JP2001025661A - Production of spherical carrier for catalyst deposition - Google Patents
Production of spherical carrier for catalyst depositionInfo
- Publication number
- JP2001025661A JP2001025661A JP11197796A JP19779699A JP2001025661A JP 2001025661 A JP2001025661 A JP 2001025661A JP 11197796 A JP11197796 A JP 11197796A JP 19779699 A JP19779699 A JP 19779699A JP 2001025661 A JP2001025661 A JP 2001025661A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- magnesia
- alumina
- spherical
- hydrate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 230000008021 deposition Effects 0.000 title 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 112
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 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 25
- 150000004676 glycans Chemical class 0.000 claims abstract description 17
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 17
- 239000005017 polysaccharide Substances 0.000 claims abstract description 17
- 239000000017 hydrogel Substances 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 21
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229940080237 sodium caseinate Drugs 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentanal Chemical compound OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 2
- 102000011632 Caseins Human genes 0.000 claims description 2
- 108010076119 Caseins Proteins 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 39
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 11
- 239000000969 carrier Substances 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical group [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 229960000292 pectin Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は触媒担体として、あ
るいは吸着剤などと用いられるシリカ−マグネシア球形
担体またはシリカ−アルミナ−マグネシア球形担体の製
造方法に関するものであり、さらに詳しくは主原料であ
るシリカ−マグネシア水和物ペーストまたはシリカ−ア
ルミナ−マグネシア水和物ペーストの細孔構造とほぼ同
様の細孔構造を有する球形担体を容易に作製でき、かつ
外表面から内部まで均質なシリカ−マグネシア組成物あ
るいはシリカ−アルミナ−マグネシア組成物からなる触
媒担持用球形担体の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a silica-magnesia spherical carrier or a silica-alumina-magnesia spherical carrier used as a catalyst carrier or as an adsorbent, and more particularly to a silica as a main raw material. -A spherical carrier having a pore structure substantially similar to that of magnesia hydrate paste or silica-alumina-magnesia hydrate paste can be easily produced, and a homogeneous silica-magnesia composition from the outer surface to the inner portion Alternatively, the present invention relates to a method for producing a spherical carrier for supporting a catalyst comprising a silica-alumina-magnesia composition.
【０００２】[0002]
【従来の技術】シリカ−マグネシア組成物あるいはシリ
カ−アルミナ−マグネシア組成物からなる担体はシリカ
−アルミナ担体やボリア−アルミナ担体に比べて、酸強
度は弱いものの、酸量は約２倍量と酸点が多く存在して
おり、石油の接触水添反応において目的とする留分の収
率を増加することができる水素化選択性に優れているた
め、石油化学工業において触媒担体として広範囲に使用
されている。2. Description of the Related Art A carrier comprising a silica-magnesia composition or a silica-alumina-magnesia composition has a lower acid strength than a silica-alumina carrier or a boria-alumina carrier, but has an acid amount of about twice that of a silica-alumina carrier or a boria-alumina carrier. It is widely used as a catalyst carrier in the petrochemical industry because it has many points and has excellent hydrogenation selectivity that can increase the yield of the target fraction in the catalytic hydrogenation reaction of petroleum. ing.
【０００３】さて一般に球形担体は触媒活性金属を担持
し、固定床反応器や移動床反応器に充填して用いられる
が、球形であるため反応器へ充填が均一であり、かつ抜
き出しが容易であり、また運転中に反応物質の流れのバ
イパスを起こさせる、いわゆるチャンネリングを抑制す
ることができるという利点を有する。さらに移動床反応
器では反応器内で流動あるいは自重により下方に僅かず
つ移動していく反応形式においては球形であることが必
須の要件となっている。このような球形担体は、油中滴
下法、転動造粒法などにより製造されている。例えば、
油中滴下法によるアルミナ球形担体は、へキサメチレン
テトラミンや尿素などのような高温で分解してアンモニ
アを発生する試薬を用いて、そのアルカリ性によりアル
ミナゾルをゲル化させる方法を採っているために、表面
が平滑で比較的均一な真球に近い球形担体が製造でき
る。そしてアルミナゾルをゲル化させるため外表面から
内部まで均質であり、細孔構造は大部分が直径５０オン
グストローム以下のミクロ細孔で形成されている。[0003] Generally, a spherical carrier carries a catalytically active metal and is used by being packed in a fixed-bed reactor or a moving-bed reactor. However, since the spherical carrier is spherical, it is uniformly filled in the reactor and can be easily extracted. Yes, and has the advantage that so-called channeling, which causes a bypass of the reactant flow during operation, can be suppressed. Further, in a moving bed reactor, a spherical shape is an essential requirement in a reaction system in which the reactor moves gradually downward by flow or its own weight in the reactor. Such a spherical carrier is manufactured by an in-oil dripping method, a tumbling granulation method, or the like. For example,
Alumina spherical carrier by the drop-in-oil method uses a reagent that decomposes at high temperature to generate ammonia, such as hexamethylenetetramine or urea, and uses a method of gelling alumina sol by its alkalinity. A spherical carrier having a smooth surface and a relatively uniform spherical shape can be produced. In order to gel the alumina sol, the alumina sol is uniform from the outer surface to the inside, and the pore structure is mostly formed of micropores having a diameter of 50 Å or less.
【０００４】一方、転動造粒法によるアルミナ球形担体
は、調湿したアルミナ水和物粉体を転動して粒子を形成
させた後、水噴霧と調湿したアルミナ水和物粉体の供給
を交互に行って厚密化しながら粒成長させるため、表面
は多少粗く球形分布の広いやや真球度の低い球形担体が
製造される。そして調湿したアルミナ水和物粉体を転動
して粒成長させるため、外表面と内部の間に層が形成さ
れ、細孔構造はミクロ細孔からマクロ細孔まで広範囲な
分布を有しているものの、製造コストが安いため広く使
用されている。[0004] On the other hand, an alumina spherical carrier formed by the tumbling granulation method rolls a conditioned alumina hydrate powder to form particles, and then sprays water and humidifies the conditioned alumina hydrate powder. Since the grains are grown while increasing the density by alternately supplying them, a spherical carrier having a somewhat rough surface and a wide spherical distribution and a slightly low sphericity is produced. Then, a layer is formed between the outer surface and the inner surface to roll and grow the hydrated alumina hydrate powder, and the pore structure has a wide distribution from micropores to macropores. However, it is widely used due to its low manufacturing cost.
【０００５】[0005]
【発明が解決しようとする課題】ところで、移動床反応
器用の球形担体としては、該担体が流動および／または
移動していく反応形式であるので、耐摩耗性の性能が特
に要求され、球形は均一で表面が平滑であることが重要
である。したがって移動床反応器用の球形担体として
は、油中滴下法で製造され球形担体が主に用いられてい
る。しかしながら油中滴下法で製造された球形担体は前
記したように球形は均一で表面が平滑であり、外表面か
ら内部まで均質であるが、大部分が直径５０オングスト
ローム以下のミクロ細孔で占められているため細孔によ
る影響が現れ、ガス系の反応に用いる触媒のように、特
に反応速度が大きく活性の低下が細孔閉塞や表面を覆う
物理的な被毒に起因するような条件下での使用は難し
い。一般に、触媒の性能は触媒担体の細孔特性と密接な
関係にあることから、反応の種類、反応条件に適合した
物理的性状をもつ担体が要求されている。By the way, a spherical carrier for a moving bed reactor is of a reaction type in which the carrier flows and / or moves. Therefore, abrasion resistance performance is particularly required. It is important that the surface be uniform and smooth. Therefore, as a spherical carrier for a moving bed reactor, a spherical carrier produced by a dropping method in oil is mainly used. However, as described above, the spherical carrier produced by the drop-in-oil method has a uniform spherical shape and a smooth surface, and is homogeneous from the outer surface to the inside, but is mostly occupied by micropores having a diameter of 50 Å or less. Because of the effect of pores, such as catalysts used for gas-based reactions, especially under conditions where the reaction rate is large and the decrease in activity is due to pore blockage or physical poisoning covering the surface Is difficult to use. In general, since the performance of a catalyst is closely related to the pore characteristics of a catalyst carrier, a carrier having physical properties suitable for the type of reaction and reaction conditions is required.
