JPS62252378A - Manufacture of porous silica carrier - Google Patents
Manufacture of porous silica carrierInfo
- Publication number
- JPS62252378A JPS62252378A JP61093660A JP9366086A JPS62252378A JP S62252378 A JPS62252378 A JP S62252378A JP 61093660 A JP61093660 A JP 61093660A JP 9366086 A JP9366086 A JP 9366086A JP S62252378 A JPS62252378 A JP S62252378A
- Authority
- JP
- Japan
- Prior art keywords
- silicic acid
- slurry
- silica gel
- amount
- added
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 172
- 239000000377 silicon dioxide Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 71
- 239000002002 slurry Substances 0.000 claims description 68
- 235000012239 silicon dioxide Nutrition 0.000 claims description 67
- 239000000741 silica gel Substances 0.000 claims description 53
- 229910002027 silica gel Inorganic materials 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 description 50
- 239000002245 particle Substances 0.000 description 46
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910052753 mercury Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000011325 microbead Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 etc. Chemical class 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は多孔性シリカの製造方法に関するものであって
、さらに詳しくは大きな細孔容積と強い粒子強度を有す
る多孔性シリカ担体の製造法に係る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing porous silica, and more specifically to a method for producing a porous silica carrier having a large pore volume and strong particle strength. It depends.
［従来の技術］
多孔性シリカ粒子は、食品、医薬品の分野で、また触媒
担体、吸着剤、乾燥剤等として、従来から広く使用され
ているが、その用途によって多孔性シリカ粒子は、使用
目的に適った性状を有していなければならない。例えば
、触媒担体として使用する多孔性シリカ粒子には、大き
な細孔容積と強い粒子強度が要求される。[Prior Art] Porous silica particles have been widely used in the food and pharmaceutical fields, and as catalyst carriers, adsorbents, desiccants, etc.; It must have properties suitable for. For example, porous silica particles used as catalyst supports require large pore volumes and strong particle strength.
触媒担体に使用される多孔性シリカ粒子の製造方法とし
て、特開昭６１−４．０８１３号公報には、酸性シリカ
ゾルのｐＨを急激にアルカリ側に上昇させてゲル化させ
る方法により、細孔容積が大きく、シャープな細孔分布
を有する多孔性シリカ粒子を製造する技術が開示されて
いる。また、特開昭５８−１３５１１９号公報には、Ｓ
ｉＯ，濃度が特定されたシリカゾルをゲル化させ、これ
にアンモニア水のようなアルカリを加えてｐＨを５〜１
０に調整してから、ゲル化物に５０〜９５℃で水熱処理
を施し１次いでこれを酸水溶液で処理し。As a method for producing porous silica particles used as a catalyst carrier, JP-A-61-4.0813 discloses a method in which the pH of an acidic silica sol is rapidly raised to the alkaline side to form a gel, which reduces the pore volume. A technique for producing porous silica particles having a large pore size and a sharp pore distribution has been disclosed. Also, in Japanese Patent Application Laid-Open No. 58-135119, S
iO, silica sol with a specified concentration is gelled, and an alkali such as aqueous ammonia is added to this to adjust the pH to 5-1.
After adjusting to 0, the gelled product was subjected to hydrothermal treatment at 50 to 95°C, and then treated with an acid aqueous solution.
しかる後、低い温度で乾燥することにより、細孔容積の
大きいシリカ粒子の製造方法が記載されている。さらに
また、特開昭５９−２３２９１１号公報には、アルカリ
ケイ酸塩と鉱酸との反応によリシリカ粒子を製造する方
法に於いて、反応液中のＳｉＯ□濃度を１２〜２５ｗｔ
％の範囲に保持すると共に反応温度を３０℃以下に保持
しながら。A method for producing silica particles with a large pore volume by subsequently drying at a low temperature is described. Furthermore, JP-A No. 59-232911 discloses a method for producing resilica particles by the reaction of an alkali silicate and a mineral acid, in which the SiO□ concentration in the reaction solution is adjusted to 12 to 25 wt.
% while keeping the reaction temperature below 30°C.
反応時のｐＨを第１段目では１．５〜５．０に、第２段
目では６〜ｌＯに維持して反応を２段階で行わせ、吸油
量の大きいシリカ粒子を得る方法が教示されている。It teaches a method to obtain silica particles with large oil absorption by carrying out the reaction in two stages by maintaining the pH during the reaction at 1.5 to 5.0 in the first stage and 6 to 1O in the second stage. has been done.
［発明が解決しようとする問題点コ
上に紹介した方法で製造されるシリカ粒子を含めて、従
来の多孔性シリカ粒子は、一般にその細孔容積が０．６
〜１．２ｍｌ／ｇ程度で□ある。然るに、成る種の化学
反応系で使用される触媒では、細孔容積が１．０〜２．
５ｍｌ／ｇ程度で、平均細孔直径が１００〜１０００人
の範囲にあり、しがち粒子強度が大きいシリカ担体が要
求されているが、従来のシリカ粒子ではこの要請に応え
ることができない。ちなみに、シリカ粒子として大きな
細孔容積を備えていても、粒子強度が小さいものは触媒
担体として使用した際に粉化しゃすく、触媒反応の実施
に支障を来す原因になるので、この種のシリカ粒子は触
媒担体として工業的には利用できない。[Problems to be Solved by the Invention] Conventional porous silica particles, including silica particles produced by the method introduced above, generally have a pore volume of 0.6.
It is □ at about 1.2 ml/g. However, catalysts used in certain types of chemical reaction systems have pore volumes of 1.0 to 2.
A silica carrier with a particle size of about 5 ml/g, an average pore diameter in the range of 100 to 1000 pores, and a high particle strength is required, but conventional silica particles cannot meet this demand. Incidentally, even if silica particles have a large pore volume, particles with low particle strength will turn into powder when used as a catalyst carrier, causing problems in carrying out the catalytic reaction. Silica particles cannot be used industrially as a catalyst support.
シリカ担体も他の触媒担体同様、その細孔容積及び平均
細孔直径が大きくかればなるほど、粒子強度は低下する
のが通例である。しかして、本発明の目的は、非常に大
きな細孔容積と細孔直径を有しながら、粒子強度も大き
い多孔性シリカ担体の製造法を提供することにある。As with other catalyst supports, the larger the pore volume and average pore diameter of the silica carrier, the lower the particle strength. Therefore, an object of the present invention is to provide a method for producing a porous silica carrier having a very large pore volume and pore diameter and also having high particle strength.
［問題点を解決するための手段］ 本発明の方法は、シリカゲル粒子を骨材に。[Means for solving problems] The method of the present invention uses silica gel particles as aggregate.
