containing an active metal on the catalyst carrier, and immersion impregnation is performed by immersing the catalyst carrier in a supported aqueous solution containing an active metal. This is a method of supporting an active metal on a catalyst carrier. However, during impregnation, the catalyst carrier is cracked, chipped or pulverized due to the pressure increase that occurs because the gas inside the pores of the catalyst and the supported liquid are not replaced rapidly, and mechanical strength is increased. Is further reduced.
【０００３】キャタリスト サホ゜ーツ アント゛ サホ゜ーティト゛ キャタリスツ(Cata
lyst Supports And Supported Catalysts;P40-41(198
7))には、アルミナ担体に担持液を含浸する際、触媒担
体の細孔内の担持液の気泡の圧力Ｐはヤング−ラプラス
式則に従う次式で示されている。 Ｐ−Ｐ0＝（２γ／ｒ）cosα ここで、Ｐ0；大気圧、γ；気固界面における表面張
力、ｒ；触媒担体の細孔半径、α；担持液の担体への接
触角である。アルミナ−水の場合、cosα＝１、γ＝７
×１０2N・m-1を例にとり、細孔半径が２．５nmである
と、細孔内の気泡に生じる圧力は、５６０barと非常に
高くなる。この圧力が含浸の際、触媒を破壊する原因で
あることが示されている。そして、その解決策としてこ
の気泡が、水に溶解、拡散し、触媒担体外に拡散しやす
いように減圧下で含浸を行う脱気含浸が有効であると述
べている。Catalist Supports Cat Supports
lyst Supports And Supported Catalysts; P40-41 (198
In (7)), the pressure P of the bubbles of the carrier liquid in the pores of the catalyst carrier when impregnating the carrier liquid into the alumina carrier is shown by the following equation according to the Young-Laplace equation rule. P−P 0 = (2γ / r) cosα where P 0 is atmospheric pressure, γ is the surface tension at the gas-solid interface, r is the pore radius of the catalyst carrier, α is the contact angle of the carrier liquid with the carrier. . In the case of alumina-water, cos α = 1, γ = 7
× takes 10 2 N · m -1 as an example, when the pore radius is 2.5 nm, a pressure generated in bubbles in the pores, very high and 560Bar. This pressure has been shown to be the cause of catalyst destruction during impregnation. Then, as a solution, it is described that degassing impregnation in which the bubbles are dissolved and diffused in water and impregnated under reduced pressure so that they easily diffuse out of the catalyst carrier.
【０００４】[0004]
【発明が解決しようとする課題】しかし、脱気含浸は、
設備のコストが高いという問題点がある。更に、一次粒
子のアスペクト比が３０以下の触媒担体は、細孔径分布
がシャープであるため良好な触媒活性が得られるが触媒
担体強度としては比較的脆く、従来の担持水溶液では細
孔径の分布が小さいため速やかに細孔内部の気体との気
液置換が行われず含浸時の強度劣化が特に大きいという
問題点がある。本発明は、上記の問題点に鑑み、担持液
を触媒担体に含浸させ、活性金属を担持する際の触媒担
体の強度劣化を抑制することができる安価な触媒担体の
担持方法を提供するものである。アスペクト比とは粉体
の一次粒子の短軸と長軸の比のことを言い、例えば粉体
の一次粒子の透過型電子顕微鏡によって写真を撮り、無
差別に10個の粒子について短軸、長軸の長さをはかり、
その比を求めたものである。However, the degassing impregnation is
There is a problem that the cost of equipment is high. Further, a catalyst carrier having an aspect ratio of primary particles of 30 or less has a narrow pore size distribution and thus can obtain good catalyst activity, but is relatively fragile in terms of catalyst support strength. Since it is small, gas-liquid replacement with the gas inside the pores is not performed promptly, and there is a problem that strength deterioration during impregnation is particularly large. In view of the above problems, the present invention provides an inexpensive method for supporting a catalyst carrier that can impregnate a catalyst carrier with a supporting liquid and suppress the strength deterioration of the catalyst carrier when supporting an active metal. is there. Aspect ratio refers to the ratio of the short axis to the long axis of the primary particles of the powder.For example, take a photograph of the primary particles of the powder with a transmission electron microscope, and indiscriminately determine the short axis and long axis of 10 particles. Measure the length of the shaft,
