JPS62252312A - Production of hydrous silicic acid - Google Patents
Production of hydrous silicic acidInfo
- Publication number
- JPS62252312A JPS62252312A JP9466586A JP9466586A JPS62252312A JP S62252312 A JPS62252312 A JP S62252312A JP 9466586 A JP9466586 A JP 9466586A JP 9466586 A JP9466586 A JP 9466586A JP S62252312 A JPS62252312 A JP S62252312A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- sulfuric acid
- concentrated sulfuric
- pump
- reaction
- 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
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 42
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 230000005070 ripening Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 239000004115 Sodium Silicate Substances 0.000 description 13
- 229910052911 sodium silicate Inorganic materials 0.000 description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は珪酸アルカリ水溶液と酸の中和反応による含水
珪酸の製造方法に関し、特に濃硫酸を用いる含水珪酸の
工業的に有利な製造方法に関する４［従来の技術］
珪酸ソーダの如き珪酸アルカリ水溶液と硫酸の如き鉱酸
の中和反応による含水珪酸の製造方法が多数提案されて
おり、周知のものとなっている。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing hydrated silicic acid by neutralizing an aqueous alkali silicate solution and an acid, and particularly relates to an industrially advantageous method for producing hydrated silicic acid using concentrated sulfuric acid. 4 [Prior Art] Many methods for producing hydrated silicic acid by a neutralization reaction between an aqueous alkali silicate solution such as sodium silicate and a mineral acid such as sulfuric acid have been proposed and are well known.
例えば、特公昭５６−２１７２６号公報、特公昭５１−
２５２３５号公報、特公昭３８−１７６５１号公報及び
特公昭３９−１２０７号公報等には、硫酸による中和反
応を少なくとも２回に分けて行ない且つその間に熟成さ
せることからなる含水珪酸の製造方法が記載されている
。For example, Japanese Patent Publication No. 56-21726, Japanese Patent Publication No. 51-
Japanese Patent Publication No. 25235, Japanese Patent Publication No. 38-17651, Japanese Patent Publication No. 39-1207, etc. disclose a method for producing hydrated silicic acid, which comprises carrying out a neutralization reaction with sulfuric acid in at least two steps and aging the reaction in between. Are listed.
他方、上記中和反応において、反応系を渦巻ポンプにて
循環させて含水珪酸を生成させることも知られている（
特公昭５１−２８５９７号公報）。On the other hand, in the above neutralization reaction, it is also known to generate hydrous silicic acid by circulating the reaction system with a centrifugal pump (
(Special Publication No. 51-28597).
［発明が解決しようとする問題点］
珪酸アルカリ水溶液から、ゴム、プラスチックス等への
各種の添加剤として用いられる微粉含水珪酸を製造する
場合、いわゆる湿式法の微粉含水珪酸を如何に安価に製
造するかが最も重要且つ基本的課題となっている。[Problems to be Solved by the Invention] When producing fine powdered hydrated silicic acid used as various additives for rubber, plastics, etc. from an aqueous alkali silicate solution, how to inexpensively produce fine powdered hydrated silicic acid by a so-called wet method. The most important and fundamental issue is whether to do so.
従来の工業的製法においては、多くの場合、珪酸アルカ
リ水溶液及び硫酸等の鉱酸はかなり稀釈された状態で母
液中の５ｉ０２濃度の低いところで含水珪酸が製造され
ていた。In conventional industrial production methods, in many cases, hydrated silicic acid is produced using an aqueous alkali silicate solution and a mineral acid such as sulfuric acid in a considerably diluted state at a low 5i02 concentration in the mother liquor.
この理由は液濃度が高くなると、極部的なゲル化が生じ
易く、微細で均一な含水珪酸粒子の生成が困難となるか
らである。The reason for this is that when the liquid concentration becomes high, local gelation tends to occur, making it difficult to produce fine and uniform hydrated silicic acid particles.
例えば、特公昭３８−１７６５１号公報及び特公昭３９
−１２０７号公報においては、硫酸を１００〜２００ｙ
／１（Ｈ２Ｏ）の濃度に稀釈して用いており、また、特
公昭５１−２８５９７号公報の如き循環型の製法におい
ても５５％Ｈ２ＳＯ，程度の硫酸が用られている。For example, Japanese Patent Publication No. 38-17651 and Japanese Patent Publication No. 39
-1207 publication, 100 to 200 y of sulfuric acid
Sulfuric acid is used after being diluted to a concentration of 1/1 (H2O), and sulfuric acid of about 55% H2SO is also used in a circulation type production method such as that disclosed in Japanese Patent Publication No. 51-28597.
