JPH11510427A - Controlled porosity transition element carbides and nitrides - Google Patents
Controlled porosity transition element carbides and nitridesInfo
- Publication number
- JPH11510427A JPH11510427A JP8533616A JP53361696A JPH11510427A JP H11510427 A JPH11510427 A JP H11510427A JP 8533616 A JP8533616 A JP 8533616A JP 53361696 A JP53361696 A JP 53361696A JP H11510427 A JPH11510427 A JP H11510427A
- Authority
- JP
- Japan
- Prior art keywords
- nitrides
- transition element
- carbides
- compounds
- carbide
- 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
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 17
- 230000007704 transition Effects 0.000 title claims abstract description 9
- 150000001247 metal acetylides Chemical class 0.000 title claims description 11
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 3
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 3
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Ceramic Products (AREA)
Abstract
(57)【要約】 本発明は気孔容積と分布を制御した押出形材の遷移元素の炭化物と窒化物のその酸化物からの製法に関する。メソとマクロの気孔率がポリマー有機分子（例えば微結晶性セルロース）により生成する、このポリマー有機分子は燃焼後により多く開孔した多孔性構造体を生成する。成形法は解こう性と押出し性のある中間化合物の取得を含む、気孔直径が５０Åよりも大きいこれらの化合物の製造は、より多く開孔した多孔構造体がより大きい分子の触媒反応を可能とするので、触媒反応での用途範囲がある。更に、熱と物質拡散法に関連する問題即ち、極めて活性の高い触媒及び／又は極めて高い発熱反応を取扱う時に生じる問題はこのようにして殆んど生じない。 (57) Abstract The present invention relates to a method for producing a transition element of carbide and nitride from an oxide thereof in an extruded profile with controlled pore volume and distribution. Meso and macro porosity is generated by polymeric organic molecules (eg, microcrystalline cellulose), which produce a more open porous structure after combustion. The molding process involves obtaining intermediate compounds that are peptizable and extrudable, and the production of these compounds with pore diameters greater than 50 ° allows more open pore structures to catalyze larger molecules. Therefore, there is a range of applications in catalytic reactions. Furthermore, the problems associated with heat and mass diffusion processes, ie, the problems encountered when dealing with very active catalysts and / or very high exothermic reactions, are thus largely absent.
Description
【発明の詳細な説明】 気孔率制御済み遷移元素炭化物と窒化物 本発明は、例えば異性化反応若しくは水素添加反応、又は推進システムでのヒ ドラジン分解の如きガス発生に使用する反応での触媒用途で用いる、気孔容積と 分布を制御した、押出形材の遷移元素の炭化物と窒化物をその酸化物から製造す る方法に関する。 炭化物と窒化物は炭素と窒素を遷移金属酸化物の結晶性網構造体中に取込むこ とで形成した割込み型合金である。これらの合金は、各種金属（例えばイリジウ ム、白金、パラジウム）に類似の触媒活性を有する金属特性を示す。かかる化合 物の重要な特性は、硬度が極めて高いこと以外に耐食性があり、融点が高いこと である。これらの性質の直接的結果として、炭化物と窒化物は触媒作用だけでな く、切削工具、構造部品等にも用いられる。触媒作用での用途はブダール(Bouda rt)チームによる、表面積の大きい炭化物と窒化物の製法の開発に基づく。この 製法は、窒化物の場合はアンモニアガスを用い、炭化物の場合は水素とメタンの 混合物を用い、この前駆体酸化物の温度を均一で平滑に上昇させて遷移金属酸化 物を還元することから成る。この製法は表面積の大きい物質を生成するが、得ら れた多孔性構造体は制御できず、気孔直径は５０Å以下である。 本発明は、意図される気孔率を有する、押出形材（extruded shape）の遷移元 素の炭化物と窒化物が得られる点で既存技術と異る。本製法は、遷移金属の酸、 タングステンではタングステン酸、モリブデンではモリブデン酸を解こう状態で 得ることにある。低温で生成するときは、コロイド状で得られるこれらの酸を粉 末状で粉末状の微結晶性セルロースと混合する。 この工程のあと、稀水酸化アンモニウム溶液を解こう剤として用いて混合物を 解こうする。次いで、生成物を押出機を用いて押出す。押出された生成物の熱処 理は６０℃での乾燥とその後の１２０℃で乾燥から成り、乾燥時間は両方とも約 １２時間である。この後、６００℃で３時間か焼して酸を対応する酸化物に転換 し、酸中の残留セルロースを燃焼させる。このセルロースの除去で生成酸化物を 多孔性とし、この多孔性は酸と混合させたこの化合物を濃縮させるか、又は解こ う剤として用いた水酸化アンモニウムの含有量で制御できる。この工程の後、炭 化物と窒化物が、窒化物の場合はアンモニアガス雰囲気で、炭化物の場合は水素 とメタンとの雰囲気で均一で平滑にこれら前駆物質を加熱して得られる。 典型的例 図１は炭化モリブデンの場合での本方法で得られた多孔性構造体を示す。Ｙ軸 は比容積増分（ｄ／ｄＶ）（ｃｍ3／ｇ）であり、Ｖは気孔比容積であり、Ｄは 気孔直径であるＸ軸は気孔直径（Å）を対数尺度で示す。