ケイ酸液をバインダーにそれぞれ使用して、シリカゲル
粒子を、バインダーに用いたケイ酸液由来のシリカによ
って相互に結合させるものであって□、その方法は、Ｓ
ｉＯ，濃度が１〜６０ ｗｔ％の範□囲に撚るシリカゲ
ルスラリーに、アルカリ水溶液を添加してスラリーのｐ
Ｈを８．５以上に保持しつつ液温を５０℃以上に保持し
ながら、１分間当りのケイ酸液の添加□量が５ｉ０２量
に換算して、□前記シリカゲルスラリーに含まれるＳ
ｉ Ｏ２量の１／１０００以下になる添加速度で。A silicic acid solution is used as a binder, and silica gel particles are bonded to each other by the silica derived from the silicic acid solution used as a binder.
An alkaline aqueous solution is added to the silica gel slurry to be twisted to a concentration of iO in the range of 1 to 60 wt%.
While maintaining H at 8.5 or higher and the liquid temperature at 50°C or higher, the amount of silicic acid solution added per minute is converted to 5i02, and the amount of S contained in the silica gel slurry is
i At an addition rate that is 1/1000 or less of the amount of O2.
且つケイ酸液の添加総量がＳｉＯ□量に換算して、前記
シリカゲルスラリーに含まれる５ｉＯ２ｉの５０ｗｔ％
を越えない範囲内で、ケイ酸液を前記のシリカゲルスラ
リーに添加し、次いでこの混合スラリーを乾燥して焼成
することからなる。In addition, the total amount of silicic acid solution added is 50 wt% of 5iO2i contained in the silica gel slurry in terms of SiO□ amount.
The process consists of adding a silicic acid liquid to the silica gel slurry within a range not exceeding , and then drying and calcining the mixed slurry.
本発明に係る第２の方法は、ＳｉＯ□濃度が１〜６０ｗ
ｔ％の範囲にあるシリカゲルスラリーに、アルカリ水溶
液を添加してスラリーのｐＨを８．５以上に保持しつつ
、液温を５０℃以上に保持しながら、１分間当りのケイ
酸液の添加量が５ｉ０２量に換算して、前記シリカゲル
スラリーに含まれるＳ ｉ Ｏ，、量の１／１０００以
下になる添加速度で、且つケイ酸液の添加総量がＳ ｉ
Ｏ。In the second method according to the present invention, the SiO□ concentration is 1 to 60 w.
Add an alkaline aqueous solution to the silica gel slurry in the range of t% to maintain the pH of the slurry at 8.5 or higher and the liquid temperature at 50°C or higher, and add the amount of silicic acid solution per minute. is added at a rate such that S i O, contained in the silica gel slurry is 1/1000 or less of the amount of S i O contained in the silica gel slurry, and the total amount of silicic acid liquid added is
O.
量に換算して、前記シリカゲルスラリーに含まれるＳ
ｉ Ｏ，量の５０ｗｔ％を越えない範囲内で。S contained in the silica gel slurry in terms of amount
i O, within a range not exceeding 50 wt% of the amount.
ケイ酸液を前記のシリカゲルスラリーに添加し、次いで
（ａ）ケイ酸液が添加されたシリカゲルスラリーに酸を
加えてｐＨを７以下に低下させる操作、
（ｂ）操作（ａ）の後、アルカリ水溶液を添加してスラ
リーのｐＨを８．５以上に保持しつつ、液温を５０℃以
上に保持しながら、１分間当りのケイ酸液の添加量が５
ｉ０２量に換算して、前記ケイ酸液が添加されたシリカ
ゲルスラリーに含まれる総ＳｉＯ□量の１ ／１０００
以下になる添加速度で、且つケイ酸液の添加総量がＳｉ
Ｏ２量に換算して、前記ケイ酸液が添加されたシリカゲ
ルスラリーに含まれる総ＳｉＯ□量の５０ｗｔ％を越え
ない範囲内で、ケイ酸液をシリカゲルスラリーに添加す
る操作、を１回又は複数回繰り返し、得られた混合スラ
リーを乾燥して焼成することからなる。A silicic acid solution is added to the silica gel slurry, and then (a) an acid is added to the silica gel slurry to which the silicic acid solution has been added to lower the pH to 7 or less, (b) after operation (a), an alkali While adding the aqueous solution and maintaining the pH of the slurry at 8.5 or higher and the liquid temperature at 50°C or higher, the amount of silicic acid solution added per minute was 5.
In terms of iO2 amount, 1/1000 of the total SiO□ amount contained in the silica gel slurry to which the silicic acid solution was added.
The addition rate is as follows, and the total amount of silicic acid liquid added is Si
Adding the silicic acid liquid to the silica gel slurry once or multiple times within a range that does not exceed 50 wt% of the total SiO□ amount contained in the silica gel slurry to which the silicic acid liquid has been added, in terms of O2 amount. The process consists of repeating the process several times, drying and firing the resulting mixed slurry.
［作 用コ
本発明の方法で使用されるシリカゲルスラリーは、市販
のシリカゲルを水に分散させたものであっても差し支え
ないが、シリカゲルは骨材となるものなので、ゲル構造
が強いものを選ぶことが好ましい０本発明のシリカゲル
スラリーはまた、市販のシリカゾルから調製することも
できる。この場合のシリカゾルには、その濃度が１νｔ
％以上、好ましくは５〜４０１ｔ％の範囲にあるものを
使用することを可とする。シリカゾルの濃度が１ｗｔ％
以下であると、これから得られるシリカゲルには強固な
ゲル構造を期待できないからである。シリカゾルのゲル
化には、公知の方法がいずれも採用可能であるが、シリ
カゾルに酸を添加してｐＨを一旦酸性域にした後、アル
カリ水溶液を添加し・てゲル化させる方法は。[Function] The silica gel slurry used in the method of the present invention may be one obtained by dispersing commercially available silica gel in water, but since silica gel serves as an aggregate, choose one with a strong gel structure. The silica gel slurry of the present invention can also be prepared from commercially available silica sols. In this case, the silica sol has a concentration of 1νt
% or more, preferably in the range of 5 to 401 t%. The concentration of silica sol is 1wt%
If it is below, the silica gel obtained from this cannot be expected to have a strong gel structure. Any known method can be used to gel the silica sol, but there is a method in which an acid is added to the silica sol to bring the pH to an acidic range, and then an alkaline aqueous solution is added to form a gel.