特公昭５１−２５２３５号公報においては、撹拌型反応
槽にて原料鉱酸として８０％ｌｌ２ＳＯ，程度の濃硫酸
を用いているが、本発明者らの実験によれば、９０％Ｈ
，ＳＯ，以上、特に９８％濃硫酸を用いて撹拌下に珪酸
ソーダ水溶液と反応させることは殆んど不可能であった
。In Japanese Patent Publication No. 51-25235, concentrated sulfuric acid of about 80% 11 SO is used as the raw mineral acid in a stirred reaction tank, but according to experiments by the present inventors, 90% H
, SO, in particular, it was almost impossible to react with an aqueous sodium silicate solution using 98% concentrated sulfuric acid under stirring.
濃硫酸を用いる場合、多量の稀釈熱と中和熱が発生して
添加と同時に強い発熱の為、暴発的に液が飛散するなど
の危険を伴うと同時に反応系は極部的なゲル化を生じ、
均一な微細な含水珪酸粒子の生成は期待できない。When using concentrated sulfuric acid, a large amount of heat of dilution and neutralization is generated and a strong heat is generated at the same time as it is added, so there is a danger that the liquid may suddenly scatter, and at the same time, the reaction system may become partially gelled. arise,
Generation of uniform, fine hydrated silicic acid particles cannot be expected.
［問題点を解決するための手段］
本発明者らは原料硫酸を稀釈することなく、直接濃硫酸
を原料として使用することに臨み、上記問題点を鋭意検
討し、濃硫酸の使用に成功して本発明を完成した。[Means for solving the problem] The present inventors attempted to use concentrated sulfuric acid directly as a raw material without diluting the raw material sulfuric acid, and after intensively studying the above problems, succeeded in using concentrated sulfuric acid. The present invention was completed.
すなわち、本発明は珪酸アルカリ水溶液と酸との中和反
応による含水珪酸の製造方法において、（ａ）反応系を
７０℃以上の温度条件下でポンプ循環し；
（ｂ）酸が濃硫酸であり、この濃硫酸をポンプ循環系の
反応槽への戻り口付近の循環パイプ内に添加し；
（ｃ）濃硫酸の添加を少なくとも２回に分けて断続的に
行ない；且つ
（ｄ）濃硫酸の添加を中断する際、ポンプ循環の能力を
低下して熟成する、
ことを特徴とする含水珪酸の製造方法にかかるものであ
る。That is, the present invention provides a method for producing hydrated silicic acid by a neutralization reaction between an aqueous alkali silicate solution and an acid, in which (a) the reaction system is pump-circulated at a temperature of 70° C. or higher; (b) the acid is concentrated sulfuric acid; , add this concentrated sulfuric acid into the circulation pipe near the return port to the reaction tank of the pump circulation system; (c) add the concentrated sulfuric acid intermittently in at least two times; and (d) add the concentrated sulfuric acid The present invention relates to a method for producing hydrated silicic acid, which is characterized in that, when the addition is interrupted, the ability of pump circulation is reduced to allow ripening.
［作 用］ 以下に、本発明の含水珪酸の製造方法を詳述する。[Work] Below, the method for producing hydrated silicic acid of the present invention will be explained in detail.
本発明において使用する原料珪酸アルカリ水溶液は、Ｓ
ｉ Ｏｚ／ Ｍ ２０モル比（Ｍはアルカリ金属を表
わす）が２〜４の範囲のもので、特に、ＪＩＳＢ号珪酸
ソーダが好適であり、これを水で稀釈してＳ ｉ Ｏ２
として５〜１５重量％、特に５〜１０重量％の範囲にあ
る濃度のものを用いる。The raw material alkali silicate aqueous solution used in the present invention is S
i Oz/M 20 The molar ratio (M represents an alkali metal) is in the range of 2 to 4, and JISB sodium silicate is particularly suitable, and this is diluted with water to form S i O2.
A concentration in the range of 5 to 15% by weight, particularly 5 to 10% by weight is used.
他方、原料鉱酸としては濃硫酸を用い、これが本発明方
法の重要な特徴の１つとなっている。On the other hand, concentrated sulfuric acid is used as the raw mineral acid, which is one of the important features of the method of the present invention.
ここに濃硫酸というのは、９０重量％Ｈ２ＳＯ。Concentrated sulfuric acid here means 90% by weight H2SO.
以上の硫酸をいい、勿論９８重量％Ｈ，Ｓ○、でも差支
えない。It refers to the above sulfuric acid, and of course, 98% by weight H, SO may also be used.
珪酸アルカリ水溶液と酸の反応は実際には複雑であるが
、珪酸ソーダ水溶液と硫酸の反応を例にとって反応式で
表わせば次のように示すことができる。The reaction between an alkali silicate aqueous solution and an acid is actually complicated, but if the reaction between a sodium silicate aqueous solution and sulfuric acid is taken as an example, it can be expressed as a reaction formula as follows.