【０００６】本発明はこれらの課題を解決すべくなされ
たものであり、主原料に用いるシリカ−マグネシア水和
物ペーストあるいはシリカ−アルミナ−マグネシア水和
物ペーストの細孔構造とほぼ同様な細孔構造を有し、球
形が均一であり、また表面が平滑であって、外表面から
内部まで均質なシリカ−マグネシア組成物あるいはシリ
カ−アルミナ−マグネシア組成物からなる触媒担持用球
形担体の製造方法を提供することを目的とするものであ
る。The present invention has been made to solve these problems, and has a pore having substantially the same pore structure as a silica-magnesia hydrate paste or a silica-alumina-magnesia hydrate paste used as a main raw material. A method for producing a catalyst-supporting spherical carrier comprising a silica-magnesia composition or a silica-alumina-magnesia composition having a structure, a uniform sphere, a smooth surface, and a uniform surface from the outer surface to the inside. It is intended to provide.
【０００７】[0007]
【発明を解決するための手段】上記目的を達成するため
本発明は、シリカ−マグネシア水和物ペースト、あるい
はシリカ−マグネシア水和物にアルミナ水和物を添加し
たシリカ−アルミナ−マグネシア水和物ペーストに多糖
類溶液を加えて混合し、濃度を調整したスラリーを多価
金属イオンを含む溶液中へ滴下して球状のヒドロゲルを
形成させ、ついで熟成し、洗浄した後乾燥、焼成する触
媒担持用球形担体の製造方法を特徴とするものであり、
前記水和物ペーストに加える多糖類溶液は濃度１．０〜
３．０重量％の低メトキシルペクチン、アルギン酸ナト
リウムまたはカゼイン酸ナトリウムであり、また前記水
和物ペーストへの多糖類溶液の添加量は該水和物ペース
トを酸化物換算した重量に対して３〜１０倍量であっ
て、さらに前記スラリーはシリカ−マグネシアあるいは
シリカ−アルミナ−マグネシアを酸化物換算で５〜２０
重量％の範囲に濃度を調整されており、前記多価金属イ
オン溶液は、濃度０．５〜３．０重量％のカルシウム、
アルミニウム、マグネシウム、バリウムまたはストロン
チウムのうち少なくとも１種からなり、また前記洗浄後
の球状のシリカ−マグネシアヒドロゲルあるいはシリカ
−アルミナ−マグネシアヒドロゲルの乾燥温度は６０〜
１２０℃であり、また焼成温度は４００〜７００℃であ
ることを特徴とする。In order to achieve the above object, the present invention provides a silica-magnesia hydrate paste or a silica-alumina-magnesia hydrate obtained by adding alumina hydrate to silica-magnesia hydrate. A polysaccharide solution is added to the paste, mixed, and the slurry whose concentration has been adjusted is dropped into a solution containing polyvalent metal ions to form a spherical hydrogel, which is then aged, washed, dried, and calcined. Characterized by a method for producing a spherical carrier,
The polysaccharide solution added to the hydrate paste has a concentration of 1.0 to
3.0% by weight of low methoxyl pectin, sodium alginate or sodium caseinate; and the amount of the polysaccharide solution added to the hydrate paste is 3 to 3 parts by weight of the hydrate paste in terms of oxide. 10 times the amount, and the slurry is prepared by converting silica-magnesia or silica-alumina-magnesia into oxides in an amount of 5 to 20 times.
The concentration of the polyvalent metal ion solution is adjusted to a range of 0.5 to 3.0% by weight of calcium,
The spherical silica-magnesia hydrogel or the silica-alumina-magnesia hydrogel after washing is composed of at least one of aluminum, magnesium, barium and strontium, and has a drying temperature of 60 to
120 ° C., and the firing temperature is 400 to 700 ° C.
【０００８】[0008]
【発明の実施の形態】本発明において主原料の１つであ
るシリカ−マグネシア水和物ペーストを製造する方法と
しては、沈着法、混合法などの一般的な製造方法が適用
でき、例えばシリカを主成分とする水溶性化合物溶液を
加水分解して生成するシリカ水和物スラリーにマグネシ
アを主成分とする水溶性化合物溶液を添加して得られた
シリカ−マグネシア水和物スラリーを濾過・洗浄して得
られたシリカ−マグネシア水和物ゲルを用いることがで
き、あるいはシリカを主成分とする塩基性水溶液とマグ
ネシアを主成分とする酸性水溶液との加水分解により生
成するシリカ−マグネシア水和物スラリーを濾過・洗浄
して得られたシリカ−マグネシア水和物ゲルを用いるこ
ともできる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a method for producing a silica-magnesia hydrate paste which is one of the main raw materials in the present invention, a general production method such as a deposition method and a mixing method can be applied. A silica-magnesia hydrate slurry obtained by adding a magnesia-based water-soluble compound solution to a silica hydrate slurry formed by hydrolyzing a water-soluble compound solution containing a main component is filtered and washed. The silica-magnesia hydrate gel obtained by hydrolyzing a silica-magnesia hydrate gel obtained by the hydrolysis of a basic aqueous solution mainly containing silica and an acidic aqueous solution mainly containing magnesia can be used. Can be used. A silica-magnesia hydrate gel obtained by filtering and washing is also usable.
【０００９】また他の主原料であるシリカ−アルミナ−
マグネシア水和物ペーストを製造する方法としては、前
記と同様にして生成したシリカ−マグネシア水和物スラ
リーにアルミナを主成分とする水溶性化合物溶液を添加
して、シリカ−アルミナ−マグネシア水和物スラリーを
得、該スラリーを前記と同様に濾過・洗浄してシリカ−
アルミナ−マグネシア水和物ゲルを用いることができ、
あるいはアルミナを主成分とする水溶性化合物溶液を加
水分解して生成するアルミナ水和物スラリーを濾過・洗
浄して得られたアルミナ水和物ゲルと前記と同様にして
得られたシリカ−マグネシア水和物ゲルとを混練する混
合法を用いることができる。Another main raw material, silica-alumina-
As a method of producing a magnesia hydrate paste, a silica-alumina-magnesia hydrate is prepared by adding a water-soluble compound solution containing alumina as a main component to a silica-magnesia hydrate slurry produced in the same manner as described above. A slurry was obtained, and the slurry was filtered and washed in the same manner as described above to obtain silica-
Alumina-magnesia hydrate gel can be used,
Alternatively, an alumina hydrate gel obtained by filtering and washing an alumina hydrate slurry formed by hydrolyzing a water-soluble compound solution containing alumina as a main component, and silica-magnesia water obtained in the same manner as described above A mixing method of kneading with a hydrate gel can be used.