ゲル構造が強いシリカゲルが得られる点で好ましい。市
販のシリカゲルを水に分散させる場合でも、或いはシリ
カゾルから調製する場合でも、本発明で使用するシリカ
ゲルスラリーは、そのＳｉＯ２濃度が１〜６０ｗｔ％の
範囲に調整される。This is preferable in that a silica gel with a strong gel structure can be obtained. Whether commercially available silica gel is dispersed in water or prepared from silica sol, the silica gel slurry used in the present invention is adjusted to have an SiO2 concentration in the range of 1 to 60 wt%.
６０ｗｔ％以上では攪拌によってスラリー全体を均一に
所望のｐＨに維持することが難しく、また、１ｗｔ％以
下ではシリカ担体の生産効率が低く、経済的でない。If it is more than 60 wt%, it is difficult to uniformly maintain the entire slurry at a desired pH by stirring, and if it is less than 1 wt%, the production efficiency of the silica carrier is low and it is not economical.
バインダーとして使用されるケイ酸液は、水ガラスをイ
オン交換樹脂にて脱アルカリすることで得ることができ
る。ケイ酸液にバインダーとしての機能を発揮させるた
めには、その濃度（Ｓ １０２１度）は８すｔ％以下、
一般的には１〜５ｔｚｔ％の゛範囲にあることが望まし
い、これ以上高濃度であると、ケイ酸液はゾル化ないし
はゲル化しやすくなり、ゾル化ないしはゲル化すると、
バインダーとしての機能が著しく低下するからである。The silicic acid liquid used as a binder can be obtained by dealkalizing water glass with an ion exchange resin. In order for the silicic acid liquid to function as a binder, its concentration (S 1021 degrees) must be 8% or less,
In general, it is desirable that the concentration be in the range of 1 to 5 tzt%.If the concentration is higher than this, the silicic acid solution tends to become a sol or a gel, and when it becomes a sol or a gel,
This is because the function as a binder is significantly reduced.
本発明の方法に於いては、シリカゲルスラリーに対する
ケイ酸液の添加を、連続的にもまた所続的にも行うこと
ができるが、ケイ酸液の添加に際しては次の条件が順守
されなければならない。In the method of the present invention, the silicic acid solution can be added to the silica gel slurry either continuously or intermittently, but the following conditions must be met when adding the silicic acid solution: It won't happen.
第１の条件はケイ酸液が添加されるスラリーの液温を５
０℃以上、好ましくは８０℃以上に保持し、ｐＨを８．
５以上、好ましくは９以上に保持することである。その
理由は液温やｐＨ値が低いと、シリカの溶解度を充分高
めることができないことによる。尚、液温を１００℃以
上にする場合は、加圧容器が通常使用される。スラリー
のｐＨはケイ酸液が添加される間中、常に８．５以上、
好ましくは９以上に保持される関係で、ケイ酸液の添加
に際しては、これと同時にアルカリ水溶液がスラリーに
添加される。この場合のアルカリ水溶液としては、アン
モニア水、水溶性アミン類、水酸化ナトリウム水溶液な
どが使用可能である。このうち、アンモニア水の使用は
、アルカリ金属などの不純物をスラリーに持ち込まず、
従って不純物の洗浄除去を省略できる点で、極めて望ま
しい。The first condition is that the temperature of the slurry to which the silicic acid solution is added is 5.
The temperature is maintained at 0°C or higher, preferably 80°C or higher, and the pH is adjusted to 8.
It is to be kept at 5 or more, preferably 9 or more. The reason for this is that when the liquid temperature and pH value are low, the solubility of silica cannot be sufficiently increased. Note that when the liquid temperature is 100° C. or higher, a pressurized container is usually used. The pH of the slurry is always 8.5 or higher during the addition of the silicic acid solution.
When adding the silicic acid solution, an alkaline aqueous solution is added to the slurry at the same time so that the ratio is preferably maintained at 9 or higher. As the alkaline aqueous solution in this case, ammonia water, water-soluble amines, sodium hydroxide aqueous solution, etc. can be used. Among these, the use of ammonia water does not introduce impurities such as alkali metals into the slurry.
Therefore, it is extremely desirable since cleaning and removal of impurities can be omitted.
ケイ酸液添加に際しての第２の条件は、添加速度と添加
総量に関するものであって、ケイ酸液の添加速度は、１
分間当りのケイ酸液の添加量がＳｉ○２量換算で、シリ
カゲルスラリーに含まれるＳｉＯ□量の１ ／１０００
以下でなければならず、また添加総量は、Ｓ ｉ Ｏ，
量換算で、シリカゲルスラリーに含まれるＳｉＯ２量の
５０ｗｔ％を越えない範囲にある。The second condition when adding silicic acid liquid is related to the addition rate and total amount of addition, and the addition rate of silicic acid liquid is 1
The amount of silicic acid solution added per minute is equivalent to the amount of Si○2, which is 1/1000 of the amount of SiO□ contained in the silica gel slurry.
The total amount added must be less than or equal to S i O,
In terms of amount, the amount does not exceed 50 wt% of the amount of SiO2 contained in the silica gel slurry.
本発明者等が得た知見によれば、ケイ酸液の添加速度を
上記の規定値より増大させてシリカゲルスラリーにケイ
酸液を添加した場合には、他の条件を本発明と同一に維
持しても、大細孔容積で高粒子強度の多孔性シリカ担体
を得ることができない。このことから１本発明の方法に
より、大細孔容積で高粒子強度の多孔性シリカ担体が製
造できる理由を、次のように考えることができる。According to the knowledge obtained by the present inventors, when the silicic acid liquid is added to the silica gel slurry by increasing the addition rate of the silicic acid liquid from the above specified value, other conditions are maintained the same as in the present invention. However, it is not possible to obtain a porous silica support with a large pore volume and high particle strength. From this, the reason why a porous silica carrier with a large pore volume and high particle strength can be produced by the method of the present invention can be considered as follows.