図中、領域１として示 すモード１は座標がＸ＝４０、Ｙ＝０．０８であり、炭化物又は窒化物への前駆 酸化物の転換中に生ずる気孔率を表わす。モード２は座標がＸ＝１０００、Ｙ＝ ０．１５でポリマー物質の燃焼で生じた気孔率を表わし、これらのＸとＹ値は使 用ポリマーの含有量と種類で変わる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of catalysts in controlled porosity transition element carbides and nitrides , for example in isomerization reactions or hydrogenation reactions, or in reactions used for gas generation such as hydrazine decomposition in propulsion systems. The present invention relates to a method for producing carbides and nitrides of transition elements of extruded profiles from oxides thereof with controlled pore volume and distribution. Carbides and nitrides are interrupted alloys formed by incorporating carbon and nitrogen into a crystalline network of transition metal oxides. These alloys exhibit metallic properties with catalytic activity similar to various metals (eg, iridium, platinum, palladium). Important properties of such compounds are, apart from being very high in hardness, corrosion resistance and a high melting point. As a direct result of these properties, carbides and nitrides are used not only in catalysis, but also in cutting tools, structural parts and the like. Catalytic applications are based on the development of high surface area carbide and nitride processes by the Boudart team. This method uses ammonia gas for nitrides, and a mixture of hydrogen and methane for carbides, and reduces the transition metal oxide by uniformly and smoothly raising the temperature of this precursor oxide. Become. Although this process produces a large surface area material, the resulting porous structure is uncontrollable and the pore diameter is less than 50 °. The present invention differs from the prior art in that transition element carbides and nitrides of the extruded shape having the intended porosity are obtained. The method is to obtain transition metal acid, tungstic acid for tungsten, and molybdic acid for molybdenum in a dissolving state. When produced at low temperatures, these acids, obtained in colloidal form, are mixed with powdered and powdered microcrystalline cellulose. After this step, the mixture is peptized using a dilute ammonium hydroxide solution as a peptizer. The product is then extruded using an extruder. The heat treatment of the extruded product consists of drying at 60 ° C. followed by drying at 120 ° C., both for a drying time of about 12 hours. This is followed by calcination at 600 ° C. for 3 hours to convert the acid to the corresponding oxide, burning off the residual cellulose in the acid. The removal of the cellulose renders the resulting oxide porous, which can be controlled by concentrating the compound mixed with the acid or by the content of ammonium hydroxide used as a peptizer. After this step, carbides and nitrides are obtained by uniformly and smoothly heating these precursors in an ammonia gas atmosphere in the case of nitrides and in an atmosphere of hydrogen and methane in the case of carbides. Typical Example FIG. 1 shows a porous structure obtained by the method in the case of molybdenum carbide. The Y-axis is the specific volume increment (d / dV) (cm 3 / g), V is the pore specific volume, D is the pore diameter, and the X-axis is the pore diameter (Å) on a logarithmic scale. In the figure, Mode 1 shown as Region 1 has coordinates X = 40 and Y = 