The ratio is obtained.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記問題点
を解決するため、担持液、特にその表面張力に着目して
鋭意検討を続けた結果、担持液の表面張力を有機溶剤の
添加で制御することにより、触媒の細孔内部の気体と担
持液の気液置換が速やかに行われないために生ずる圧力
上昇によって発生する触媒表面や内部の亀裂の抑制、機
械的強度の改善、粉化の抑制等ができることを見い出し
た。In order to solve the above problems, the inventors of the present invention have conducted extensive studies focusing on the supporting liquid, particularly the surface tension of the supporting liquid. As a result, the surface tension of the supporting liquid is increased by adding an organic solvent. By controlling with, control of cracks on the catalyst surface and inside caused by pressure rise caused by gas-liquid replacement of the gas inside the catalyst pores with the supported liquid is not performed promptly, improvement of mechanical strength, powder It has been found that it is possible to suppress the conversion.
【０００６】すなわち、本発明は、一次粒子のアスペク
ト比が30以下であるアルミナ担体にMo,Ni,Coからなる活
性金属を単独若しくは２種以上を含む担持液を含浸する
方法において、前記担持液に溶解度パラメーターの水素
結合項と極性項の和が溶解度パラメーターの分子間力
項、極性項、水素結合項の和の40％以上である有機溶剤
を添加して、該担持液の表面張力を40dyn/cm以下として
から含浸することを特徴とする触媒担体の含浸方法であ
る。That is, the present invention provides a method of impregnating an alumina carrier having an aspect ratio of primary particles of 30 or less with a carrier liquid containing an active metal composed of Mo, Ni, Co alone or in combination of two or more. To the organic solvent whose sum of the hydrogen bond term and the polar term of the solubility parameter is 40% or more of the sum of the intermolecular force term, the polar term and the hydrogen bond term of the solubility parameter, the surface tension of the supporting liquid is adjusted to 40 dyn. It is a method of impregnating a catalyst carrier, which comprises impregnating the material with a content of not more than / cm.
【０００７】本発明の理解を容易にするため、具体的か
つ詳細に説明する。触媒担体の基本組成は主として、Al
2O3であり、数十nm以下の細孔を有している。そして、
その一次粒子のアスペクト比は30以下のものである。担
持液は、活性金属であるMo、Ni、Coを含む塩を単独また
複数溶解した液である。例えば、一般的に用いられる塩
は、ヘプタモリブデン酸アンモニウム塩、硝酸コバルト
塩、硝酸ニッケル塩、炭酸コバルト塩、炭酸ニッケル塩
等である。To facilitate understanding of the present invention, a specific and detailed description will be given. The basic composition of the catalyst carrier is mainly Al
2 O 3 and has pores of several tens of nm or less. And
The aspect ratio of the primary particles is 30 or less. The supporting liquid is a liquid in which one or more salts containing active metals Mo, Ni, and Co are dissolved. For example, commonly used salts are ammonium heptamolybdate, cobalt nitrate, nickel nitrate, cobalt carbonate, nickel carbonate and the like.
【０００８】本発明者らは、上記の粉末で作製された担
体に様々な表面張力を有する担持液を含浸し、機械的強
度や亀裂の発生状況を比較した。その結果、担持液の表
面張力が40dyn/cmより大きいと、触媒が有する細孔内部
の気体と担持液との気液置換が速やかに行われず、細孔
内部の圧力上昇が発生し、触媒表面に亀裂が生じ機械的
強度が低下する。従って、担持液の表面張力は40dyn/cm
以下にすることが有効である。The present inventors impregnated a carrier made of the above powder with a carrier liquid having various surface tensions, and compared the mechanical strength and the occurrence of cracks. As a result, when the surface tension of the supported liquid is larger than 40 dyn / cm, gas-liquid replacement between the gas inside the pores of the catalyst and the supported liquid is not performed promptly, and a pressure increase inside the pores occurs, and the catalyst surface Cracks occur in the steel and the mechanical strength decreases. Therefore, the surface tension of the supporting liquid is 40 dyn / cm.
