JP6161966B2 - Mixer and method for producing metal oxide sol using the same - Google Patents
Mixer and method for producing metal oxide sol using the same Download PDFInfo
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- JP6161966B2 JP6161966B2 JP2013122429A JP2013122429A JP6161966B2 JP 6161966 B2 JP6161966 B2 JP 6161966B2 JP 2013122429 A JP2013122429 A JP 2013122429A JP 2013122429 A JP2013122429 A JP 2013122429A JP 6161966 B2 JP6161966 B2 JP 6161966B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 title description 21
- 150000004706 metal oxides Chemical class 0.000 title description 21
- 150000007522 mineralic acids Chemical class 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 24
- 230000003068 static effect Effects 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 5
- 125000005623 silicon oxoacid group Chemical group 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 11
- -1 oxoacid alkali metal Chemical class 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance 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
- 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 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Description
本発明は、新規な金属アルカリ水溶液と無機酸との混合器、および、この混合器を用いた金属酸化物ゾルの製造方法に関する。詳しくは、対向した２つの原料供給管と該原料供給管の結合部に連結した排出管とを有する金属アルカリ水溶液と無機酸との混合器において、前記排出管の途中に静止型混合器を設けることによる、低い圧力損失で高い混合強度が得られる混合器、および、この混合器を用いた金属酸化物ゾルの製造方法に関する。 The present invention relates to a novel metal alkali aqueous solution and inorganic acid mixer, and a method for producing a metal oxide sol using this mixer. Specifically, in a mixer of an aqueous alkali metal solution and an inorganic acid having two opposing raw material supply pipes and a discharge pipe connected to a joint of the raw material supply pipes, a static mixer is provided in the middle of the discharge pipe The present invention relates to a mixer capable of obtaining a high mixing strength with a low pressure loss, and a method for producing a metal oxide sol using the mixer.
金属酸化物ゾルは、ゾル・ゲル転移、ゲル化物の高い比表面積、高耐熱性等の特性を有する物質であり、工業的な利用が進められている。例えば、シリカゾルは水処理剤や製紙用歩留まり剤等、アルミナゾルは触媒単体や帯電防止剤等、として有用に用いられている。 A metal oxide sol is a substance having properties such as sol-gel transition, high specific surface area of a gelled product, and high heat resistance, and is being industrially used. For example, silica sol is useful as a water treatment agent, a papermaking retention agent, and the like, and alumina sol is useful as a catalyst alone or an antistatic agent.
金属オキソ酸アルカリ金属塩水溶液を用いて金属酸化物ゾルを製造する方法としては、塩酸、硫酸等の無機酸により中和する方法か、あるいは対イオンがＨ＋とされている陽イオン交換樹脂（以下、「酸型陽イオン交換樹脂」）を用いる方法によりアルカリ金属を水素原子へと置換して、金属酸化物ゾルを得る方法が挙げられる。 As a method for producing a metal oxide sol using an aqueous metal oxoacid alkali metal salt solution, a method of neutralizing with an inorganic acid such as hydrochloric acid or sulfuric acid, or a cation exchange resin in which the counter ion is H + ( Hereinafter, a method of obtaining a metal oxide sol by substituting an alkali metal with a hydrogen atom by a method using an “acid type cation exchange resin”).
これらの製造方法の中で、酸により中和することによって金属酸化物ゾルを製造する方法は、製造コストが抑制できることから工業的に有用に用いられている。 Among these production methods, a method for producing a metal oxide sol by neutralizing with an acid is industrially useful because production costs can be suppressed.