【００１０】そしてシリカを主成分とする水溶性化合物
としては、珪酸ナトリウム、四塩化珪素、コロイダルシ
リカなどの水溶液を用いることができ、またマグネシア
を主成分とする水溶性化合物としては、硫酸マグネシウ
ム、硝酸マグネシウム、塩化マグネシウムなどの水溶液
を用いることができ、さらにアルミニウムを主成分とす
る水溶性化合物としては、硝酸アルミニウム、硫酸アル
ミニウム、塩化アルミニウム、アルミン酸ナトリウムな
どの水溶液を用いることができる。つぎに前記シリカ−
マグネシア水和物ゲルあるいはシリカ−アルミナ−マグ
ネシア水和物ゲルを撹拌混合したペーストに濃度１．０
〜３．０重量％の多糖類溶液を該水和物ペーストを酸化
物換算した重量に対して３〜１０倍量添加する。As the water-soluble compound containing silica as a main component, an aqueous solution of sodium silicate, silicon tetrachloride, colloidal silica or the like can be used. As the water-soluble compound containing magnesia as a main component, magnesium sulfate, An aqueous solution such as magnesium nitrate or magnesium chloride can be used, and as the water-soluble compound containing aluminum as a main component, an aqueous solution such as aluminum nitrate, aluminum sulfate, aluminum chloride, or sodium aluminate can be used. Next, the silica
A magnesia hydrate gel or a silica-alumina-magnesia hydrate gel was stirred and mixed at a concentration of 1.0.
A polysaccharide solution of about 3.0% by weight is added in an amount of 3 to 10 times the weight of the hydrate paste in terms of oxide.
【００１１】本発明において、シリカ−マグネシア水和
物ペーストあるいはシリカ−アルミナ−マグネシア水和
物ペーストに添加する多糖類溶液としては、低メトキシ
ル（Ｌ．Ｍ．）ペクチン、アルギン酸ナ卜リウム、カゼ
イン酸ナトリウムなどであり、温水に対する溶解性を考
慮すると該多糖類溶液の濃度を１．０〜３．０重量％の
範囲とすることが好ましい。３．０重量％を超える濃度
にしてもよいが溶解させるために長時間を要する問題が
あり、また１．０重量％未満では溶解時間は多少短縮で
きるが溶液の濃度が低いため添加する溶液量が増し、ひ
いては多糖類溶液を加えた混合スラリーの濃度調整がし
難くなるからである。また多糖類溶液の添加量をシリカ
−マグネシア水和物ペーストあるいはシリカ−アルミナ
−マグネシア水和物ペーストを酸化物換算した重量に対
して３〜１０倍量とするのは、３倍量未満の添加量では
好適な球形の形状の担体が得られず、一方１０倍量を超
えて添加しても真球度を高めるためのさらなる効果が得
られないからである。ついで該多糖類溶液を加え混合し
たスラリーの濃度をシリカ−マグネシアあるいはシリカ
−アルミナ−マグネシアを酸化物換算で５〜２０重量％
の範囲に調整する。In the present invention, the polysaccharide solution to be added to the silica-magnesia hydrate paste or the silica-alumina-magnesia hydrate paste includes low methoxyl (LM) pectin, sodium alginate, caseinate, and the like. Sodium, etc., and considering the solubility in warm water, the concentration of the polysaccharide solution is preferably in the range of 1.0 to 3.0% by weight. The concentration may exceed 3.0% by weight, but there is a problem that it takes a long time to dissolve, and if it is less than 1.0% by weight, the dissolution time can be shortened somewhat, but the concentration of the solution is low, so the amount of solution to be added is small. This makes it difficult to adjust the concentration of the mixed slurry to which the polysaccharide solution has been added. Further, the addition amount of the polysaccharide solution is 3 to 10 times the weight of the silica-magnesia hydrate paste or the silica-alumina-magnesia hydrate paste in terms of oxide, and the addition amount is less than 3 times. This is because a suitable spherical shaped carrier cannot be obtained in the amount, and even if added in an amount exceeding 10 times, no further effect for increasing the sphericity is obtained. Then, the concentration of the slurry obtained by adding and mixing the polysaccharide solution was adjusted to 5 to 20% by weight of silica-magnesia or silica-alumina-magnesia in terms of oxide.
Adjust to the range.
【００１２】本発明において、スラリー濃度をシリカ−
マグネシアあるいはシリカ−アルミナ−マグネシアを酸
化物換算で５〜２０重量％とするのは、該スラリーを口
径一定の滴下口から滴下する際、濃度が２０重量％を超
えるとスラリーの粘度が高くなり液滴の落下速度を一定
に制御し難く、ひいては不均一な大きさの楕円球形が形
成されてしまうからであり、また濃度が５重量％未満で
は不揃いの泪状球形が形成されてしまうからである。つ
ぎにシリカ−マグネシア水和物ペーストあるいはシリカ
−アルミナ−マグネシア水和物ペーストに多糖類溶液を
加えて混合し、濃度を調整したスラリーを多価金属イオ
ンを含む溶液中へ滴下して球状のシリカ−マグネシアヒ
ドロゲルあるいは球状のシリカ−アルミナ−マグネシア
ヒドロゲルを形成させ、熟成し、洗浄した後乾燥、焼成
し、シリカ−マグネシア組成物あるいはシリカ−アルミ
ナ−マグネシア組成物からなる球形担体を得る。In the present invention, the slurry concentration is adjusted to silica-
The reason why magnesia or silica-alumina-magnesia is adjusted to 5 to 20% by weight in terms of oxide is that when the slurry is dropped from a dropper having a fixed diameter, if the concentration exceeds 20% by weight, the viscosity of the slurry increases and the This is because it is difficult to control the falling speed of the droplet to be constant, and thus an elliptical sphere having an uneven size is formed, and when the concentration is less than 5% by weight, an irregular tear-like sphere is formed. . Next, a polysaccharide solution is added to the silica-magnesia hydrate paste or silica-alumina-magnesia hydrate paste and mixed, and the slurry whose concentration has been adjusted is dropped into a solution containing polyvalent metal ions to obtain spherical silica. Forming a magnesia hydrogel or spherical silica-alumina-magnesia hydrogel, aging, washing, drying and calcining to obtain a spherical carrier comprising a silica-magnesia composition or a silica-alumina-magnesia composition;
【００１３】本発明に用いる多価金属イオン溶液として
はカルシウム、アルミニウム、マグネシウム、バリウ
ム、ストロンチウムなどの二価の金属イオンを含む金属
塩の中から選ぶことが好ましく、２種および／または３
種の混合溶液を用いることもできる。該多価金属イオン
溶液の濃度としては０．５〜３．０重量％の範囲にする
ことが好ましく、その理由は、０．５重量％未満の濃度
では好適な球形担体が得られず、一方３．０重量％を超
える濃度にしてもよいが好適な球形担体を得るためのさ
らなる効果が得られないからである。The polyvalent metal ion solution used in the present invention is preferably selected from metal salts containing divalent metal ions such as calcium, aluminum, magnesium, barium and strontium.
Mixed solutions of the species can also be used. It is preferable that the concentration of the polyvalent metal ion solution be in the range of 0.5 to 3.0% by weight, because if the concentration is less than 0.5% by weight, a suitable spherical carrier cannot be obtained. Although the concentration may be higher than 3.0% by weight, no further effect for obtaining a suitable spherical carrier can be obtained.
【００１４】以上説明した手順で得たシリカ−マグネシ
アあるいはシリカ−アルミナ−マグネシアを主体とする
球状のヒドロゲルを熟成し、ついで温度６０〜１２０℃
で１０〜１５時間乾燥し、温度４００〜７００℃の範囲
で焼成することによってシリカ−マグネシア組成物ある
いはシリカ−アルミナ−マグネシア組成物からなる触媒
担持用球形担体を製造することができる。なお４００〜
７００℃の温度範囲で焼成する理由は、４００℃未満の
温度では多糖類溶液が完全に分解することができずに炭
素物質が残存してしまい、一方７００℃を超える温度で
はシリカ−マグネシアではシンターリングによりホルス
テライトあるいはエンスタタイト構造が形成され著しく
比表面積が減少し触媒担体として適用するのが困難であ
るからである。The spherical hydrogel mainly composed of silica-magnesia or silica-alumina-magnesia obtained by the above-described procedure is aged, and then a temperature of 60 to 120 ° C.