The following is effective.
【０００９】担持液の表面張力を40dyn/cm以下に下げる
には、担持液と相溶性のある有機溶剤を添加する方法と
界面活性剤を添加する方法がある。担持液に界面活性剤
を添加して表面張力を低下させることを試みた場合、こ
のような界面活性物質はそのほとんどが気液界面に集ま
り、見かけ上、担持液の表面張力は減少するものの実際
に表面張力が減少しているのは担持液の表面近傍の極一
部に限られ、その他の大部分の溶液部には界面活性剤の
寄与がないので表面張力が減少しない。このため、この
ような界面活性剤を含んだ担持液で噴霧含浸を行うと、
結果として高い表面張力をもつ液滴が含浸され、亀裂の
発生、機械的強度の低下、欠け、粉化等が生じる。この
ことから担持液の表面張力の低下は、あくまで個々の溶
剤分子間の凝集力の低下により得られることが必要であ
り、界面活性剤の使用は好ましくない。In order to reduce the surface tension of the supporting liquid to 40 dyn / cm or less, there are a method of adding an organic solvent compatible with the supporting liquid and a method of adding a surfactant. When attempting to lower the surface tension by adding a surfactant to the supporting liquid, most of these surface-active substances gather at the gas-liquid interface, and although the surface tension of the supporting liquid apparently decreases, The surface tension is reduced only in a very small part in the vicinity of the surface of the supporting liquid, and the surface tension is not reduced because the surfactant does not contribute to most other solution parts. Therefore, when spray impregnation is carried out with a supporting liquid containing such a surfactant,
As a result, the liquid droplets having a high surface tension are impregnated, and cracks are generated, mechanical strength is reduced, chips are generated, and powdering occurs. From this, it is necessary that the reduction of the surface tension of the supporting liquid is obtained by the reduction of the cohesive force between the individual solvent molecules, and the use of the surfactant is not preferable.
【００１０】有機溶剤の溶解度パラメーターの水素結合
項と極性項の和が溶解度パラメーターの分子間力項、極
性項、水素結合項の和の40％以上である有機溶剤は水と
一定の相溶性を有し、水より表面張力が低い。従って、
このような有機溶剤を添加すると水溶液の表面張力を下
げることができる。一般概念として、界面活性剤と有機
溶剤とでは一部にオーバーラップする範疇の液体であ
り、厳格な区別が困難な場合があるが、本発明の範囲で
規定する有機溶剤では界面活性剤的性質、すなわち、気
体-液体界面に自発的に集まるような性質を有するもの
は含まない。本発明者らは上記の有機溶剤のうち一種も
しくは複数を担持水溶液を添加して表面張力を40dyn/cm
以下にした担持液を作製し試験を行った。その結果、含
浸後の担体の機械的強度が改善され触媒の含浸工程が好
適に実施できることがわかった。本発明で使用可能な有
機溶剤は、溶解度パラメーターの水素結合項と極性項の
和が溶解度パラメーターの分子間力項、極性項、水素結
合項の和の40％以上であり、具体的にはアルコール類、
ケトン類、カルボン酸類、エーテル類、エステル類等が
あるが、効果の程度、入手の容易さ、安全性、コスト等
から、エタノール、プロパノール、ブタノール、アセト
ン、メチルエチルケトン等がより好ましい。これらは触
媒の活性に影響を与えない。溶解度パラメーターの水素
結合項と極性項の和が溶解度パラメーターの分子間力
項、極性項、水素結合項の和の40％未満である有機溶剤
は、水との相溶性が乏しいため担持液の表面張力を40dy
n/cm以下まで低下させる量を添加すると相分離して好適
に実施できない。An organic solvent in which the sum of the hydrogen bond term and the polar term of the solubility parameter of the organic solvent is 40% or more of the sum of the intermolecular force term, the polar term and the hydrogen bond term of the solubility parameter has a certain compatibility with water. It has a lower surface tension than water. Therefore,
Addition of such an organic solvent can reduce the surface tension of the aqueous solution. As a general concept, a surfactant and an organic solvent are liquids in a category that partially overlap each other, and strict distinction may be difficult, but the organic solvent defined in the scope of the present invention has a surfactant-like property. That is, it does not include those having the property of spontaneously gathering at the gas-liquid interface. The present inventors added an aqueous solution carrying one or more of the above organic solvents to increase the surface tension to 40 dyn / cm.
