JP2013534470A - 触媒担体、触媒並びにそれらの製造および使用 - Google Patents
触媒担体、触媒並びにそれらの製造および使用 Download PDFInfo
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- JP2013534470A JP2013534470A JP2013515956A JP2013515956A JP2013534470A JP 2013534470 A JP2013534470 A JP 2013534470A JP 2013515956 A JP2013515956 A JP 2013515956A JP 2013515956 A JP2013515956 A JP 2013515956A JP 2013534470 A JP2013534470 A JP 2013534470A
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- JP
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- Prior art keywords
- particles
- catalyst
- hydrogel
- aging
- silica
- Prior art date
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- Granted
Links
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
Description
a)アルカリ金属ケイ酸塩の酸性化により15重量%〜33重量%の固形分を有するシリカヒドロゲルを供すること、
b)ヒドロゲル粒子中にシリカヒドロゲルを形成すること、
c)ヒドロゲル粒子を1時間以上、pH3.5以下で洗浄して、実質的に塩を除去すること、
d)40℃〜水性エージング溶液の沸点までのエージング温度で4時間以上エージングさせて、pH3〜5を有する水分散液を供するために設けられた水性エージング溶液とヒドロゲル粒子とを接触させて、エージングさせたヒドロゲル粒子を供すること、
e)35mN/m以下の表面張力を有する液体溶媒でエージングさせたヒドロゲル粒子の溶媒交換を行い、エージングさせたヒドロゲル粒子中の水溶液が実質的に液体溶媒によって置換されること、および
f)エージングさせたヒドロゲル粒子から液体溶媒を実質的に除去して、触媒担体粒子を供することを含んで成る。
例えばミル等を使用して押しつぶすことによりセットしたゲルを粉砕して、粒子中に形成されてよい。これは、任意の更なる化学処理により理論上の時間スケール内で生じさせることが可能である。ヒドロゲル粒子が大き過ぎると、ヒドロゲル粒子内外の化学拡散が過剰に長い時間を要するかもしれない。又、ゾルは、適当な大きさの球状のゲル粒子中にゾルを形成するためにスプレーされてよい。スプレーセッティングは本明細書に記載の塩基セットヒドロゲルに特に有用である。
Claims (20)
- 1.5cm3/g以上の細孔容積および600m2/g以上の表面積を有する細孔構造を有する触媒担体粒子の作成方法であって、
a)アルカリ金属ケイ酸塩の酸性化により、15重量%〜33重量%の固形含量を有するシリカヒドロゲルを供すること、
b)ヒドロゲル粒子中にシリカヒドロゲルを形成すること、
c)pH3、5以下で1時間以上の間ヒドロゲル粒子を洗浄して、実質的に塩を除去すること、
d)ヒドロゲル粒子をpH3〜5を有する水性分散液を供するために設けられた水性エージング溶液と、40℃〜エージング溶液の沸点までの温度で、4時間以上のエージング期間接触させて、エージングさせたヒドロゲル粒子を供すること、
e)35mN/m以下の表面張力を有する液体溶媒でエージングさせたヒドロゲル粒子の溶媒交換を行い、それによって、エージングさせたヒドロゲル粒子中の水溶液を実質的に液体溶媒に置換すること、および
f)エージングさせたヒドロゲル粒子から液体溶媒を実質的に除去して、触媒担体粒子を供することを含んで成る、方法。 - エージング期間が4〜30時間、好ましくは4〜20時間である、請求項1に記載の方法。
- 工程d)でのエージング後かつ工程e)での溶媒交換前に、工程d)のエージングさせたヒドロゲルをpH3未満まで酸性化する、請求項1又は2に記載の方法。
- 水性エージング溶液がエージングさせたヒドロゲル粒子を供するためにヒドロゲル粒子と接触しつつ、実質的に一定のpH3〜5を有する水性分散液を供するために設けられたバッファーを有して成る、請求項1〜3のいずれかに記載の方法。
- バッファーがカルボン酸塩/カルボン酸のバッファーである、請求項4に記載の方法。
- 大気圧以下の圧力で溶媒を除去する、請求項1〜5のいずれかに記載の方法。
- エージング前のヒドロゲル粒子が、150℃で乾燥後洗浄されたヒドロゲルで測定可能な表面積920m2/g以上を有する、請求項1〜6のいずれかに記載の方法。
- エージング前のヒドロゲル粒子が、溶媒交換後洗浄されたヒドロゲルで測定可能な細孔容積1.3cm3/g以下を有する、請求項1〜7のいずれかに記載の方法。
- シリカキセロゲルが少なくとも90重量%のシリカを有して成る、請求項1〜8のいずれかに記載の方法。
- 触媒担体粒子が1.8cm3/g以上の細孔容積を有する、請求項1〜9のいずれかに記載の方法。
- 触媒担体粒子が800m2/g以上の表面積を有する、請求項1〜10のいずれかに記載の方法。
- エージング温度は、pH3でエージングする際60℃〜エージング溶液の沸点であり、pH5でエージングする際40℃〜71℃である、請求項1〜11のいずれかに記載の方法。
- 請求項1〜12のいずれかに記載の方法により得られた触媒担体粒子。
- 100mlのスラリー当たり12.5gの触媒担体を有するスラリー状の沸騰して、脱塩された水で25℃で測定される際pH6以下を供する、請求項13に記載の触媒担体粒子。
- 20〜1000重量ppmのソーダ含量を有した、請求項13又は14に記載の触媒担体粒子。
- 1.5cm3/g以上の細孔容積および600m2/g以上の表面積を有した少なくとも90重量%のシリカを有して成るシリカキセロゲルである触媒担体粒子であって、
100mlのスラリー当たり12.5gの触媒担体を有したスラリー状の沸騰して、脱塩された水で25℃で測定される際、触媒担体粒子はpH6以下を供する、触媒担体粒子。 - 細孔構造内に沈着した触媒金属の化合物を有して成る請求項13〜16のいずれかに記載の触媒担体粒子を有して成る触媒前駆体であって、触媒金属がクロムを有して成る、触媒前駆体。
- 30分〜15時間の活性期間に200〜1200℃の温度で非還元雰囲気で請求項17に記載の触媒前駆体を加熱することで得られた又は得られる、オレフィン重合触媒。
- 請求項18に記載のオレフィン重合触媒の存在下で重合を行うことを特徴とする、1つ又はそれよりも多いC2〜C8のα−アルケンの重合方法。
- 低メルトインデックス・ポリマーを生じさせるため1つ又はそれよりも多いC2〜C8のα−アルケンの重合のための請求項18に記載のオレフィン重合触媒の使用。
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