酸により中和する製造方法としては、金属オキソ酸アルカリ金属塩水溶液として珪酸ソーダ水溶液を用い、金属酸化物ゾルであるシリカゾルを製造する方法として、Ｙ字管型の混合器を用いてそれぞれの溶液を高速で衝突させ、衝突後の混合液を流速１ｍ／秒以上の流速で流出させることで、均質なシリカゾルを製造する方法が提案されている。（特許文献１、２等）
金属酸化物ゾルを製造する際、そのｐＨは重要である。なぜならば、ゾル・ゲル転移にかかる時間、ゲル化物の比表面積、等の物性が大きく変動するからである。そのため、均一でないｐＨで製造された場合、ｐＨの調整を行うための設備を設置し、ｐＨ調整剤にてｐＨの調整を行う後工程を要することとなる。よって、ｐＨ調整をバッチ運転にて行うためのタンクやポンプ等の設備が必要となり、かつ、運転制御についても連続運転と比較して煩雑となる。また、原料混合後に短時間でゾル・ゲル転移のような状態変化を生じる物質の場合、後工程でのｐＨ調整は不可能となる。
As a production method for neutralizing with an acid, a sodium silicate aqueous solution is used as the metal oxo acid alkali metal salt aqueous solution, and as a method for producing a silica sol which is a metal oxide sol, each solution is prepared using a Y-shaped mixer. Has been proposed to produce a homogeneous silica sol by causing the mixture to collide at a high speed and causing the mixed solution after the collision to flow out at a flow rate of 1 m / sec or more. (
The pH is important when producing the metal oxide sol. This is because the physical properties such as the time required for the sol-gel transition and the specific surface area of the gelled product greatly vary. Therefore, when it manufactures by non-uniform | heterogenous pH, the post process which installs the equipment for adjusting pH and adjusts pH with a pH adjuster will be needed. Therefore, facilities such as a tank and a pump for performing pH adjustment in batch operation are required, and operation control is complicated as compared with continuous operation. In addition, in the case of a substance that causes a state change such as sol-gel transition in a short time after mixing raw materials, pH adjustment in a subsequent process becomes impossible.
このように、連続的に均一なｐＨで製造することにより、後工程にて所望のｐＨへ調整する調整設備を省略することができ、かつ連続運転が可能となる。特に、原料混合後に短時間でゲル化や固形化する物質については、ｐＨを調整する時間が短いことから、連続的に均一なｐＨで製造することは非常に有用な製造方法である。 Thus, by continuously producing at a uniform pH, it is possible to omit the adjustment equipment for adjusting to a desired pH in a subsequent process, and continuous operation is possible. In particular, for a substance that gels or solidifies in a short time after mixing raw materials, it is a very useful production method to produce continuously at a uniform pH because the time for adjusting the pH is short.
また、金属酸化物ゾルの均一なｐＨでの連続製造を目的として、二液混合後の排出管の途中にｐＨ計を設け、該ｐＨメーターの指示値から金属オキソ酸アルカリ金属塩水溶液および／又は無機酸の供給量を調節する方法を既に提案した。（特願２０１３−１０３１０７号） In addition, for the purpose of continuous production of the metal oxide sol at a uniform pH, a pH meter is provided in the middle of the discharge pipe after mixing the two liquids, and the alkali metal salt of metal oxoacid and / or the A method for adjusting the supply of inorganic acid has already been proposed. (Japanese Patent Application No. 2013-103107)
しかしながら、排出管の途中にｐＨメーターを設ける方法で中性に近い（例えばｐＨ５）均一なｐＨの金属酸化物ゾルを連続的に製造しようとした場合、二液の混合効果を高めるために衝突時の流速を１０ｍ／秒としても十分な混合が得られないことが分かった。なお、一般的に二液の衝突速度が高い方が高い混合効果を得られるが、ある程度以上では原料を加速するために必要なデメリットが、混合効果のメリットを上回ってしまう。 However, when trying to continuously produce a metal oxide sol with a uniform pH near the neutrality (for example, pH 5) by providing a pH meter in the middle of the discharge pipe, in order to enhance the mixing effect of the two liquids, It was found that sufficient mixing could not be obtained even at a flow rate of 10 m / sec. In general, the higher the collision speed of the two liquids, the higher the mixing effect can be obtained. However, the demerit necessary for accelerating the raw material exceeds the merit of the mixing effect above a certain level.
従って、排出管を通る液が局所的に酸やアルカリになり、二液混合後の排出管の途中にｐＨ計を設けた場合、該ｐＨ計の指示値が安定せず、また仮に安定していたとしても一定時間の間に得られた金属酸化物ゾルをまとめてｐＨを測定した場合、排出管途中に設けたｐＨ計と値が異なり、ｐＨが目的範囲から外れた金属酸化物ゾルが排出され、さらに、均一なｐＨでの連続製造を目的として排出管の途中に設けたｐＨメーターの値から金属オキソ酸アルカリ金属塩水溶液および／又は無機酸の供給量を調整する制御を行おうとした場合は供給量の調整以外の事由でｐＨが変動するため制御が成り立たず、目的とする均一なｐＨの金属酸化物ゾルを連続的に製造することができない問題があった。 Therefore, when the liquid passing through the discharge pipe becomes locally acidic or alkaline, and a pH meter is provided in the middle of the discharge pipe after mixing the two liquids, the indicated value of the pH meter is not stable and is temporarily stable. Even if the pH of the metal oxide sols obtained during a certain period of time is measured together, the value is different from the pH meter installed in the middle of the discharge pipe, and the metal oxide sol with a pH outside the target range is discharged. In addition, for the purpose of continuous production at a uniform pH, the control of adjusting the supply amount of the metal oxoacid alkali metal salt aqueous solution and / or inorganic acid from the value of the pH meter provided in the middle of the discharge pipe However, since the pH fluctuates due to reasons other than the adjustment of the supply amount, the control cannot be realized, and there is a problem that the desired metal oxide sol having a uniform pH cannot be continuously produced.