すなわち、ケイ酸液を上記の添加速度でシリカゲルスラ
リーに添加すると、当初はスラリー中に溶解するが、添
加を続ける間にケイ酸は過飽和になって分散状態にある
シリカゲル粒子（骨材）上に析出し、これがバインダー
となって粒子同志を結合させる。ケイ酸液の添加を低速
度で行えば、上記の溶解−過飽和−析出を反復させるこ
とができるので、先に結合した粒子同志がさらに互いに
結合する事態が繰り返され、その結果として当初スラリ
ーに分散していた個々のシリカゲル粒子は、適当な粒子
間隙を保ちながら凝集して結合するため、これを乾燥、
焼成することで大細孔容積で高粒子強度の多孔性シリカ
担体が製造できるものと推察される。これに引き換え、
ケイ酸液の添加速度が高い場合は、添加されたケイ酸が
独自にゲル化してしまうため、バインダーとしての機能
を発揮できず、それ故に所望の多孔性シリカ担体を得る
ことができないものと考えられる。従って１本発明では
ケイ酸液の添加速度が極めて重要であって、シリカゲル
スラリーに対する１分間当りのケイ酸液の添加量は、Ｓ
ｉＯ２量換算でシリカゲルスラリーに含まれるＳｉＯ２
量の１ ／１０００以下とすることが必要であり、好ま
しい添加速度は１ ／４０００〜１ ／２００００の範
囲内にある。In other words, when a silicic acid solution is added to a silica gel slurry at the above-mentioned addition rate, it initially dissolves in the slurry, but as the addition continues, the silicic acid becomes supersaturated and dissolves onto the dispersed silica gel particles (aggregate). This precipitates and becomes a binder that binds the particles together. If the silicic acid solution is added at a low rate, the above-mentioned dissolution-supersaturation-precipitation process can be repeated, so that the previously bonded particles are further bonded to each other, and as a result, the particles initially dispersed in the slurry are The individual silica gel particles that had been used for a long time aggregate and bond while maintaining appropriate particle gaps, so they are dried and bonded together.
It is presumed that by firing, a porous silica carrier with a large pore volume and high particle strength can be produced. In exchange for this,
It is thought that if the addition rate of the silicic acid solution is high, the added silicic acid will gel on its own and will not be able to perform its function as a binder, making it impossible to obtain the desired porous silica carrier. It will be done. Therefore, in the present invention, the addition rate of the silicic acid liquid is extremely important, and the amount of the silicic acid liquid added per minute to the silica gel slurry is S
SiO2 contained in silica gel slurry in terms of iO2 amount
It is necessary that the amount is 1/1000 or less, and the preferable addition rate is within the range of 1/4000 to 1/20000.
ケイ酸液の添加総量について言えば、その量が余り多す
ぎると、適当な粒子間隙を保ちながら凝集して結合した
シリカゲル粒子の間隙部が。Regarding the total amount of silicic acid solution added, if the amount is too large, the gaps between the silica gel particles will aggregate and bond while maintaining appropriate particle gaps.
ケイ酸の析出によって閉塞されてしまう心配がある。こ
の意味から、ケイ酸液の添加総量は、ケイ酸液を添加せ
んとするシリカゲルスラリーの濃度を考慮して選定する
ことが好ましいが。There is a concern that it may be blocked by silicic acid precipitation. In this sense, it is preferable that the total amount of the silicic acid liquid to be added be selected in consideration of the concentration of the silica gel slurry to which the silicic acid liquid is to be added.
一般的には添加総量はＳ ｉ Ｏ，量換算で、シリカゲ
ルスラリーに含まれるＳ ｉ Ｏ，量の５０ｗｔ％を越
えない範囲内にある。Generally, the total amount added is within a range not exceeding 50 wt% of the amount of S i O contained in the silica gel slurry, in terms of S i O amount.
本発明の方法に於いて、シリカゲルスラリーに対するケ
イ酸液の添加を断続的に行う場合には、各回のケイ酸液
添加操作の間に、酸を添加してスラリーのｐＨを７以下
に低下させる操作を介在させることが好ましい、そして
、この操作で使用する酸としては、塩酸、硫酸、硝酸等
の鉱酸、酢酸、シュウ酸、ギ酸等の有機酸を任意に使用
することができる。In the method of the present invention, when the silicic acid liquid is added intermittently to the silica gel slurry, an acid is added between each silicic acid liquid addition operation to lower the pH of the slurry to 7 or less. It is preferable to intervene the operation, and as the acid used in this operation, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, etc., and organic acids such as acetic acid, oxalic acid, formic acid, etc. can be arbitrarily used.
スラリーのｐＨを７以下に低下させる操作を介在させる
ことが、スラリー中のシリカゲルに如何なる作用を及ぼ
すかは、現在のとこ為、必ずしも明らかではない、しか
しながら、スラリーのｐＨを酸性域にシフトさせる操作
を介在させた方が、介在させない場合より、最終的に得
られるシリカ担体の粒子強度が向上する事実から見て、
酸性域へのシフトは、シリカゲル粒子間の結合力増強に
、大いに貢献しているものと推察される。At present, it is not necessarily clear what effect intervening an operation to lower the pH of the slurry to 7 or less will have on the silica gel in the slurry. Judging from the fact that the particle strength of the final silica support is improved when silica is present, compared to when it is not present,
It is presumed that the shift to the acidic region greatly contributes to the enhancement of the bonding force between silica gel particles.
スラリーを酸性域にシフトさせる操作を介在させたか否
かに拘らず、所定量のケイ酸液を添加し終わったシリカ
ゲルスラリーは、常法通り乾燥される。シリカ担体を成
型物として取得したい場合には、必要に応じてスラリー
を脱水後、所望の寸法及び形状に成型してから乾燥する
ことが望ましい。また１球状粒子を取得したい場合には
、スラリーを噴震乾燥することが好ましい。乾燥後は、
空気中で３００〜１１００℃の温度で焼成することによ
り２本発明の目的物たる大細孔容積で高粒子強度の多孔
性シリカ担体を得ることができる。The silica gel slurry to which a predetermined amount of the silicic acid solution has been added is dried in a conventional manner, regardless of whether or not an operation of shifting the slurry to an acidic region is performed. When it is desired to obtain a silica carrier as a molded product, it is desirable to dehydrate the slurry as necessary, mold it into a desired size and shape, and then dry it. Moreover, when it is desired to obtain one spherical particle, it is preferable to spray-dry the slurry. After drying,
By firing in air at a temperature of 300 DEG to 1100 DEG C., a porous silica carrier with a large pore volume and high particle strength, which is the object of the present invention, can be obtained.
このようにして製造されたシリカ担体は、いろいろな用
途に使用できる。例えば、特願昭６０−１１７１９号の
方法によって、平均粒径５μのシリカマイクロビーズを
作ることができる。このシリカマイクロビーズの細孔容
積は１．０〜２．５ｃｃ／ｇと大きいため、これらを液
体クロマトグラフの担体として使用すれば非常に有効で
ある。また同様にタンパク質等の分取用担体などにも使
用できる。さらに、濾過助剤としても有効である。The silica carrier produced in this way can be used for various purposes. For example, silica microbeads with an average particle size of 5 μm can be produced by the method disclosed in Japanese Patent Application No. 11719/1980. Since the pore volume of these silica microbeads is as large as 1.0 to 2.5 cc/g, their use as a carrier for liquid chromatography is very effective. It can also be similarly used as a carrier for fractionating proteins and the like. Furthermore, it is effective as a filter aid.