By drying at 10 to 15 hours at a temperature of 400 to 700 ° C., a spherical carrier for supporting a catalyst comprising a silica-magnesia composition or a silica-alumina-magnesia composition can be produced. 400 ~
The reason for calcination in the temperature range of 700 ° C. is that if the temperature is lower than 400 ° C., the polysaccharide solution cannot be completely decomposed and the carbon material remains, while if the temperature exceeds 700 ° C., sintering is not possible with silica-magnesia. This is because the ring forms a forsterite or enstatite structure and the specific surface area is significantly reduced, making it difficult to apply as a catalyst carrier.
【００１５】[0015]
【実施例】本発明の実施例を比較例とともに説明する。
なお以下に示す細孔特性は水銀圧入法により測定し、水
銀の表面張力を４８０ｄｙｎ／ｃｍ、水銀と測定試料と
の接触角を１４０°で計算したものである。 ［実施例１］内容積５０リットルの撹拌機付きステンレ
ス製反応槽に、水２０リットルを入れ、４０℃まで加温
して保持し、撹拌しつつ珪酸ナトリウム水溶液７０００
ｇ（ＳｉＯ２として６４５ｇ）と塩化マグネシウム水溶
液７０００ｇ（ＭｇＯとして３５０ｇ）とを同時もしく
はほぼ同時に全量滴下し、熟成してｐＨ７．８のシリカ
−マグネシア水和物スラリーを得た。つぎに該スラリー
に水酸化ナトリウム水溶液３０００ｇ（ＮａＯＨとして
６００ｇ）を全量滴下し、熟成してｐＨ１０．５のシリ
カ−マグネシア水和物スラリーを得た。ついで該スラリ
ーを濾過し、Ｎａ２Ｏが０．１重量％以下になるまで洗
浄してＭｇＯとして３５重量％含むシリカ−マグネシア
水和物ケーキ（ａ）を得た。このシリカ−マグネシア水
和物ケーキ（ａ）の一部を８０℃の温度で１５時間乾燥
し、６００℃の温度で３時間焼成してシリカ−マグネシ
ア固形物（ａ′）を得た。EXAMPLES Examples of the present invention will be described together with comparative examples.
The pore characteristics shown below were measured by the mercury intrusion method, and the surface tension of mercury was calculated at 480 dyn / cm, and the contact angle between mercury and the measurement sample was calculated at 140 °. Example 1 20 liters of water was put into a 50 liter stainless steel reaction tank equipped with a stirrer, heated to 40 ° C. and maintained, and stirred while an aqueous sodium silicate solution 7000 was used.
g (645 g of SiO 2 ) and 7000 g of magnesium chloride aqueous solution (350 g of MgO) were simultaneously or almost simultaneously dripped, and the mixture was aged to obtain a silica-magnesia hydrate slurry having a pH of 7.8. Next, 3000 g of an aqueous sodium hydroxide solution (600 g as NaOH) was added dropwise to the slurry, followed by aging to obtain a silica-magnesia hydrate slurry having a pH of 10.5. Then, the slurry was filtered and washed until Na 2 O became 0.1% by weight or less to obtain a silica-magnesia hydrate cake (a) containing 35% by weight as MgO. A part of the silica-magnesia hydrate cake (a) was dried at a temperature of 80 ° C. for 15 hours and calcined at a temperature of 600 ° C. for 3 hours to obtain a silica-magnesia solid (a ′).
【００１６】一方該シリカ−マグネシア水和物ケーキ
（ａ）５４１ｇ（ＳｉＯ２−ＭｇＯとして１００ｇ）に
濃度１．５重量％のアルギン酸ナトリウム溶液５００ｇ
（ＳｉＯ２−ＭｇＯに対して５倍量）を加え十分撹拌混
合してＳｉＯ２−ＭｇＯ固形分濃度として９．６重量％
のスラリーを得た。ついで該スラリーを口径４．５ｍｍ
の滴下口から濃度１．２重量％の塩化カルシウム溶液を
入れた内容積１０リットルの撹拌機付きパイレックス製
反応槽に滴下して球状のヒドロゲルを形成させ、５分間
熟成後球状のヒドロゲルを取り出し、水洗して８０℃の
温度で１５時間乾燥し、６００℃の温度で２時間焼成し
てシリカ−マグネシア球形担体Ａ（実施例１）を得た。
得られたシリカ−マグネシア固形物（ａ′）の細孔特性
およびシリカ−マグネシア球形担体Ａの細孔特性と物理
性状について下記する表１に示す。On the other hand, 541 g of the silica-magnesia hydrate cake (a) (100 g as SiO 2 -MgO) was mixed with 500 g of a 1.5% by weight sodium alginate solution.
(5 times the amount of SiO 2 -MgO) and sufficiently stirred and mixed to obtain a SiO 2 -MgO solid content concentration of 9.6% by weight.
Was obtained. Then, the slurry was 4.5 mm in diameter.
Was dropped into a 10 liter Pyrex reaction tank equipped with a stirrer containing a 1.2% by weight calcium chloride solution through a dropping port to form a spherical hydrogel. After aging for 5 minutes, the spherical hydrogel was taken out. The resultant was washed with water, dried at a temperature of 80 ° C. for 15 hours, and calcined at a temperature of 600 ° C. for 2 hours to obtain a silica-magnesia spherical carrier A (Example 1).
Table 1 below shows the pore properties of the obtained silica-magnesia solid (a ') and the pore properties and physical properties of the silica-magnesia spherical carrier A.
【００１７】表１から分る通り、本発明の実施例１に係
るシリカ−マグネシア球形担体の製造方法によれば、主
原料のシリカ−マグネシア水和物ケーキの細孔特性とほ
ぼ同等の細孔特性を有し、かつ破壊強度も強く、ほぼ真
球のシリカ−マグネシア球形担体が製造できた。As can be seen from Table 1, according to the method for producing a silica-magnesia spherical carrier according to Example 1 of the present invention, the pores having substantially the same pore characteristics as those of the silica-magnesia hydrate cake as the main raw material. The silica-magnesia spherical carrier having characteristics and high breaking strength was almost spherical.
【００１８】［実施例２、３］実施例１における珪酸ナ
トリウム水溶液と同時もしくはほぼ同時に滴下する塩化
マグネシウム水溶液の量を３３００ｇ（ＭｇＯとして１
６５ｇ）、１２９００ｇ（ＭｇＯとして６４５ｇ）と変
化させたこと以外は実施例１と同様の方法でＭｇＯとし
て２０重量％含むシリカ−マグネシア水和物ケーキ
（ｂ）とＭｇＯとして５０重量％含むシリカ−マグネシ
ア水和物ケーキ（ｃ）、およびシリカ−マグネシア固形
物（ｂ′）、（ｃ′）を得た。一方それぞれのケーキ
（ｂ）、（ｃ）を用いて球形担体Ａを得た実施例１の方
法とほぼ同様の方法でシリカ−マグネシア球形担体Ｂ
（実施例２）およびシリカ−マグネシア球形担体Ｃ（実
施例３）を得た。得られたシリカ−マグネシア固形物
（ｂ′）、（ｃ′）の細孔特性およびシリカ−マグネシ
ア球形担体Ｂ、Ｃの細孔特性と物理性状について下記す
る表１に併せて示す。Examples 2 and 3 The amount of the aqueous solution of magnesium chloride dropped simultaneously or almost simultaneously with the aqueous solution of sodium silicate in Example 1 was 3300 g (1 mg as MgO).