本発明者らは、上記の課題を解決するために鋭意検討を重ねた結果、金属アルカリ水溶液と無機酸が合流する合流部に連結した排出管の途中に静止型混合器と該静止型混合器の下流にｐＨメーターとを設けることにより上記課題が解決することを見いだした。即ち、二液の衝突混合における混合が不十分であっても静止型混合器により十分に混合が行われることで、前記排出管途中における静止型混合器の下流に設置したｐＨメーターの指示値の変動が極めて小さくなり、また、一定時間の間に排出された金属酸化物ゾルをまとめてｐＨを測定した値と同じとなる。よって、ｐＨが目的範囲から外れた金属アルカリと無機酸の混合物が排出されることが無く、ｐＨメーターの値から金属アルカリおよび／又は無機酸の供給量を調整する制御も問題なく行えることを見出し、本発明を完成させるに至った。
As a result of intensive studies in order to solve the above problems, the present inventors have found that a static mixer and the static mixer are disposed in the middle of a discharge pipe connected to a merging portion where a metal alkali aqueous solution and an inorganic acid merge . It has been found that the above-mentioned problems can be solved by providing a pH meter downstream of the above. That is, even if the mixing in the two-liquid collision mixing is insufficient, the mixing is sufficiently performed by the static mixer, so that the indication value of the pH meter installed downstream of the static mixer in the middle of the discharge pipe The fluctuation is extremely small, and is the same as the value obtained by measuring the pH of the metal oxide sols discharged during a certain time. Therefore, it has been found that a mixture of a metal alkali and an inorganic acid whose pH is out of the target range is not discharged, and that the control of adjusting the supply amount of the metal alkali and / or inorganic acid from the value of the pH meter can be performed without any problem. The present invention has been completed.
即ち本発明は、１５〜１８０°の角度で対向した２つの原料供給管と該原料供給管の結合部に連結した排出管とを有する金属アルカリ水溶液と無機酸との混合器からなる金属酸化物ゾルの反応装置において、前記排出管の途中に静止型混合器と該静止型混合器の下流にｐＨメーターとを設けたことを特徴とする金属酸化物ゾルの反応装置である。
That is, the present invention provides a metal oxide comprising a mixture of an aqueous alkali metal solution and an inorganic acid having two raw material supply pipes opposed at an angle of 15 to 180 ° and a discharge pipe connected to a joint portion of the raw material supply pipes . In the sol reaction apparatus , the metal oxide sol reaction apparatus is characterized in that a static mixer is provided in the middle of the discharge pipe, and a pH meter is provided downstream of the static mixer .
本発明の方法によれば、金属アルカリ水溶液と無機酸を混合する混合器において衝突混合による混合が不十分であっても静止型混合器により混合が十分行われ、よって前記排出管から排出される反応液（ゾル）のｐＨ値の変動が極めて小さくなる。 According to the method of the present invention, even if the mixing by collision mixing is insufficient in the mixer for mixing the metal alkali aqueous solution and the inorganic acid, the mixing is sufficiently performed by the static mixer, and is thus discharged from the discharge pipe. The fluctuation of the pH value of the reaction liquid (sol) becomes extremely small.
以下、本発明についてさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明に用いる混合器としては、基本的には２つの原料供給管が合流し、該合流部にて１つの排出管と連結し、前記排出管の途中に静止型混合器を設けてなる構造を有する。 The mixer used in the present invention basically has a structure in which two raw material supply pipes are joined, connected to one discharge pipe at the joining section, and a static mixer is provided in the middle of the discharge pipe. Have
図１に本発明に使用する混合器の一例を示す。 FIG. 1 shows an example of a mixer used in the present invention.