また、この大きな細孔容積の中に、例えば色素を含浸さ
せれば、色素担体としても利用できる。Furthermore, if the large pore volume is impregnated with, for example, a dye, it can be used as a dye carrier.
色素にて直接蒲鉾に模様を入れると、色素が不必要な所
までにじんで鮮明な模様が得られない欠点がある。しか
し１色素担体を用いて模様を入れると、にじむことがな
いので明確な模様を有するかまぼこを得ることができる
。しかもこの担体の粒径は５μと小さいため１口当たり
に関しても不都合がない。If you directly apply a pattern to kamaboko with dye, the disadvantage is that the dye bleeds into unnecessary areas, making it impossible to obtain a clear pattern. However, if a pattern is created using a single dye carrier, there will be no smudging and it is possible to obtain a kamaboko with a clear pattern. Moreover, since the particle size of this carrier is as small as 5 μm, there is no problem in terms of per-portion.
また１本発明のシリカ担体の細孔に香水を含浸させると
、従来のマイクロビーズに比較して細孔容積が３〜８倍
もあるため、含浸量を増加させることにより、長持ちす
る香水含有シリカ担体を得ることができる。同様にして
、防カビ剤を含浸させれば、効果が大きく、長持ちする
防カビ剤含有シリカマイクロビーズを得ることができる
。In addition, when the pores of the silica carrier of the present invention are impregnated with perfume, the pore volume is 3 to 8 times that of conventional microbeads. A carrier can be obtained. Similarly, by impregnating them with a fungicide, it is possible to obtain fungicide-containing silica microbeads that are highly effective and last a long time.
さらにまた、本発明のシリカ担体を噴霧乾燥によって平
均粒径６０〜１００μの球状粒子とし。Furthermore, the silica carrier of the present invention is formed into spherical particles with an average particle size of 60 to 100 μm by spray drying.
これを所定の温度で焼成することにより、触媒担体とす
ることも可能である０例えばこの種の触媒担体に、硫酸
バナジルと硫酸カリウムを含浸させて、５００℃で焼成
すれば、無水フタル酸触媒を製造することができる。By firing this at a predetermined temperature, it is possible to use it as a catalyst carrier. For example, if this type of catalyst carrier is impregnated with vanadyl sulfate and potassium sulfate and fired at 500°C, a phthalic anhydride catalyst can be obtained. can be manufactured.
上記した以外にも、本発明の方法で製造されるシリカ担
体は、細孔容積が大きく、粒子強度が高いことから、様
々な用途に使用できる可能性を有している。In addition to the above, the silica carrier produced by the method of the present invention has a large pore volume and high particle strength, so it has the possibility of being used for various purposes.
［実 施 例コ
実施例１
内容積５０ｆｉのスチームジャケット付きタンクに、Ｓ
ｉｎ２濃度２０％のシリカゾル２０ｋｇを収め、これを
攪拌しつつ濃度６３％の硝酸を加えてｐＨを０．７５と
した後、攪拌を続けながら濃度１５％のアンモニア水を
加えてｐＨを９．５とすることにより、シリカヒドロゲ
ルを得た。[Example Example 1] In a steam jacketed tank with an internal volume of 50fi,
Put 20 kg of silica sol with a concentration of 20% in2 in it, add nitric acid with a concentration of 63% while stirring to bring the pH to 0.75, and then add aqueous ammonia with a concentration of 15% while stirring to bring the pH to 9.5. By doing so, a silica hydrogel was obtained.
このゲルを高速攪拌機に供給してＳｉｎ、濃度１６％の
シリカゲルスラリーを調製し、これを８０℃に加温後、
濃度１５％のアンモニア水を加えてｐＨを９．５に調節
し、これにＳｉＯ□濃度５％。This gel was fed to a high-speed stirrer to prepare a silica gel slurry with a concentration of 16%, and after heating it to 80°C,
Ammonia water with a concentration of 15% was added to adjust the pH to 9.5, and to this was added a SiO□ concentration of 5%.
ｐＨ２，８３のケイ酸液を１８．５ｇ／分の速度で、総
量８８８０ｇ添加してスラリー（Ｘ）を得た。A total amount of 8880 g of a silicic acid solution having a pH of 2.83 was added at a rate of 18.5 g/min to obtain a slurry (X).
前記のケイ酸液はＳ ｉ Ｏ，濃度５％の水ガラスを陽
イオン交換樹脂で処理して調製したものであり、ケイ酸
液の添加に際しては、濃度１５％のアンモニア水を同時
に添加すると共に、加温を継続して常時スラリーのｐＨ
を９．５に、液温を８０℃に保持した。The silicic acid solution mentioned above was prepared by treating water glass with a concentration of 5% with a cation exchange resin, and when adding the silicic acid solution, aqueous ammonia with a concentration of 15% was added at the same time. , keep the pH of the slurry constant by continuing heating.
was maintained at 9.5 and the liquid temperature at 80°C.
上記のようにして得られたスラリー（Ｘ）を噴震乾燥し
１次いで４００℃で３時間焼成してシリカ担体を製造し
た。この担体の水銀圧入法による細孔容積は１．６ｃｃ
／ｇ、 Ｂ Ｅ Ｔ法による表面積は１５５ｒｒｒ／ｇ
であった。また、下記のような粒子強度評価法による粒
子強度は、 １１．９であった。The slurry (X) obtained as described above was spun-dried and then calcined at 400° C. for 3 hours to produce a silica carrier. The pore volume of this carrier by mercury intrusion method is 1.6cc.
/g, surface area by BET method is 155rrr/g
Met. Further, the particle strength according to the particle strength evaluation method described below was 11.9.
亘土伎皮■負蒸
シリカ担体を目開き４４μの篩にかけて篩上の試料Ｌｏ
ｇを採取する。この試料を５０ｇの水と共に１００ｃｃ
のビーカーに入れて軽く攪拌した後、出力３００Ｗ、
１９．５ｋ Ｈｚの超音波発振器の先端をビーカーに入
れ、１０分間粉砕する。次いで、ビーカーの内容物を目
開き４４μの篩にあけ、篩上を水で洗い、篩下金量を１
１０℃で１６時間乾燥する。この乾燥物を秤量し、次式
に従って粒子強度を算出した。Wadokipi ■ Pass the negative vaporized silica carrier through a 44μ sieve and sample Lo on the sieve.
Collect g. 100cc of this sample with 50g of water
After putting it in a beaker and stirring it lightly, the output is 300W,
Place the tip of a 19.5 kHz ultrasonic oscillator in the beaker and triturate for 10 minutes. Next, pour the contents of the beaker into a 44μ sieve, wash the top of the sieve with water, and reduce the amount of gold under the sieve to 1.