65 g) and 12900 g (645 g as MgO) in the same manner as in Example 1, except that the silica-magnesia hydrate cake (b) containing 20% by weight as MgO and silica-magnesia containing 50% by weight as MgO. A hydrate cake (c) and silica-magnesia solids (b '), (c') were obtained. On the other hand, a silica-magnesia spherical carrier B was obtained in substantially the same manner as in Example 1 in which a spherical carrier A was obtained using each of the cakes (b) and (c).
(Example 2) and a silica-magnesia spherical carrier C (Example 3) were obtained. The pore properties of the obtained silica-magnesia solids (b ') and (c') and the pore properties and physical properties of the silica-magnesia spherical carriers B and C are also shown in Table 1 below.
【００１９】表１から分る通り、本発明の実施例２およ
び実施例３に係るシリカ−マグネシア球形担体の製造方
法によれば、主原料のシリカ−マグネシア水和物のマグ
ネシア含有量を変化させても、それぞれのシリカ−マグ
ネシア水和物ケーキの細孔特性とほぼ同等の細孔特性を
有し、かつ破壊強度も強く、ほぼ真球のシリカ−マグネ
シア球形担体が製造できた。As can be seen from Table 1, the magnesia content of the silica-magnesia hydrate as the main raw material is changed according to the method for producing the silica-magnesia spherical carrier according to Examples 2 and 3 of the present invention. However, almost spherical silica-magnesia spherical carriers having substantially the same pore characteristics as those of the respective silica-magnesia hydrate cakes and having high breaking strength were produced.
【００２０】［比較例１、２］実施例１で得たシリカ−
マグネシア水和物ケーキ（ａ）に添加する濃度１．５重
量％のアルギン酸ナトリウム溶液の添加量をＳｉＯ２−
ＭｇＯに対してそれぞれ１倍量、１５倍量としたこと以
外は実施例１におけるシリカ−マグネシア球形担体Ａを
得た方法とほぼ同様の方法でシリカ−マグネシア球形担
体Ｄ（比較例１）およびシリカ−マグネシア球形担体Ｅ
（比較例２）を得た。得られたシリカ−マグネシア球形
担体Ｄ、Ｅの細孔特性と物理性状について下記する表１
に併せて示す。Comparative Examples 1 and 2 The silica obtained in Example 1
The amount of the 1.5 wt% sodium alginate solution to be added to the magnesia hydrate cake (a) was changed to SiO 2 −
Silica-magnesia spherical carrier D (Comparative Example 1) and silica-magnesia spherical carrier D (Comparative Example 1) were obtained in substantially the same manner as in the method of obtaining silica-magnesia spherical carrier A in Example 1 except that the amount was 1 and 15 times the amount of MgO, respectively. -Magnesia spherical carrier E
(Comparative Example 2) was obtained. Table 1 below shows the pore characteristics and physical properties of the obtained silica-magnesia spherical carriers D and E.
Are shown together.
【００２１】表１から分る通り、多糖類溶液の添加量が
本発明の範囲外にある比較例１および２に係る方法で製
造して得られたシリカ−マグネシア球形担体Ｄは細孔特
性についてはよいが、触媒担体の形状が楕円状になり、
またシリカ−マグネシア球形担体Ｅは細孔特性が変化
し、破壊強度も弱かった。As can be seen from Table 1, the silica-magnesia spherical carrier D obtained by the method according to Comparative Examples 1 and 2 in which the amount of the polysaccharide solution added is out of the range of the present invention, has a small pore characteristic. Is good, but the shape of the catalyst support becomes elliptical,
In addition, the silica-magnesia spherical carrier E had a changed pore property and a low breaking strength.
【００２２】［比較例３、４］実施例１で得たシリカ−
マグネシア水和物ケーキ（ａ）に濃度１．５重量％のア
ルギン酸ナトリウム溶液を５倍量と水とを加え十分撹拌
混合した、スラリーのＳｉＯ２−ＭｇＯ固形分濃度を３
重量％と該スラリーを加熱濃縮しＳｉΟ２−ＭｇＯ固形
分濃度を２５重量％としたこと以外は実施例１における
シリカ−マグネシア球形担体Ａを得た方法と同様の方法
でシリカ−マグネシア球形担体Ｆ（比較例３）およびシ
リカ−マグネシア球形担体Ｇ（比較例４）を得た。得ら
れたシリカ−マグネシア球形担体ＦおよびＧの細孔特性
と物理性状について下記する表１に併せて示す。Comparative Examples 3 and 4 The silica obtained in Example 1
Magnesia hydrate cake (a) the concentration of 1.5% by weight of the sodium alginate solution was thoroughly stirred mixture was added a 5-fold amount of water, and the SiO 2 -MgO solid concentration of the slurry 3
Wt% and the slurry heated concentrated SiΟ 2 -MgO solid concentration of 25 wt% and was except that silica in Example 1 - magnesia spherical carrier A silica in a manner similar to that was obtained - magnesia spherical carrier F (Comparative Example 3) and a silica-magnesia spherical carrier G (Comparative Example 4) were obtained. The pore characteristics and physical properties of the obtained silica-magnesia spherical carriers F and G are also shown in Table 1 below.
【００２３】表１から分る通り、スラリーの濃度が本発
明の範囲外にある比較例３および４に係る方法で製造し
て得たシリカ−マグネシア球形担体Ｆ、Ｇは細孔特性に
ついてはよいが担体の形状が楕円状で、かつ粒径が不揃
いであった。As can be seen from Table 1, the silica-magnesia spherical carriers F and G obtained by the methods according to Comparative Examples 3 and 4 having a slurry concentration outside the range of the present invention have good pore characteristics. However, the shape of the carrier was elliptical and the particle size was irregular.
【００２４】［実施例４、５］実施例１に示すシリカ−
マグネシア球形担体Ａの製造方法で濃度１．２重量％の
塩化カルシウム溶液の替わりにそれぞれ濃度０．５重量
％の塩化アルミニウム溶液および、濃度１．２重量％の
塩化カルシウム溶液と濃度０．５重量％の塩化アルミニ
ウム溶液を重量比で１：１の混合溶液とを用いたこと以
外は実施例１とほぼ同様の方法でシリカ−マグネシア球
形担体Ｈ（実施例４）およびシリカ−マグネシア球形担
体Ｉ（実施例５）を得た。得られたシリカ−マグネシア
球形担体Ｈ、Ｉの細孔特性と物理性状について下記する
表１に併せて示す。[Examples 4 and 5] The silica shown in Example 1
In the production method of the magnesia spherical carrier A, instead of the calcium chloride solution having a concentration of 1.2% by weight, an aluminum chloride solution having a concentration of 0.5% by weight and a calcium chloride solution having a concentration of 1.2% by weight and a concentration of 0.5% were used instead. % Of an aluminum chloride solution and a mixed solution having a weight ratio of 1: 1 were used in the same manner as in Example 1 to obtain a silica-magnesia spherical carrier H (Example 4) and a silica-magnesia spherical carrier I ( Example 5) was obtained. The pore characteristics and physical properties of the obtained silica-magnesia spherical carriers H and I are also shown in Table 1 below.