図１に示すように、この混合器は、金属アルカリ水溶液または無機酸が供給される原料供給管１，１’が合流部３にて結合し、該結合部３にて排出管２が連結しており、金属アルカリ水溶液と無機酸との反応生成物は、該排出管の途中に設置された静止型混合器５を通過した後に混合装置から排出される。
As shown in FIG. 1, in this mixer, raw material supply pipes 1 and 1 ′ to which a metal alkali aqueous solution or an inorganic acid is supplied are coupled at a junction 3 and a
当該原料供給管１，１’は、金属アルカリ水溶液と無機酸とを衝突させるために１５〜１８０°の角度で対向して設けられている（図１では９０°である）。この角度は好ましくは９０〜１５０°である。 The raw material supply pipes 1, 1 ′ are provided to face each other at an angle of 15 to 180 ° (90 ° in FIG. 1) in order to cause the metal alkali aqueous solution and the inorganic acid to collide with each other. This angle is preferably 90 to 150 °.
当該原料供給管１，１’には必要に応じ、二液の衝突混合における混合強度を調整することを目的として、原料供給管１，１’において原料の流速を調整するための絞り部を設けたものを使用することも可能である。 The raw material supply pipes 1, 1 ′ are provided with a throttle for adjusting the flow rate of the raw materials in the raw material supply pipes 1, 1 ′ for the purpose of adjusting the mixing strength in the two-liquid collision mixing, as necessary. It is also possible to use
本発明に用いる静止型混合器は、十分な混合に必要となる圧力損失が小さいものであれば公知のものが特に限定されることなく採用でき、例えば株式会社ノリタケ製のスタティックミキサー、株式会社ナノクス製のラモンドナノミキサー、株式会社フジキン製の混合君、シンユー技研株式会社製のスーパースタティックミキサー、等が使用できる。 The static mixer used in the present invention is not particularly limited as long as the pressure loss required for sufficient mixing is small, and can be employed without any particular limitation. For example, a static mixer manufactured by Noritake Co., Ltd., Nanocus Co., Ltd. Lamond nano mixer manufactured by Fujikin Co., Ltd., Fujikin Co., Ltd., Shin-Yu Giken Co., Ltd. super static mixer, etc. can be used.
このように、排出管の途中に静止型混合器を設置することで金属アルカリ水溶液と無機酸とを十分に混合することができ、よって前記排出管途中における静止型混合器の下流に設置したｐＨメーターの指示値の変動が極めて小さくなる。
Thus, by installing a static mixer in the middle of the discharge pipe, it is possible to sufficiently mix the aqueous metal alkali solution and the inorganic acid, and thus the pH installed downstream of the static mixer in the middle of the discharge pipe. Fluctuation of the meter reading becomes extremely small.
また、反応生成物のｐＨを監視することを目的として、静止型混合器の下流の排出管途中にｐＨメーター４を設置する。さらに、反応生成物を均一なｐＨで連続生産することを目的として、前記ｐＨメーターの指示値から金属アルカリ水溶液および／または無機酸の供給量を調整する制御を行うことも可能である。
Further, for the purpose of monitoring the pH of the reaction product, a pH meter 4 is installed in the middle of the discharge pipe downstream of the static mixer . Furthermore, for the purpose of continuously producing the reaction product at a uniform pH, it is possible to control the supply amount of the metal alkali aqueous solution and / or the inorganic acid from the indicated value of the pH meter.
本発明の混合器は金属アルカリ水溶液と無機酸とを混合し、金属酸化物ゾルを製造するために用いられる。 The mixer of the present invention is used to produce a metal oxide sol by mixing an aqueous metal alkali solution and an inorganic acid.
本発明に用いる無機酸としては、硫酸、塩酸、硝酸等が挙げられ、特に硫酸が好適に用いられる。均質な金属酸化物ゾルを得るためには、無機酸の濃度は１から６Ｎ、とすることが好ましく、２から５Ｎとすることがより好ましい。 Examples of the inorganic acid used in the present invention include sulfuric acid, hydrochloric acid, nitric acid and the like, and sulfuric acid is particularly preferably used. In order to obtain a homogeneous metal oxide sol, the concentration of the inorganic acid is preferably 1 to 6N, and more preferably 2 to 5N.