Dry at 10°C for 16 hours. This dried material was weighed and the particle strength was calculated according to the following formula.
粒子強度＝ 廿りへ占へ−”ｘｔｏ。Particle strength = 廿にしえへ-”xto.
実施例２
実施例１と同様にして得られたスラリー（Ｘ）を８０℃
に保持しながら、濃度６３％の硝酸を加えてｐＨを６．
１とした。この状態で１０分間攪拌した後、濃度１５％
のアンモニア水をこれに加えてｐＨを再度９．５とした
。Example 2 Slurry (X) obtained in the same manner as Example 1 was heated to 80°C.
While maintaining the pH at 6.3%, add 63% nitric acid to bring the pH to 6.
It was set to 1. After stirring in this state for 10 minutes, the concentration was 15%.
of ammonia water was added thereto to adjust the pH to 9.5 again.
このスラリーにＳｉｎ、濃度５％のケイ酸液を実施例１
と同様な条件で添加した後（但し。Example 1 Adding Sin to this slurry, silicic acid solution with a concentration of 5%
After adding under the same conditions as (however.
添加総量は２３４０ｇとした）、これを噴霧乾燥し、さ
らに４００℃で３時間焼成してシリカ担体を得た。この
シリカ担体の水銀圧入法による細孔容積は２．３３ｃｃ
／ｇ、平均細孔直径は７００人、表面積は１６１ｍ／ｇ
であった。また粒子強度は２６．５であった・
比較例１
実施例１と同様にして得たシリカヒドロゲルスラリーを
、液温８０℃、ｐＨ９，５の条件で８時間熟成した後、
これを噴震乾燥し、さらに実施例１と同様な条件で焼成
してシリカ担体を得た。The total amount added was 2340 g), which was spray-dried and further calcined at 400° C. for 3 hours to obtain a silica carrier. The pore volume of this silica carrier by mercury intrusion method is 2.33cc.
/g, average pore diameter is 700 people, surface area is 161m/g
Met. The particle strength was 26.5.Comparative Example 1 After aging the silica hydrogel slurry obtained in the same manner as in Example 1 for 8 hours at a liquid temperature of 80°C and a pH of 9.5,
This was spun-dried and then fired under the same conditions as in Example 1 to obtain a silica carrier.
このシリカ担体の水銀圧入法による細孔容積は０．９ｃ
ｃ／ｇ、平均細孔直径は１７０人１表面積は１２２ｄ１
ｇであった。また粒子強度は９１．２であった。The pore volume of this silica support by mercury intrusion method is 0.9c.
c/g, average pore diameter is 170 people 1 surface area is 122 d1
It was g. Moreover, the particle strength was 91.2.
比較例２
シリカヒドロゲルスラリーの熟成時間を８時間から１０
．１時間に変更した以外は比較例１と同様にしてシリカ
担体を得た。このシリカ担体の水銀圧入法による細孔容
積は０．９ｃｃ／ｇ、表面積は１２０ｎ？／ｇ、粒子強
度は８９．５であった。Comparative Example 2 Aging time of silica hydrogel slurry ranged from 8 hours to 10 hours
．． A silica carrier was obtained in the same manner as in Comparative Example 1 except that the time was changed to 1 hour. The pore volume of this silica carrier by mercury intrusion method is 0.9 cc/g, and the surface area is 120 n? /g, and the particle strength was 89.5.
実施例３
実施例１に於けるケイ酸液の添加総量だけを変更し、４
４４０ｇとした以外は実施例１と全く同様にしてシリカ
担体を得た。この担体の水銀圧入法による細孔容積は１
．２５ｃｃ／ｇ、平均細孔直径は１９０人、表面積は１
５１ｒｒｒ／ｇであった。また粒子強度は１３．０であ
った。Example 3 Only the total amount of silicic acid liquid added in Example 1 was changed, and 4
A silica carrier was obtained in exactly the same manner as in Example 1 except that the amount was changed to 440 g. The pore volume of this carrier by mercury intrusion method is 1
．． 25cc/g, average pore diameter 190, surface area 1
It was 51rrr/g. Moreover, the particle strength was 13.0.
実施例４
実施例１に於けるケイ酸液の添加速度だけを変更し、７
５ｇ１分とした以外は実施例１と全く同様にしてシリカ
担体を得た。この担体の水銀圧入法による細孔容積は１
．５２ｃｃ／ｇ、平均細孔直径は２０５人、表面積は１
４８ｒｒｒ／ｇであった。また粒子強度は１１．４であ
った。Example 4 Only the addition rate of the silicic acid liquid in Example 1 was changed, and 7
A silica carrier was obtained in exactly the same manner as in Example 1, except that the amount was changed to 5 g for 1 minute. The pore volume of this carrier by mercury intrusion method is 1
．． 52cc/g, average pore diameter is 205 people, surface area is 1
It was 48rrr/g. Moreover, the particle strength was 11.4.
実施例５
実施例１に於けるケイ酸液の添加総量だけを変更し、７
２０００ｇとした以外は実施例１と全く同様にしてシリ
カ担体を得た。この担体の水銀圧入法による細孔容積は
１．７１ｃｃ／ｇ、平均細孔直径は２２０人、表面積は
１４７ｒｒｆ’／ｇであった。また粒子強度は２．１で
あった。Example 5 Only the total amount of silicic acid liquid added in Example 1 was changed, and 7
A silica carrier was obtained in exactly the same manner as in Example 1 except that the amount was 2000 g. The pore volume of this carrier by mercury porosimetry was 1.71 cc/g, the average pore diameter was 220 cc/g, and the surface area was 147 rrf'/g. Moreover, the particle strength was 2.1.
実施例６
実施例１に於けるｐＨを８．６とした以外は実施例１と
全く同様にしてシリカ担体を得た。この担体の水銀圧入
法による細孔容積は１．５５ｃｃ／ｇ、平均細孔直径は
２００人１表面積は１５８ｒｒｒ／ｇであった。また粒
子強度は１４．７であった。Example 6 A silica carrier was obtained in exactly the same manner as in Example 1 except that the pH in Example 1 was changed to 8.6. The pore volume of this carrier by mercury intrusion method was 1.55 cc/g, and the average pore diameter was 158 rrr/g per 200 people. Moreover, the particle strength was 14.7.