The following supporting liquid was prepared and tested. As a result, it has been found that the mechanical strength of the carrier after impregnation is improved and the impregnation step of the catalyst can be preferably carried out. The organic solvent that can be used in the present invention, the sum of the hydrogen bond term and the polar term of the solubility parameter is 40% or more of the sum of the intermolecular force term, the polar term and the hydrogen bond term of the solubility parameter, and specifically, the alcohol. Kind,
Although there are ketones, carboxylic acids, ethers, esters and the like, ethanol, propanol, butanol, acetone, methyl ethyl ketone and the like are more preferable in terms of degree of effect, availability, safety, cost and the like. These do not affect the activity of the catalyst. The organic solvent whose sum of the hydrogen bond term and polar term of the solubility parameter is less than 40% of the sum of the intermolecular force term, polar term and hydrogen bond term of the solubility parameter has poor compatibility with water, so the surface of the carrier liquid Tension 40 dy
If the amount is decreased to n / cm or less, phase separation occurs and it cannot be suitably performed.
【００１１】尚、溶解度パラメーター(δ)とは、物質の
凝集エネルギー密度の平方根であり、δ＝((δd)2＋(δ
p)2＋(δh)2)1/2で表される。なお、δdは分子間力項、
δpは極性項、δhは水素結合項である。本発明で使用で
きる有機溶剤は、(δp＋δh)／(δd＋δp＋δh)≧0.40
である有機溶剤である。以下本発明の実施例について説
明する。The solubility parameter (δ) is the square root of the cohesive energy density of a substance, and δ = ((δd) 2 + (δ
It is represented by p) 2 + (δh) 2 ) 1/2 . Δd is the intermolecular force term,
δp is a polar term and δh is a hydrogen bond term. The organic solvent that can be used in the present invention is (δp + δh) / (δd + δp + δh) ≧ 0.40
Is an organic solvent. Examples of the present invention will be described below.
【００１２】[0012]
【実施例１】平均アスペクト比30以下の一次粒子から形
成され、10nm程度の中心細孔径を有し、担体強度11.3MP
a、亀裂を有する担体の割合20％の触媒担体（平均触媒
径；1/12インチ）にヘプタモリブデン酸アンモニウム塩
水溶液に溶解度パラメーターの分子間力項、極性項、水
素結合項の和のうち極性項と水素結合項の和の割合が57
％であるイソプロパノールを濃度5mol％混在させた担持
液（表面張力35dyn/cm）を噴霧含浸し、130℃で乾燥し
た。乾燥後の強度は、10.9MPaに、亀裂の有する割合は4
0％、粉化した割合は5％であった。これを更に、同等な
イソプロパノールを濃度5mol％を含む表面張力35dyn/cm
を有するニッケルの硝酸塩の担持液を連続的に同様に含
浸すると強度は10.8MPaに、亀裂の有する割合は45％、
粉化した割合は10％となった。このように、含浸による
触媒担体の強度劣化は小さく、また、亀裂の有する割
合、粉化する触媒の割合の増加も少ない。これを500℃
で焼成し得られた触媒の脱硫活性、脱金属活性は比較例
の触媒と同等であった。[Example 1] A primary particle having an average aspect ratio of 30 or less, a central pore diameter of about 10 nm, and a carrier strength of 11.3MP
a, The ratio of the intermolecular force term, polar term, and hydrogen bond term of the solubility parameter in the aqueous solution of ammonium heptamolybdate in a catalyst carrier (average catalyst diameter; 1/12 inch) with a ratio of cracked carrier of 20% is polar. The ratio of the sum of the term and the hydrogen bond term is 57
% Of isopropanol mixed in a concentration of 5 mol% was spray-impregnated with a supporting liquid (surface tension of 35 dyn / cm) and dried at 130 ° C. The strength after drying is 10.9 MPa, and the ratio of cracks is 4
0% and powdered ratio was 5%. This was further treated with an equivalent isopropanol concentration of 5 mol% and a surface tension of 35 dyn / cm.