本発明に用いる金属アルカリ水溶液としては、下記式１で表される金属オキソ酸アルカリ金属塩を好適に使用することができる。また、二つ以上の金属オキソ酸アルカリ金属塩を混合して使用することもできる。 As the metal alkali aqueous solution used in the present invention, a metal oxoacid alkali metal salt represented by the following formula 1 can be preferably used. Further, two or more metal oxo acid alkali metal salts may be mixed and used.
ｍ（Ｍ２Ｏ）・ｎ（Ｍ’Ｏｌ） （式１）
（式中のｍ、ｎは正の整数を示し、lはＭの価数の２分の１の数値を示し、Ｍはアルカリ金属原子を示し、Ｍ’はアルカリ金属以外の金属原子および半金属原子を示す。）
式１におけるアルカリ金属原子としては、ナトリウムやカリウム等が挙げられ、特にナトリウムが好適に用いられる。式１におけるアルカリ金属以外の金属原子および半金属原子としては、ケイ素、アルミニウム等が挙げられ、特にケイ素が好適に用いられる。上記式（１）で示される金属オキソ酸アルカリ金属塩を具体的に例示すると、ケイ酸ソーダ、アルミン酸ソーダ等が挙げられる。
m (M 2 O) · n (M′O 1 ) (Formula 1)
(In the formula, m and n are positive integers, l is a half of the valence of M, M is an alkali metal atom, and M ′ is a metal atom or metalloid other than alkali metal. Indicates an atom.)
Examples of the alkali metal atom in Formula 1 include sodium and potassium, and sodium is particularly preferably used. Examples of metal atoms and metalloid atoms other than the alkali metal in Formula 1 include silicon and aluminum, and silicon is particularly preferably used. Specific examples of the metal oxoacid alkali metal salt represented by the above formula (1) include sodium silicate, sodium aluminate and the like.
上記式（１）で示される金属アルカリを無機酸と混合することにより、Ｍ’の酸化物ゾルが調製される。例えばケイ酸ソーダ〔ｍ（Ｎａ２Ｏ）・ｎ（ＳｉＯ２）〕からは、シリカゾル（ｘＳｉＯ２）が得られる。 An M ′ oxide sol is prepared by mixing a metal alkali represented by the above formula (1) with an inorganic acid. For example, silica sol (xSiO 2 ) is obtained from sodium silicate [m (Na 2 O) · n (SiO 2 )].
上記金属オキソ酸アルカリ金属塩は通常固体であるため、本発明においては水溶液にして用いられる。この水溶液は、希釈等により適宜濃度調整を行ってから使用することができる。金属オキソ酸アルカリ金属塩水溶液に含まれるアルカリ金属濃度、および、金属および半金属濃度は、均質な金属酸化物ゾルを得ることができれば特に制限されるものではない。 Since the metal oxoacid alkali metal salt is usually a solid, in the present invention, it is used as an aqueous solution. This aqueous solution can be used after the concentration is appropriately adjusted by dilution or the like. The alkali metal concentration, and the metal and metalloid concentrations contained in the metal oxoacid alkali metal salt aqueous solution are not particularly limited as long as a homogeneous metal oxide sol can be obtained.
例えば、珪酸ソーダ水溶液を用いてシリカゾルを製造するのであれば、高濃度であると微細なゲルが発生し不均一となり、低濃度では得られるシリカ分が少量となるため、Ｎａ２Ｏ濃度は１から２０質量％であるのが好ましく、より好ましくは３から１０質量％であり、ＳｉＯ２濃度は１から３０質量％が好ましく、より好ましくは１０から２０質量％である。 For example, if a silica sol is produced using an aqueous solution of sodium silicate, a high concentration causes a fine gel to be generated and becomes non-uniform, and a low concentration results in a small amount of silica, so the Na 2 O concentration is 1 To 20 mass%, more preferably 3 to 10 mass%, and the SiO 2 concentration is preferably 1 to 30 mass%, more preferably 10 to 20 mass%.
本発明においては、上記金属オキソ酸アルカリ金属塩水溶液と無機酸とを互いに対向した配管中に流すことによって連続的に衝突させる。 In the present invention, the metal oxoacid alkali metal salt aqueous solution and the inorganic acid are caused to collide continuously by flowing through pipes facing each other.