【００２５】表１から分る通り、本発明の実施例４およ
び５に係るシリカーマクネシア球形担体の製造方法によ
れば塩化カルシウム溶液の替わりに塩化アルミニウム溶
液を用いても、塩化カルシウム溶液と塩化アルミニウム
溶液の混合溶液を用いても、シリカ−マグネシア水和物
ケーキの細孔特性とほぼ同等の細孔特性を有し、かつ破
壊強度も強く、ほぼ真球のシリカ−マグネシア球形担体
が製造できた。As can be seen from Table 1, according to the method for producing spherical silica-macnesia carriers according to Examples 4 and 5 of the present invention, even if an aluminum chloride solution is used instead of a calcium chloride solution, Even when a mixed solution of an aluminum chloride solution is used, a substantially spherical silica-magnesia spherical carrier having substantially the same pore characteristics as the silica-magnesia hydrate cake, having a high breaking strength, and a substantially spherical shape is produced. did it.
【００２６】［実施例６］内容積５０リットルの撹拌機
付きステンレス製反応槽に、水２５リットルを入れ、７
０℃まで加温し、保持し、撹拌しつつ硫酸アルミニウム
水溶液３１８０ｇ（Ａ１２Ｏ３）として２５８ｇ）とア
ルミン酸ナトリウム水溶液２３１０ｇ（Ａｌ２Ｏ３とし
て２９０ｇ）とを同時もしくはほぼ同時に全量滴下し、
熟成して得たｐＨ９．５のアルミナ水和物スラリーを濾
過し、Ｎａ２Ｏが０．１重量％以下になるまで洗浄して
アルミナ水和物ケーキを得た。またシリカ−マグネシア
水和物は実施例１に示すシリカ−マグネシア水和物ケー
キ（ａ）を得た方法とほぼ同様の方法でＭｇＯとして３
５重量％含むシリカ−マグネシア水和物ケーキを得た。Example 6 25 liters of water was placed in a 50 liter stainless steel reaction tank equipped with a stirrer.
Warmed to 0 ° C., and held, stirred simultaneously or almost whole amount simultaneously added dropwise and 290 g) as an aqueous solution of aluminum sulfate 3180g (A1 2 O 3) as a 258 g) and aqueous sodium aluminate solution 2310g (Al 2 O 3 while,
The alumina hydrate slurry of pH 9.5 obtained by aging was filtered and washed until Na 2 O became 0.1% by weight or less to obtain an alumina hydrate cake. The silica-magnesia hydrate was prepared as MgO in the same manner as in Example 1 except that silica-magnesia hydrate cake (a) was obtained.
A silica-magnesia hydrate cake containing 5% by weight was obtained.
【００２７】一方前記シリカ−マグネシア水和物ケーキ
２７００ｇ（ＳｉＯ２−ＭｇＯとして５００ｇ）と前記
アルミナ水和物ケーキ１１３０ｇ（Ａｌ２Ｏ３として２
１５ｇ）とを双腕型ニーダ中で十分混合してシリカ−ア
ルミナ−マグネシア水和物ペースト（ｊ）を得た。この
シリカ−マグネシア水和物ケーキの一部を８０℃の温度
で１５時間乾燥し、６００℃の温度で３時間焼成してシ
リカ−アルミナ−マグネシア固形物（ｊ′）を得た。つ
いで該シリカ−アルミナ−マグネシア水和物ペースト５
４０ｇ（ＳｉＯ２−Ａｌ２Ｏ３−ＭｇＯとして１００
ｇ）に濃度１．５重量％のアルギン酸ナトリウム溶液５
００ｇ（ＳｉＯ２−Ａ１２Ｏ３−ＭｇＯに対して５倍
量）を加え十分撹拌混合し、ＳｉＯ２−Ａｌ２Ｏ３−Ｍ
ｇＯ固形分濃度として９．６重量％のスラリーを得た。
その後該スラリーを口径４．５ｍｍの滴下口から濃度
１．２重量％の塩化カルシウム溶液を入れた内容積１０
リットルの撹拌機付きパイレックス製反応槽に滴下し、
球状のヒドロゲルを形成させて５分間熟成した後球状の
ヒドロゲルを取り出して水洗し、８０℃の温度で１５時
間乾燥し、６００℃の温度で２時間焼成してシリカ−ア
ルミナ−マグネシア球形担体Ｊ（実施例６）を得た。得
られたシリカ−アルミナ−マグネシア固形物（ｊ′）の
細孔特性およびシリカ−アルミナ−マグネシア球形担体
（ｊ′）の細孔特性と物理性状について下記する表１に
併せて示す。On the other hand, 2700 g of the silica-magnesia hydrate cake (500 g as SiO 2 -MgO) and 1130 g of the alumina hydrate cake ( 2 g as Al 2 O 3)
And 15 g) were sufficiently mixed in a double-arm kneader to obtain a silica-alumina-magnesia hydrate paste (j). A part of the silica-magnesia hydrate cake was dried at a temperature of 80 ° C. for 15 hours and calcined at a temperature of 600 ° C. for 3 hours to obtain a silica-alumina-magnesia solid (j ′). Then, the silica-alumina-magnesia hydrate paste 5
40 g (100 as SiO 2 —Al 2 O 3 —MgO)
g) a 1.5 wt% sodium alginate solution 5
00 g (5 times the amount of SiO 2 -A1 2 O 3 -MgO), and sufficiently stirred and mixed, and then mixed with SiO 2 -Al 2 O 3 -M.
A slurry having a gO solid content of 9.6% by weight was obtained.
Thereafter, the slurry was poured from a dropping port having a diameter of 4.5 mm into an inner volume 10 containing a 1.2% by weight calcium chloride solution.
Liter of Pyrex reactor with stirrer,
After the spherical hydrogel was formed and aged for 5 minutes, the spherical hydrogel was taken out, washed with water, dried at a temperature of 80 ° C. for 15 hours, and calcined at a temperature of 600 ° C. for 2 hours to obtain a silica-alumina-magnesia spherical carrier J ( Example 6) was obtained. The pore properties of the obtained silica-alumina-magnesia solid (j ') and the pore properties and physical properties of the silica-alumina-magnesia spherical carrier (j') are also shown in Table 1 below.
【００２８】表１から分る通り、本発明の実施例６に係
るシリカ−アルミナ−マグネシア球形担体の製造方法に
よれば、主原料のシリカ−アルミナ−マグネシア水和物
ペーストの細孔特性とほぼ同等の細孔特性を有し、かつ
破壊強度も強く、ほぼ真球のシリカ−アルミナ−マグネ
シア球形担体が製造できた。As can be seen from Table 1, according to the method for producing a silica-alumina-magnesia sphere carrier according to Example 6 of the present invention, the pore characteristics of the silica-alumina-magnesia hydrate paste as the main raw material were substantially the same as those of the silica-alumina-magnesia hydrate paste. An almost spherical silica-alumina-magnesia spherical carrier having the same pore characteristics and high breaking strength was produced.
【００２９】［実施例７、８］実施例６におけるシリカ
−マグネシア水和物ケーキ１０８０ｇ（ＳｉＯ２−Ｍｇ
Ｏとして２００ｇ）に加えるアルミナ水和物ケーキの量
をそれぞれ１２０ｇ（Ａｌ２Ｏ３として２２ｇ）、１０
５０ｇ（Ａｌ２Ｏ３として２００ｇ）と変化させたこと
以外は実施例６におけるシリカ−アルミナ−マグネシア
水和物ペースト（ｊ）を得た方法とほぼ同様な方法でＡ
ｌ２Ｏ３として１０重量％含むシリカ−アルミナ−マグ
ネシア水和物ペースト（ｋ）とＡｌ２Ｏ３として５０重
量％含むシリカ−アルミナ−マグネシア水和物ペースト
（ｌ）、およびシリカ−アルミナ−マグネシア固形物
（ｋ′）、（ｌ′）を得た。ついでそれぞれのペースト
（ｋ）、（ｌ）を用いて球形担体（Ａ）を得た実施例１
の方法と同様の方法でシリカ−アルミナ−マグネシア球
形担体Ｋ（実施例７）およびシリカ−アルミナ−マグネ
シア球形担体Ｌ（実施例８）を得た。得られたシリカ−
アルミナ−マグネシア固形物（ｋ′）、（ｌ′）の細孔
特性およびシリカ−アルミナ−マグネシア球形担体Ｋ、
Ｌの細孔特性と物理性状について下記する表１に併せて
示す。[Examples 7 and 8] 1080 g of the silica-magnesia hydrate cake (SiO 2 -Mg
The amount of the alumina hydrate cake added to 200 g as O) was 120 g (22 g as Al 2 O 3 ),
Except that the amount was changed to 50 g (200 g as Al 2 O 3 ), A was obtained in substantially the same manner as the method of obtaining the silica-alumina-magnesia hydrate paste (j) in Example 6.