When the nickel nitrate bearing liquid containing is continuously impregnated in the same manner, the strength is 10.8 MPa, the ratio of cracks is 45%,
The powdered ratio was 10%. As described above, the strength deterioration of the catalyst carrier due to the impregnation is small, and the ratio of cracks and the ratio of the powdered catalyst are small. This is 500 ℃
The desulfurization activity and demetallization activity of the catalyst obtained by calcination in Example 3 were the same as those of the catalyst of Comparative Example.
【００１３】[0013]
【比較例１】10nmの中心細孔径を有していて、担体強度
11.3MPa、亀裂を有する割合20％の触媒担体にモリブデ
ンの担持量8〜10wt％を溶解したヘプタモリブデン酸ア
ンモニウム塩水溶液の担持液（表面張力70dyn/cm）を噴
霧含浸し130℃で乾燥した。その強度は6.1MPaに、亀裂
の有する割合は80％、粉化する割合は50％となった。こ
れを更に、表面張力69dyn/cmを有するニッケルの硝酸塩
の担持液を連続的に同様に含浸、乾燥を行うと強度は5.
8MPaに低下し、亀裂の有する割合は90％、粉化する割合
は60％に増加した。[Comparative Example 1] A carrier having a central pore diameter of 10 nm and a carrier strength
A carrier solution (surface tension 70 dyn / cm) of ammonium heptamolybdate aqueous solution in which a supported amount of molybdenum of 8 to 10 wt% was dissolved in a catalyst carrier of 11.3 MPa and a crack ratio of 20% was spray impregnated and dried at 130 ° C. Its strength was 6.1 MPa, the rate of cracks was 80%, and the rate of pulverization was 50%. Further, this is continuously impregnated with a supporting solution of nickel nitrate having a surface tension of 69 dyn / cm in the same manner, and the strength is 5.
It decreased to 8MPa, the rate of cracks increased to 90%, and the rate of powdering increased to 60%.
【００１４】[0014]
【比較例２】実施例１の担持液のイソプロパノールの代
わりにノニオン系の界面活性剤であるポリオキシエチレ
ンアルキルエーテルを0.1wt％混在させたモリブデン系
担持液（表面張力30dyn/cm）及びニッケル系担持液（表
面張力35dyn/cm）を用い実施例１と同様に噴霧含浸し13
0℃で乾燥した。乾燥後の強度は、7.4MPaに、亀裂の有
する割合は73％、粉化する割合は、40％であった。ま
た、同様の界面活性剤を含むニッケル系の担持液で含
浸、乾燥を行うと、強度は7.1MPaに、亀裂の有する担体
の割合は80％、粉化した担体の割合は40％となった。比
較例１と同様に、触媒担体の強度劣化が大きく、また、
亀裂の有する割合、粉化する触媒の割合の増加も大き
い。Comparative Example 2 A molybdenum-based carrier liquid (surface tension 30 dyn / cm) in which 0.1 wt% of polyoxyethylene alkyl ether, which is a nonionic surfactant, is mixed in place of the isopropanol of the carrier liquid of Example 1, and a nickel-based carrier liquid. The carrier solution (surface tension 35 dyn / cm) was spray impregnated in the same manner as in Example 1 13
Dried at 0 ° C. The strength after drying was 7.4 MPa, the ratio of cracks was 73%, and the ratio of pulverization was 40%. Further, when impregnated with a nickel-based carrier liquid containing a similar surfactant and dried, the strength was 7.1 MPa, the ratio of carriers having cracks was 80%, and the ratio of powdered carriers was 40%. . Similar to Comparative Example 1, the strength deterioration of the catalyst carrier was large, and
The increase of the ratio of cracks and the ratio of powdered catalyst is also large.