金属アルカリ水溶液と無機酸との衝突速度は、遅い場合は衝突後の不均一な混合状態で長時間留まるため不均一な反応が生じる場合があり好ましくない。特にゲル転移のような変化を生じる場合は一定以上の流速が必要となる。ただし、衝突速度が高い方が高い混合効果を得られるが、ある程度以上では、原料を加速するために必要なデメリットが、混合効果のメリットを上回ってしまう。
よって金属アルカリ水溶液と無機酸との衝突速度は、好ましくは互いに１ｍ／秒以上、より好ましくは互いに５〜７ｍ／秒の範囲である。 本発明に用いる静止型混合器の圧力損失は、好ましくは５０ｋＰａ以下、より好ましくは２０ｋＰａ以下である。圧力損失が大きい方が高い混合効果を得られるが、ある程度以上では、原料を加速するために必要なデメリットが、混合効果のメリットを上回ってしまう。
When the collision speed between the metal alkali aqueous solution and the inorganic acid is slow, it is unfavorable because a non-uniform reaction may occur because it stays for a long time in the non-uniform mixed state after the collision. In particular, when a change such as gel transition occurs, a flow rate above a certain level is required. However, the higher the collision speed, the higher the mixing effect can be obtained, but the demerit necessary for accelerating the raw material exceeds the merit of the mixing effect above a certain level.
Therefore, the collision speed between the aqueous metal alkali solution and the inorganic acid is preferably 1 m / second or more, more preferably 5 to 7 m / second. The pressure loss of the static mixer used in the present invention is preferably 50 kPa or less, more preferably 20 kPa or less. A higher pressure loss can provide a higher mixing effect, but above a certain level, the demerits necessary to accelerate the raw material exceed the merit of the mixing effect.
以下、本発明を具体的に説明するため、実施例を示すが、本発明はこれらの実施例のみに制限されるものではない。また、実施例、比較例において、静止型混合器としてはシンユー技研製、スーパースタティックミキサーを用い、ｐＨの測定はメトラー・トレド株式会社製、マルチパラメータ変換機Ｍ４００ｔｙｐｅ１、および、ｐＨ電極ＩｎＰｒｏ３２５０ｉ／ＳＧ／１２０により行った。 EXAMPLES Hereinafter, examples will be shown to specifically describe the present invention, but the present invention is not limited to only these examples. In Examples and Comparative Examples, a static mixer is used as a static mixer manufactured by Shinyu Giken Co., Ltd., pH is measured by METTLER TOLEDO Co., Ltd., multi-parameter converter M400type1, and pH electrode InPro3250i / SG / 120.
実施例１
原料となる金属アルカリ水溶液としてＪＩＳ３号珪酸ソーダ水溶液を用い、無機酸として硫酸を用いて、金属酸化物ゾルであるシリカゾルを得る。珪酸ソーダ水溶液中に含まれるＳｉＯ２成分の含有量が１８質量％となるように水を加えて調整し、また、硫酸を１．７Ｎとなるように水を加えて調整した。それぞれの原料を図１に記載されている反応装置を用い、原料供給管１，１’から供給した。
Example 1
A silica sol, which is a metal oxide sol, is obtained using a JIS No. 3 sodium silicate aqueous solution as a metal alkali aqueous solution as a raw material and sulfuric acid as an inorganic acid. The content of SiO 2 components contained in the aqueous sodium silicate solution is adjusted by adding water so that 18 wt%, was also adjusted by adding water so as to 1.7N sulfuric acid. Each raw material was supplied from the raw material supply pipes 1 and 1 ′ using the reaction apparatus described in FIG.
硫酸は一定の流量で供給する目的で、混合器の上流に流量計と流量調節弁を設置し、硫酸の流量を監視して流量調節弁を調節することで硫酸の流量を一定としながら反応を行った。珪酸ソーダ水溶液は排出液のｐＨを一定とする目的で、混合器の上流に流量調節弁を排出管２の途中にｐＨメーターを設置し、ｐＨメーターにて排出液のｐＨを監視し、目標ｐＨであるｐＨ５から上下０．２以上の逸脱が生じないよう、珪酸ソーダ水溶液の流量調整弁に信号を送り該流量調整弁をＰＩＤ制御することによって供給流量を調整することで排出液のｐＨを一定にしながら反応を行った。
For the purpose of supplying sulfuric acid at a constant flow rate, a flow meter and a flow control valve are installed upstream of the mixer, and the reaction is carried out while keeping the flow rate of sulfuric acid constant by monitoring the flow rate of sulfuric acid and adjusting the flow control valve. went. For the purpose of keeping the pH of the effluent solution constant, the sodium silicate aqueous solution is equipped with a flow control valve upstream of the mixer and a pH meter installed in the middle of the
硫酸と珪酸ソーダ水溶液の衝突混合における流速は５ｍ／秒となるよう、原料供給管１，１’において絞り部を設けて流速の調整を行った。 The flow rate was adjusted by providing a constriction in the raw material supply pipes 1 and 1 ′ so that the flow rate in the collision mixing of sulfuric acid and sodium silicate aqueous solution was 5 m / sec.