Silica-alumina-magnesia hydrate paste containing 10% by weight as l 2 O 3 (k), silica-alumina-magnesia hydrate paste containing 50% by weight as Al 2 O 3 (l), and silica-alumina-magnesia Solids (k ') and (l') were obtained. Next, a spherical carrier (A) was obtained using each of the pastes (k) and (l).
A silica-alumina-magnesia spherical carrier K (Example 7) and a silica-alumina-magnesia spherical carrier L (Example 8) were obtained in the same manner as in the above method. The obtained silica
The pore characteristics of the alumina-magnesia solids (k '), (l') and the silica-alumina-magnesia spherical carrier K,
The pore characteristics and physical properties of L are shown in Table 1 below.
【００３０】表１から分る通り、本発明の実施例７、８
に係るシリカ−アルミナ−マグネシア球形担体の製造方
法によれば、主原料のシリカ−アルミナ−マグネシア水
和物のアルミナ含有量を変化させても、それぞれのシリ
カ−アルミナ−マグネシア水和物ペーストの細孔特性と
ほぼ同等の細孔特性を有し、かつ破壊強度も強く、ほぼ
真球のシリカ−アルミナ−マグネシア球形担体が製造で
きた。As can be seen from Table 1, Examples 7 and 8 of the present invention.
According to the method for producing a silica-alumina-magnesia sphere carrier according to the above, even when the alumina content of the silica-alumina-magnesia hydrate as the main raw material is changed, the fineness of each silica-alumina-magnesia hydrate paste is changed. The silica-alumina-magnesia spherical carrier having almost the same spherical properties as the pores and having a high breaking strength was obtained.
【００３１】［比較例５、６］実施例６で得たシリカ−
アルミナ−マグネシア水和物ペースト（ｊ）に添加する
濃度１．５重量％のアルギン酸ナトリウム溶液の添加量
をＳｉＯ２−Ａｌ２Ｏ ３−ＭｇＯに対してそれぞれ１倍
量、１５倍量としたこと以外はシリカ−アルミナ−マグ
ネシア水和物ペースト（ｊ）を得た実施例６とほぼ同様
の方法でシリカ−アルミナ−マグネシア球形担体Ｍ（比
較例５）、シリカ−アルミナ−マグネシア球形担体Ｎ
（比較例６）を得た。得られたシリカ−アルミナ−マグ
ネシア球形担体Ｍ、Ｎの細孔特性と物理性状について下
記する表１に併せて示す。[Comparative Examples 5 and 6] The silica obtained in Example 6
Add to alumina-magnesia hydrate paste (j)
Amount of 1.5 wt% sodium alginate solution added
Is SiO2-Al2O 3-1 times each for MgO
Except that the amount was 15 times the amount of silica-alumina-mag
Almost the same as Example 6 in which Nessia hydrate paste (j) was obtained
The silica-alumina-magnesia spherical carrier M (specific ratio)
Comparative Example 5), Silica-alumina-magnesia spherical carrier N
(Comparative Example 6) was obtained. Silica-alumina-mag obtained
The pore characteristics and physical properties of the Nesia spherical carriers M and N are as follows.
Also shown in Table 1 below.
【００３２】表１から分る通り、多糖類溶液の添加量を
本発明の範囲外にある比較例５および６に係る方法で製
造して得られたシリカ−アルミナ−マグネシア球形担体
Ｍは細孔特性についてはよいが担体の形状が楕円状にな
り、シリカ−アルミナ−マグネシア球形担体Ｎは細孔特
性が変化し、破壊強度も弱かった。As can be seen from Table 1, the silica-alumina-magnesia spherical carrier M obtained by producing the polysaccharide solution by the method according to Comparative Examples 5 and 6, which is out of the scope of the present invention, has a fine pore size. Although the characteristics were good, the shape of the support became elliptical, and the silica-alumina-magnesia spherical support N changed its pore characteristics and had a low breaking strength.
【００３３】［比較例７、８］実施例６で得たシリカ−
アルミナ−マグネシア水和物ペースト（Ｊ）に濃度１．
５重量％のアルギン酸ナトリウム溶液を５倍量と水とを
加え十分撹拌混合したスラリーのＳｉＯ２−Ａｌ２Ｏ３
−ＭｇＯ固形分濃度を３重量％と該スラリーを加熱濃縮
し、ＳｉＯ２−Ａｌ２Ｏ３−ＭｇＯ固形分濃度を２５重
量％としたこと以外はシリカ−アルミナ−マグネシア水
和物ペースト（Ｊ）を得た実施例６の方法とほぼ同様の
方法でシリカ−アルミナ−マグネシア球形担体Ｏ（比較
例７）、シリカ−アルミナ−マグネシア球形担体Ｐ（比
較例８）を得た。得られたシリカ−アルミナ−マグネシ
ア球形担体Ｏ、Ｐの細孔特性と物理性状について下記す
る表１に併せて示す。Comparative Examples 7 and 8 The silica obtained in Example 6
Alumina-magnesia hydrate paste (J) has a concentration of 1.
5% by weight of a sodium alginate solution of 5% by weight and water were added, and the slurry was sufficiently stirred and mixed. The slurry was SiO 2 —Al 2 O 3
-MgO 3 wt% and the slurry solids concentration and heated concentrated, SiO 2 -Al 2 O 3 -MgO solids concentration except that a 25 wt% silica - alumina - magnesia hydrate paste (J) The silica-alumina-magnesia spherical carrier O (Comparative Example 7) and the silica-alumina-magnesia spherical carrier P (Comparative Example 8) were obtained in substantially the same manner as the method of Example 6 that was obtained. The pore characteristics and physical properties of the obtained silica-alumina-magnesia spherical carriers O and P are also shown in Table 1 below.
【００３４】表１から分る通り、スラリーにおけるシリ
カ−アルミナ−マグネシアの濃度が本発明の範囲外にあ
る比較例７および８に係る方法で製造して得たれたシリ
カ−アルミナ−マグネシア球形触媒担体Ｏ、Ｐは細孔特
性についてはよいが担体の形状が楕円状で、かつ粒径が
不揃いであった。As can be seen from Table 1, the silica-alumina-magnesia spherical catalyst carrier obtained by the method according to Comparative Examples 7 and 8 in which the concentration of silica-alumina-magnesia in the slurry is out of the range of the present invention. O and P had good pore characteristics, but had an elliptical carrier shape and irregular particle sizes.