【００１５】実施例１のイソプロパノールを担持液に混
在させると溶液全体に分散し、溶液全体の表面張力が減
少するのに対して、比較例２の界面活性剤のポリオキシ
エチレンアルキルエーテルでは活性種のほとんどが気液
界面に集まり、気液界面の表面張力は減少するもののそ
の他の大多数の溶液部は表面張力が減少しないので噴霧
含浸を行うと高い表面張力を持つ液滴が含浸され、亀裂
の発生、機械的強度の低下、欠け、粉化の発生が生じ
る。When isopropanol of Example 1 is mixed in the supporting liquid, it is dispersed in the whole solution and the surface tension of the whole solution is decreased, whereas in the polyoxyethylene alkyl ether of the surfactant of Comparative Example 2, the active species is Most of the liquid concentrates on the gas-liquid interface, and the surface tension of the gas-liquid interface decreases, but the surface tension of most of the other solution parts does not decrease.Therefore, spray impregnation impregnates droplets with high surface tension and cracks. Generation, deterioration of mechanical strength, chipping, and pulverization.
【００１６】[0016]
【発明の効果】以上説明したように、溶解度パラメータ
ーの極性項と水素結合項の和が溶解度パラメーターの分
子間力項、極性項、水素結合項の和の40％以上である有
機溶剤から選ばれる一種、若しくは複数を含むことで表
面張力を40dyn/cm以下とした担持液に含浸することで、
触媒が有する細孔内部の気体と担持液の気液置換を速や
かに行わせ、生ずる圧力上昇を抑制することができ、触
媒表面や内部に発生する亀裂で40％程の抑制、機械的強
度で1.5倍程の改善、欠け、粉化で50％程の抑制ができ
るようになった。また、実施例１、比較例１(従来法)で
作製された触媒の活性試験(脱硫活性、脱金属活性)を行
ったところ、その活性に差はなかった。特公平2-35710
の耐火物の製造法において耐火物の成形物にコロイド状
シリカ液と界面活性剤または水溶性有機物とからなる担
持液を含浸させ、必要に応じて乾燥または焼成する事お
よび、この方法により耐火物の圧縮破壊強度が向上でき
ることが示されているが、対象が耐火物であり、また液
がコロイド状シリカ液と本方法の液である触媒担持液と
は異なる。また、特公昭62ー42743のアルキレンオキシサ
イド製造用触媒では、アルカリ金属含浸液の溶媒に誘電
定数8以下の溶剤を使用することで、銀担持触媒にアル
カリ金属を特定的に導入することを可能とするものであ
るが、本方法の目的は機械的強度の低下の抑制であり目
的が全く異なる。Industrial Applicability As described above, the organic solvent is selected such that the sum of the polar term and the hydrogen bond term of the solubility parameter is 40% or more of the sum of the intermolecular force term, the polar term and the hydrogen bond term of the solubility parameter. By impregnating a supporting liquid having a surface tension of 40 dyn / cm or less by including one kind or a plurality of kinds,
The gas inside the pores of the catalyst can be quickly replaced with the supported liquid by gas-liquid exchange, and the pressure rise that occurs can be suppressed, and the cracks that occur on the surface and inside the catalyst can be suppressed by about 40% and with mechanical strength. Improvement of about 1.5 times, chipping, and powdering can be suppressed by about 50%. Further, when the activity tests (desulfurization activity, demetalization activity) of the catalysts produced in Example 1 and Comparative Example 1 (conventional method) were conducted, there was no difference in the activity. Japanese Examined Trademark 2-35710
In the method for producing a refractory, the impregnated product of the refractory is impregnated with a supporting liquid composed of a colloidal silica liquid and a surfactant or a water-soluble organic substance, and dried or fired as necessary, and the refractory is manufactured by this method. Although it has been shown that the compressive fracture strength can be improved, it is different from the catalyst-supported liquid whose object is a refractory and whose liquid is the colloidal silica liquid and the liquid of the present method. Also, in the catalyst for alkylene oxyside production of JP-B-62-42743, it is possible to specifically introduce an alkali metal into a silver-supported catalyst by using a solvent having a dielectric constant of 8 or less as the solvent for the alkali metal impregnating liquid. However, the purpose of this method is to suppress the decrease in mechanical strength, and the purpose is completely different.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/755 23/88 Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B01J 23/755 23/88 Z