0.08, and represents the porosity generated during the conversion of the precursor oxide to carbide or nitride. Mode 2 represents the porosity generated by burning the polymer material with coordinates X = 1000 and Y = 0.15, and these X and Y values vary depending on the content and type of the polymer used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０１Ｂ 21/06 Ｃ０１Ｂ 21/06 Ｚ 31/30 31/30 (72)発明者 クルズ，ジルベルト マルクェス ブラジル国 サンパウロ 12600−000 ロ レナ，ルア アドヘマル ド バルロス, 95 (72)発明者 ドジェガ−マリアダッソウ，ジェラルド フランス国 エフ−75252 パリ，セデッ クス 05，プラース ジャッシャン，ラボ ラトワール ド レアクティビテ ド シ ュルファス ツール 54，カシエ 178, ４ (72)発明者 ビュグリ，ギュイ フランス国 エフ−75012 パリ，アブニ ュ ドュ ドクツール−アルノルド−ネ テ，47／49──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI C01B 21/06 C01B 21/06 Z 31/30 31/30 (72) Inventor Cruz, Gilberto Marquez Sao Paulo, Brazil 12600-000 Lorena , Lua Adhemal de Barros, 95 (72) Inventor: Dodega-Maria d'Assou, Gerard France, F.-F. Bugli, Guy F-75012, France Paris, Abny-d'Oudoctur-Arnold-Netet, 47/49
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR9501693A BR9501693A (en) | 1995-05-11 | 1995-05-11 | Carbides and nitrides of transition elements with controlled porosity |
| BR9501693-7 | 1995-05-11 | ||
| PCT/BR1996/000011 WO1996035510A1 (en) | 1995-05-11 | 1996-03-19 | Carbides and nitrides of transition elements with controlled porosity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11510427A true JPH11510427A (en) | 1999-09-14 |
Family
ID=4061227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8533616A Pending JPH11510427A (en) | 1995-05-11 | 1996-03-19 | Controlled porosity transition element carbides and nitrides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0824371A1 (en) |
| JP (1) | JPH11510427A (en) |
| BR (1) | BR9501693A (en) |
| CA (1) | CA2219797A1 (en) |
| WO (1) | WO1996035510A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10002117A1 (en) * | 2000-01-20 | 2001-08-16 | Geesthacht Gkss Forschung | Catalysis of the hydrogen sorption kinetics of hydrides by nitrides and carbides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4271041A (en) * | 1979-02-08 | 1981-06-02 | The Board Of Trustees Of Leland Stanford Junior University | High surface area molybdenum oxycarbide catalysts |
| US4851206A (en) * | 1981-07-15 | 1989-07-25 | The Board Of Trustees Of The Leland Stanford Junior University, Stanford University | Methods and compostions involving high specific surface area carbides and nitrides |
| JPH0622680B2 (en) * | 1987-09-28 | 1994-03-30 | 工業技術院長 | Catalyst and method for producing the same |
| FR2666520B1 (en) * | 1990-09-06 | 1993-12-31 | Pechiney Recherche | METHOD FOR ACTIVATION OF THE SURFACE OF HEAVY METAL CARBIDES WITH A HIGH SPECIFIC SURFACE FOR CATALYTIC REACTIONS. |
-
1995
- 1995-05-11 BR BR9501693A patent/BR9501693A/en not_active Application Discontinuation
-
1996
- 1996-03-19 EP EP96905624A patent/EP0824371A1/en not_active Withdrawn
- 1996-03-19 JP JP8533616A patent/JPH11510427A/en active Pending
- 1996-03-19 WO PCT/BR1996/000011 patent/WO1996035510A1/en not_active Application Discontinuation
- 1996-03-19 CA CA002219797A patent/CA2219797A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CA2219797A1 (en) | 1996-11-14 |
| EP0824371A1 (en) | 1998-02-25 |
| WO1996035510A1 (en) | 1996-11-14 |
| BR9501693A (en) | 1997-09-16 |
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