比較例３
実施例１に於けるｐＨを８．６とした以外は実施例１と
全く同様にしてシリカ担体を得た。この担体の水銀圧入
法による細孔容積は０．９２ｃｃ／ｇ、平均細孔直径は
１７０人、表面積は１５０＋ｖ？／ｇであった。また粒
子強度は９０．８であった。Comparative Example 3 A silica carrier was obtained in exactly the same manner as in Example 1 except that the pH in Example 1 was changed to 8.6. The pore volume of this carrier by mercury intrusion method is 0.92 cc/g, the average pore diameter is 170, and the surface area is 150+v? /g. Moreover, the particle strength was 90.8.
実施例７
実施例１に於ける温度を５３℃とした以外は実施例１と
全く同様にしてシリカ担体を得た。この担体の水銀圧入
法による細孔容積は１．５３ｃｃ／ｇ、平均細孔直径は
１９５人、表面積は１５３ｒｒｒ／ｇであった。また粒
子強度は１５．１であった。Example 7 A silica carrier was obtained in exactly the same manner as in Example 1 except that the temperature in Example 1 was changed to 53°C. The pore volume of this carrier by mercury intrusion method was 1.53 cc/g, the average pore diameter was 195 mm, and the surface area was 153 rrr/g. Moreover, the particle strength was 15.1.
比較例４
実施例１に於ける温度を３５℃とした以外は実施例１と
全く同様にしてシリカ担体を得た。この担体の水銀圧入
法による細孔容積はＱ、８７ｃｃ／ｇ、平均細孔直径は
１４０人１表面積は１５５ｒｒｒ／ｇであった。また粒
子強度は８７．２であった。Comparative Example 4 A silica carrier was obtained in the same manner as in Example 1 except that the temperature in Example 1 was changed to 35°C. The pore volume of this carrier measured by mercury intrusion method was Q, 87 cc/g, and the average pore diameter was 140 people/155 rrr/g. Moreover, the particle strength was 87.2.
実施例８
実施例１に於けるシリカゲルスラリーのＳｉＯ２濃度１
６％を、５５％に増大させた以外は実施例１と全く同様
にしてシリカ担体を得た。この担体の水銀圧入法による
細孔容積は１．５２ｃｃ／ｇ。Example 8 SiO2 concentration 1 of silica gel slurry in Example 1
A silica carrier was obtained in exactly the same manner as in Example 1 except that 6% was increased to 55%. The pore volume of this carrier by mercury intrusion method was 1.52 cc/g.
平均細孔直径は２２０人１表面積は１５７ｒｒｆ／ｇで
あった。また粒子強度は１２．４であった。The average pore diameter was 220 people and the surface area was 157 rrf/g. Moreover, the particle strength was 12.4.
実施例９
スラリー（Ｘ）のｐＨを酸性域にシフトさせた実施例２
に於いて、ケイ酸液の添加総量を２３４０ｇから３８０
００ｇに変更した以外は実施例２と全く同様にしてシリ
カ担体を得た。この担体の水銀圧入法による細孔容積は
２．４５ｃｃ／ｇ、平均細孔直径は８５０人１表面積は
１５２ｎ？／ｇであった。また粒子強度は４．６であっ
た。Example 9 Example 2 in which the pH of slurry (X) was shifted to the acidic range
In this case, the total amount of silicic acid liquid added was changed from 2340g to 380g.
A silica carrier was obtained in exactly the same manner as in Example 2 except that the amount was changed to 00 g. The pore volume of this carrier as measured by mercury intrusion method is 2.45 cc/g, and the average pore diameter is 850 people.The surface area is 152 n? /g. Moreover, the particle strength was 4.6.
応用例
二酸化クロム１ｇをイオン交換水２００■ａに溶解し、
この溶液に実施例３で得られたシリカ担体５０ｇを浸漬
して室温にて１時間攪拌した。次いで、このスラリーを
湯浴上で加熱し、水を除去後、１２０℃で１０時間減圧
乾燥した。しかる後、この乾燥物を酸素気流下、８００
℃で５時間焼成し、固体触媒を得た。この固体触媒はク
ロムを１％ｆｔ％含有し、このものを窒素雰囲気下、室
温にてしばらく保存した。Application example: Dissolve 1 g of chromium dioxide in 200 μa of ion-exchanged water,
50 g of the silica carrier obtained in Example 3 was immersed in this solution and stirred at room temperature for 1 hour. Next, this slurry was heated on a hot water bath to remove water, and then dried under reduced pressure at 120° C. for 10 hours. After that, this dried product was heated under an oxygen stream for 800 min.
It was calcined at ℃ for 5 hours to obtain a solid catalyst. This solid catalyst contained 1% ft% of chromium and was stored for a while at room temperature under a nitrogen atmosphere.
次に、この固体触媒を使用して下記のような重合を行っ
た。Next, the following polymerization was performed using this solid catalyst.
窒素置換し、攪拌機を付した内容量２Ｑのステンレスス
チール製オートクレーブに、ＩＱのヘキサン、１ミリモ
ルのジエチルアルミニウムエトキシド及び上記の固体触
媒５００■を加えて、８０℃に加温した。エチレン分圧
が１０ｋｇ／ｃｄとなるようにエチレンをオートクレー
ブに連続的に供給し、１時間重合を行った。しかる後、
オートクレーブを開放して溶媒を除去し、重合物を乾燥
して嵩密度０．４０ｇ／ｄの真球状ポリエチレンを得た
。IQ hexane, 1 mmol of diethylaluminum ethoxide, and 500 μm of the above solid catalyst were added to a stainless steel autoclave with an internal capacity of 2Q, which was purged with nitrogen and equipped with a stirrer, and heated to 80°C. Ethylene was continuously supplied to the autoclave so that the ethylene partial pressure was 10 kg/cd, and polymerization was carried out for 1 hour. After that,
The autoclave was opened to remove the solvent, and the polymer was dried to obtain true spherical polyethylene having a bulk density of 0.40 g/d.
［発明の効果］
本発明の方法で得られるシリカ担体は、細孔容積が１．
０〜２．５ｃｃ／ｇ程度で、平均細孔直径が１００〜１
０００人の範囲にあり、しかも粒子強度が大きいため、
各種担体として極めて好適である。[Effects of the Invention] The silica support obtained by the method of the present invention has a pore volume of 1.
Approximately 0 to 2.5 cc/g, with an average pore diameter of 100 to 1
000 people, and because the particle strength is large,
It is extremely suitable as a variety of carriers.
例えば、液体クロマトグラフの担体、蒲鉾に模様を描く
際などに使用される色素担体、香水を含有させる担体な
どとして使用できる外、濾過助剤としても有用である。For example, it can be used as a carrier for liquid chromatography, a dye carrier used for drawing patterns on kamaboko, a carrier for containing perfume, and is also useful as a filter aid.