Claims (1)
アルミナ担体にMo,Ni及びCoからなる活性金属を単独若
しくは２種以上を含む担持液を含浸する方法において、
前記担持液に溶解度パラメーターの水素結合項と極性項
の和が溶解度パラメーターの分子間力項、極性項、水素
結合項の和の40％以上である有機溶剤を添加して、該担
持液の表面張力を40dyn/cm以下としてから含浸すること
を特徴とする触媒担体の含浸方法。1. A method of impregnating an alumina carrier having an aspect ratio of primary particles of 30 or less with a supporting liquid containing an active metal composed of Mo, Ni and Co alone or in combination of two or more kinds,
An organic solvent whose sum of the hydrogen bond term and the polar term of the solubility parameter is 40% or more of the sum of the intermolecular force term, the polar term and the hydrogen bond term of the solubility parameter is added to the supporting solution, and the surface of the supporting solution is added. A method for impregnating a catalyst carrier, which comprises impregnating the material with a tension of 40 dyn / cm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6170470A JPH0810627A (en) | 1994-06-30 | 1994-06-30 | Impregnation of catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6170470A JPH0810627A (en) | 1994-06-30 | 1994-06-30 | Impregnation of catalyst carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0810627A true JPH0810627A (en) | 1996-01-16 |
Family
ID=15905544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6170470A Pending JPH0810627A (en) | 1994-06-30 | 1994-06-30 | Impregnation of catalyst carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0810627A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174511B1 (en) | 1997-07-15 | 2001-01-16 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| US7390528B2 (en) | 2003-03-31 | 2008-06-24 | Seiko Epson Corporation | Method for forming functional porous layer, method for manufacturing fuel cell, electronic device, and automobile |
| CN105642336A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation technique of hydrocracking catalyst |
| CN105709801A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for chemical hydrocracking catalyst |
| CN104549429B (en) * | 2013-10-23 | 2017-02-08 | 中国石油化工股份有限公司 | Clean preparation method of hydrocracking catalyst without NOx discharging |
| KR20220031181A (en) * | 2020-09-04 | 2022-03-11 | 한국생산기술연구원 | Fabricating Method of Metal Nano Catalyst using Ionic Liquid |
-
1994
- 1994-06-30 JP JP6170470A patent/JPH0810627A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174511B1 (en) | 1997-07-15 | 2001-01-16 | Japan Energy Corporation | Pseudoboehmite powder for catalyst carrier and process for preparing the same |
| US7390528B2 (en) | 2003-03-31 | 2008-06-24 | Seiko Epson Corporation | Method for forming functional porous layer, method for manufacturing fuel cell, electronic device, and automobile |
| CN104549429B (en) * | 2013-10-23 | 2017-02-08 | 中国石油化工股份有限公司 | Clean preparation method of hydrocracking catalyst without NOx discharging |
| CN105642336A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation technique of hydrocracking catalyst |
| CN105709801A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for chemical hydrocracking catalyst |
| KR20220031181A (en) * | 2020-09-04 | 2022-03-11 | 한국생산기술연구원 | Fabricating Method of Metal Nano Catalyst using Ionic Liquid |
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