反応は、６００秒の連続製造を行い、ゲル化物を含まない均質なシリカゾルを得た。連続製造の時間に対して、目標としたｐＨから前後それぞれ０．２以上の逸脱が生じた時間の割合を目標ｐＨ逸脱割合として式２で表す。
The reaction was carried out continuously for 600 seconds to obtain a homogeneous silica sol containing no gelled product. The ratio of the time in which a deviation of 0.2 or more before and after the target pH has occurred with respect to the continuous production time is expressed by
目標ｐＨ逸脱割合（％）
＝目標ｐＨを逸脱した時間（秒）÷連続製造時間（秒）×１００ （式２）
その結果を表１に示す。
Target pH deviation rate (%)
= Time deviating from target pH (seconds) / Continuous production time (seconds) x 100 (Equation 2)
The results are shown in Table 1.
この方法で得られたシリカゾルは、目標ｐＨ逸脱割合が０％と低い値であったため、該シリカゾルを３０秒毎に取り分け、計２０ロットのサンプルを得て、各ロットについて別々に、３０℃で静置することでゾル・ゲル転移させ、水洗により副生塩を取り除き、１５０℃にて乾燥を行うことでシリカゲルを得たところ、ロット間の変動が小さく、ほぼ一定の比表面積を有するシリカゲルが得られた。 The silica sol obtained by this method had a target pH deviation rate as low as 0%. Therefore, the silica sol was separated every 30 seconds, and a total of 20 lots of samples were obtained. The silica gel was obtained by sol-gel transition by standing, removing by-product salt by washing with water, and drying at 150 ° C., and there was little variation between lots, and silica gel having a substantially constant specific surface area was obtained. Obtained.
実施例２
原料となる無機酸として、水を加えて濃度を１．７Ｎとした塩酸を用いた他は実施例１と同じ条件でシリカゾルを得た。その結果を表１に示す。
Example 2
A silica sol was obtained under the same conditions as in Example 1 except that hydrochloric acid having a concentration of 1.7 N by adding water was used as the raw material inorganic acid. The results are shown in Table 1.
実施例３
原料となる金属オキソ酸アルカリ金属塩水溶液としてアルミン酸ソーダ水溶液を用い、水を加えてＮａ２Ｏ濃度を１０質量％、Ａｌ２Ｏ３濃度を１０質量％とし、硫酸の濃度を３Ｎとした他は実施例１と同じ条件でアルミナゾルを得た。その結果を表１に示す。
Example 3
Other than using sodium aluminate aqueous solution as the raw material metal oxo acid alkali metal salt aqueous solution, adding water to make Na 2 O concentration 10% by mass, Al 2 O 3 concentration 10% by mass and sulfuric acid concentration 3N Obtained alumina sol under the same conditions as in Example 1. The results are shown in Table 1.
比較例１
排出管途中に設けた静止型混合器を取り外し、代わりに同じ長さと直径を有する直管を取り付けた他は実施例１と同じ条件でシリカゾルを得た。その結果を表１に示す。
Comparative Example 1
Silica sol was obtained under the same conditions as in Example 1 except that the static mixer provided in the middle of the discharge pipe was removed and a straight pipe having the same length and diameter was attached instead. The results are shown in Table 1.
この方法で得られたシリカゾルは、目標ｐＨ逸脱割合が４５％と高い値であったため、実施例１と同様の方法でシリカゲルを得たところ、ロット間の変動が大きく、均質な比表面積を有するシリカゲルは得られなかった。 Since the silica sol obtained by this method had a target pH deviation rate as high as 45%, silica gel was obtained by the same method as in Example 1. As a result, the lot-to-lot variation was large and the specific surface area was uniform. Silica gel was not obtained.
１，１’：原料供給管
２：排出管
３：合流部
４：ｐＨメーター
５：静止型混合器
1, 1 ': Raw material supply pipe 2: Discharge pipe 3: Merge section 4: pH meter 5: Static mixer
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