Claims (1)
カゲルスラリーに、アルカリ水溶液を添加してスラリー
のｐＨを８．５以上に保持しつつ、液温を５０℃以上に
保持しながら、１分間当りのケイ酸液の添加量がＳｉＯ
＿２量に換算して、前記シリカゲルスラリーに含まれる
ＳｉＯ＿２量の１／１０００以下になる添加速度で、且
つケイ酸液の添加総量がＳｉＯ＿２量に換算して、前記
シリカゲルスラリーに含まれるＳｉＯ＿２量の５０ｗｔ
％を越えない範囲内で、ケイ酸液を前記のシリカゲルス
ラリーに添加し、次いでこの混合スラリーを乾燥して焼
成することからなる多孔性シリカ担体の製造法。 ２、ケイ酸液の濃度がＳｉＯ＿２として８ｗｔ％以下で
ある特許請求の範囲第１項記載の方法。 ３、ＳｉＯ＿２濃度が１〜６０ｗｔ％の範囲にあるシリ
カゲルスラリーに、アルカリ水溶液を添加してスラリー
のｐＨを８．５以上に保持しつつ、液温を５０℃以上に
保持しながら、１分間当りのケイ酸液の添加量がＳｉＯ
＿２量に換算して、前記シリカゲルスラリーに含まれる
ＳｉＯ＿２量の１／１０００以下になる添加速度で、且
つケイ酸液の添加総量がＳｉＯ＿２量に換算して、前記
シリカゲルスラリーに含まれるＳｉＯ＿２量の５０ｗｔ
％を越えない範囲内で、ケイ酸液を前記のシリカゲルス
ラリーに添加し、次いで（ａ）ケイ酸液が添加されたシ
リカゲルスラリーに酸を加えてｐＨを７以下に低下 させる操作、 （ｂ）操作（ａ）の後、アルカリ水溶液を添加してスラ
リーのｐＨを８．５以上に保持 しつつ、液温を５０℃以上に保持しなが ら、１分間当りのケイ酸液の添加量が ＳｉＯ＿２量に換算して、前記ケイ酸液 が添加されたシリカゲルスラリーに含 まれる総ＳｉＯ＿２量の１／１０００以下になる添加速
度で、且つケイ酸液の添加総 量がＳｉＯ＿２量に換算して、前記ケイ 酸液が添加されたシリカゲルスラリー に含まれる総ＳｉＯ＿２量の５０ｗｔ％を越えない範囲
内で、ケイ酸液をシリカゲ ルスラリーに添加する操作、 を１回又は複数回繰り返し、得られた混合スラリーを乾
燥して焼成することからなる多孔性シリカ担体の製造法
。 ４、ケイ酸液の濃度がＳｉＯ＿２として８ｗｔ％以下で
ある特許請求の範囲第３項記載の方法。[Claims] 1. Adding an alkaline aqueous solution to a silica gel slurry with a SiO_2 concentration in the range of 1 to 60 wt% to maintain the pH of the slurry at 8.5 or higher and the liquid temperature at 50°C or higher. While the amount of silicic acid solution added per minute is
The addition rate is such that the amount of SiO_2 contained in the silica gel slurry is 1/1000 or less in terms of the amount of SiO_2 contained in the silica gel slurry, and the total amount of silicic acid liquid added is 50wt
A method for producing a porous silica carrier, which comprises adding silicic acid liquid to the silica gel slurry in an amount not exceeding %, and then drying and calcining the mixed slurry. 2. The method according to claim 1, wherein the concentration of the silicic acid solution is 8 wt% or less as SiO_2. 3. Add an alkaline aqueous solution to a silica gel slurry with a SiO_2 concentration in the range of 1 to 60 wt% to maintain the pH of the slurry at 8.5 or higher and the liquid temperature at 50°C or higher for 1 minute. The amount of silicic acid added is SiO
The addition rate is such that the amount of SiO_2 contained in the silica gel slurry is 1/1000 or less in terms of the amount of SiO_2 contained in the silica gel slurry, and the total amount of silicic acid liquid added is 50wt
Adding a silicic acid liquid to the silica gel slurry within a range not exceeding %, and then (a) adding an acid to the silica gel slurry to which the silicic acid liquid has been added to lower the pH to 7 or less, (b) After operation (a), add an alkaline aqueous solution to maintain the pH of the slurry at 8.5 or higher, maintain the liquid temperature at 50°C or higher, and increase the amount of silicic acid solution added per minute by SiO_2 amount. The silicic acid is added at a rate that is 1/1000 or less of the total amount of SiO_2 contained in the silica gel slurry to which the silicic acid liquid is added, and the total amount of the silicic acid liquid is converted to the amount of SiO_2. The operation of adding a silicic acid solution to a silica gel slurry within a range not exceeding 50 wt% of the total amount of SiO_2 contained in the silica gel slurry to which the solution has been added is repeated one or more times, and the resulting mixed slurry is dried. A method for producing a porous silica carrier, which comprises firing the porous silica carrier. 4. The method according to claim 3, wherein the concentration of the silicic acid solution is 8 wt% or less as SiO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61093660A JPH0631173B2 (en) | 1986-04-23 | 1986-04-23 | Method for producing porous silica carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61093660A JPH0631173B2 (en) | 1986-04-23 | 1986-04-23 | Method for producing porous silica carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62252378A true JPS62252378A (en) | 1987-11-04 |
| JPH0631173B2 JPH0631173B2 (en) | 1994-04-27 |
Family
ID=14088545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61093660A Expired - Fee Related JPH0631173B2 (en) | 1986-04-23 | 1986-04-23 | Method for producing porous silica carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0631173B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019049839A1 (en) | 2017-09-05 | 2019-03-14 | Showa Denko K.K. | Method for producing silica carrier, and silica carrier |
| US10919836B2 (en) | 2017-09-05 | 2021-02-16 | Showa Denko K.K. | Production method of aliphatic carboxylic acid ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5085608A (en) * | 1973-11-30 | 1975-07-10 |
-
1986
- 1986-04-23 JP JP61093660A patent/JPH0631173B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5085608A (en) * | 1973-11-30 | 1975-07-10 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019049839A1 (en) | 2017-09-05 | 2019-03-14 | Showa Denko K.K. | Method for producing silica carrier, and silica carrier |
| US10919836B2 (en) | 2017-09-05 | 2021-02-16 | Showa Denko K.K. | Production method of aliphatic carboxylic acid ester |
| US11890592B2 (en) | 2017-09-05 | 2024-02-06 | Resonac Corporation | Method for producing silica carrier, and silica carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0631173B2 (en) | 1994-04-27 |
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