【００３５】［実施例９、１０］実施例６に示すシリカ
−アルミナ−マグネシア球形担体Ｊの製造方法で濃度
１．２重量％の塩化カルシウム溶液の替わりに濃度０．
６重量％の塩化アルミニウム溶液および濃度１．２重量
％の塩化カルシウム溶液と濃度０．５重量％の塩化アル
ミニウム溶液を重量比で１：１の混合溶液とを用いたこ
と以外はシリカ−アルミナ−マグネシア球形担体Ｊを得
た実施例６とほぼ同様の方法でシリカ−アルミナ−マグ
ネシア球形担体Ｑ（実施例９）およびシリカ−アルミナ
−マグネシア球形担体Ｒ（実施例１０）を得た。得られ
たシリカ−アルミナ−マグネシア球形担体Ｑ、Ｒの細孔
特性と物理性状について下記する表１に併せて示す。[Examples 9 and 10] In the method for producing the silica-alumina-magnesia spherical carrier J shown in Example 6, the concentration was changed to 0.2% by weight instead of the calcium chloride solution having a concentration of 1.2% by weight.
A silica-alumina powder was used except that a 6% by weight aluminum chloride solution, a 1.2% by weight calcium chloride solution, and a 0.5% by weight aluminum chloride solution were used in a 1: 1 by weight mixed solution. A silica-alumina-magnesia spherical carrier Q (Example 9) and a silica-alumina-magnesia spherical carrier R (Example 10) were obtained in substantially the same manner as in Example 6 in which the magnesia spherical carrier J was obtained. The pore characteristics and physical properties of the obtained silica-alumina-magnesia spherical carriers Q and R are also shown in Table 1 below.
【００３６】表１から分る通り、塩化カルシウム溶液の
替わりに塩化アルミニウム溶液を用いても、塩化カルシ
ウム溶液と塩化アルミニウム溶液との混合溶液を用いて
も、シリカ−アルミナ−マグネシア水和物ペーストの細
孔特性とほぼ同等の細孔特性を有し、かつ破壊強度も強
く、ほぼ真球のシリカ−アルミナ−マグネシア球形担体
が製造できた。As can be seen from Table 1, the silica-alumina-magnesia hydrate paste was prepared using either an aluminum chloride solution instead of the calcium chloride solution or a mixed solution of the calcium chloride solution and the aluminum chloride solution. The silica-alumina-magnesia spherical support having substantially the same spherical properties as the fine pores and having a high breaking strength was obtained.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】以上述べた通り本発明によれば、主原料
として用いたシリカ−マグネシア水和物ペーストあるい
はシリカ−アルミナ−マグネシア水和物ペーストの細孔
特性とほぼ同一であり、形状がほぼ真球で、表面が平滑
で外部から内部まで均一であり、かつ破壊強度の強いシ
リカ−マグネシアあるいはシリカ−アルミナ−マグネシ
ア球形担体の製造方法を提供することができるので、そ
の工業的価値は高い。As described above, according to the present invention, the pore characteristics of the silica-magnesia hydrate paste or silica-alumina-magnesia hydrate paste used as the main raw material are almost the same, and the shape is almost the same. Since a method for producing a spherical carrier of silica-magnesia or silica-alumina-magnesia having a perfect sphere, a smooth surface, uniform from outside to inside, and high breaking strength can be provided, its industrial value is high.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA01 AA08 BA01A BA01B BA01C BA02A BA02B BA02C BA06A BA06B BA06C BB04A BB04B BB04C EA04X EC06Y EC07Y EC14Y EC15Y FB05 FB30 FB33 FB34 FB36 FB57 FB61 FC07 FC08 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4G069 AA01 AA08 BA01A BA01B BA01C BA02A BA02B BA02C BA06A BA06B BA06C BB04A BB04B BB04C EA04X EC06Y EC07Y EC14Y EC15Y FB05 FB30 FB33 FB34 FB36 FCB FB08
Claims (6)
るいはシリカ−マグネシア水和物にアルミナ水和物を添
加したシリカ−アルミナ−マグネシア水和物ペーストに
多糖類溶液を加えて混合し、濃度を調整したスラリーを
多価金属イオンを含む溶液中へ滴下して球状のヒドロゲ
ルを形成させ、ついで熟成し、洗浄した後乾燥、焼成す
ることを特徴とする触媒担持用球形担体の製造方法。1. A polysaccharide solution is added to a silica-magnesia hydrate paste or a silica-alumina-magnesia hydrate paste obtained by adding an alumina hydrate to a silica-magnesia hydrate paste to mix and adjust the concentration. A method for producing a spherical carrier for carrying a catalyst, characterized by dropping the slurry thus obtained into a solution containing polyvalent metal ions to form a spherical hydrogel, then aging, washing, drying and calcining.
は濃度１．０〜３．０重量％の低メトキシルペクチン、
アルギン酸ナトリウムまたはカゼイン酸ナトリウムであ
ることを特徴とする請求項１記載の触媒担持用球形担体
の製造方法。2. The polysaccharide solution to be added to the hydrate paste is low methoxyl pectin having a concentration of 1.0 to 3.0% by weight,
The method for producing a spherical carrier for supporting a catalyst according to claim 1, wherein the method is sodium alginate or sodium caseinate.
加量は該水和物ペーストを酸化物換算した重量に対して
３〜１０倍量であることを特徴とする請求項１または２
記載の触媒担持用球形担体の製造方法。3. The amount of the polysaccharide solution added to the hydrate paste is 3 to 10 times the weight of the hydrate paste in terms of oxide.
A method for producing the spherical carrier for supporting a catalyst according to the above.
いはシリカ−アルミナ−マグネシアを酸化物換算で５〜
２０重量％の範囲に濃度を調整されていることを特徴と
する請求項１〜３のいずれか１項記載の触媒担持用球形
担体の製造方法。4. The slurry is prepared by converting silica-magnesia or silica-alumina-magnesia to an oxide in an amount of from 5 to 5.
The method for producing a spherical carrier for supporting a catalyst according to any one of claims 1 to 3, wherein the concentration is adjusted within a range of 20% by weight.
〜３．０重量％のカルシウム、アルミニウム、マグネシ
ウム、バリウムまたはストロンチウムのうち少なくとも
１種からなることを特徴とする請求項１〜４のいずれか
１項記載の触媒担持用球形担体の製造方法。5. The polyvalent metal ion solution having a concentration of 0.5
The method for producing a spherical carrier for supporting a catalyst according to any one of claims 1 to 4, wherein the spherical carrier comprises at least one of calcium, aluminum, magnesium, barium, and strontium in an amount of up to 3.0% by weight.
ヒドロゲルあるいはシリカ−アルミナ−マグネシアヒド
ロゲルの乾燥温度は６０〜１２０℃であり、また焼成温
度は４００〜７００℃であることを特徴とする請求項１
〜４のいずれか１項記載の触媒担持用球形担体の製造方
法。6. The drying temperature of the spherical silica-magnesia hydrogel or the silica-alumina-magnesia hydrogel after the washing is 60 to 120 ° C., and the firing temperature is 400 to 700 ° C. 1
5. The method for producing a spherical carrier for supporting a catalyst according to any one of items 4 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11197796A JP2001025661A (en) | 1999-07-12 | 1999-07-12 | Production of spherical carrier for catalyst deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11197796A JP2001025661A (en) | 1999-07-12 | 1999-07-12 | Production of spherical carrier for catalyst deposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001025661A true JP2001025661A (en) | 2001-01-30 |
Family
ID=16380505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11197796A Pending JP2001025661A (en) | 1999-07-12 | 1999-07-12 | Production of spherical carrier for catalyst deposition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001025661A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433051A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Magnesium-containing alumina carrier and preparation method and application thereof |
-
1999
- 1999-07-12 JP JP11197796A patent/JP2001025661A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433051A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Magnesium-containing alumina carrier and preparation method and application thereof |
| CN114433051B (en) * | 2020-10-19 | 2023-05-05 | 中国石油化工股份有限公司 | Magnesia-containing alumina carrier, and preparation method and application thereof |
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