Ｎａ２Ｏ・ｎ５ｉ０２ ＋ Ｈ２Ｓ０４−ｎｓｉ０２
＋ Ｎａ２ＳＯ４＋ １１２０＝−（１）本発明につい
て、上記反応を添付工程図と共に説明する。Na2O・n5i02 + H2S04-nsi02
+Na2SO4+ 1120=-(1) Regarding the present invention, the above reaction will be explained with reference to the attached process diagram.
反応槽（３）には主撹拌機（４）及び副撹拌機（５）が
付設されており、珪酸アルカリ水溶液及び濃硫酸はそれ
ぞれ珪酸ソーダ計量槽（１）及び−ＩＡ硫酸計量槽（８
）から珪酸ソーダ仕込ポンプ（２）または濃硫酸仕込ポ
ンプ（９）を経て反応槽（３）へ導入される。The reaction tank (3) is equipped with a main stirrer (4) and a sub-stirrer (5), and the aqueous alkali silicate solution and concentrated sulfuric acid are fed into the sodium silicate measuring tank (1) and -IA sulfuric acid measuring tank (8), respectively.
) is introduced into the reaction tank (3) via the sodium silicate feed pump (2) or the concentrated sulfuric acid feed pump (9).
なお、反応槽（３）には蒸気加熱用ジャケット（１０）
が付設されている。また、２つの撹拌機のうち、副撹拌
機く５）はポンプ循環流の吐出力を助長させると共に反
応槽への分散を促進させるために作用するものであるが
、循環ポンプ（６）によるポンプ循環が効果的に行なわ
れ且つ充分な吐出量が期待される場合には必ずしも不可
欠に付設する必要はない。In addition, the reaction tank (3) is equipped with a steam heating jacket (10).
is attached. Of the two stirrers, the sub-stirrer (5) acts to increase the discharge force of the pump circulation flow and promote dispersion into the reaction tank, but the pump by the circulation pump (6) If circulation is effective and a sufficient discharge amount is expected, it is not absolutely necessary to provide this.
本発明において、反応槽（３）に仕込まれた珪酸アルカ
リ水溶液は循環ポンプ（６）を経て再び反応槽へ（３）
に循環させる循環系を構成する。この状態で、反応系の
温度を７０℃以上、特に好ましくは８０〜９５℃に保持
する。これが本発明方法の第１の特徴となる。In the present invention, the aqueous alkali silicate solution charged into the reaction tank (3) passes through the circulation pump (6) and returns to the reaction tank (3).
It constitutes a circulatory system that circulates to In this state, the temperature of the reaction system is maintained at 70°C or higher, particularly preferably from 80 to 95°C. This is the first feature of the method of the present invention.
次いで、この状態で珪酸アルカリ水溶液の中和反応を行
なうべく、本発明では濃硫酸をポンプ循環系の反応槽へ
の戻り口付近の循環パイプ内に添加する。これが本発明
方法の第２の特徴であり、最も重要な特徴となっている
。Next, in order to carry out a neutralization reaction of the aqueous alkali silicate solution in this state, in the present invention, concentrated sulfuric acid is added into the circulation pipe near the return port to the reaction tank of the pump circulation system. This is the second and most important feature of the method of the present invention.
即ち、濃硫酸の添加位置は循環パイプの所望の位置に接
続して添加するのではなく、必ず反応系が反応槽へ循環
する戻り口付近でなければならない。That is, the addition position of concentrated sulfuric acid should not be connected to a desired position of the circulation pipe, but must be near the return port where the reaction system circulates to the reaction tank.
これは本発明者らの多くの実験結果によるもので、前記
戻り口付近似外では本反応を本質的に実施することは難
かしい。This is based on the results of many experiments by the present inventors, and it is essentially difficult to carry out this reaction outside the vicinity of the return port.
一般に、本反応において濃硫酸を使用すると、単なる撹
拌下では、顕著な発熱に伴う暴発的な液の飛散を生じて
危険であるのみならず、極めて不均質な珪酸を生成し、
それ故、実施不能であり、また、撹拌と共に循環系を４
ｉＩ代しても殆んど同様の結果となる。In general, when concentrated sulfuric acid is used in this reaction, simple stirring causes not only a significant heat generation and explosive splashing of the liquid, which is not only dangerous, but also produces extremely heterogeneous silicic acid.
Therefore, it is not practicable and the circulation system is
Almost the same result is obtained even if the iI value is changed.
然るに、本発明では充分な高セン断力を与えるポンプ循
環を行なうと共に濃硫酸の添加位置を上記のように特定
することにより、濃硫酸の添加を閉鎖系で行なうと共に
循環系の反応槽内への突出力のため、濃硫酸の使用が可
能となった。However, in the present invention, by performing pump circulation that provides a sufficiently high shear force and specifying the addition position of concentrated sulfuric acid as described above, the addition of concentrated sulfuric acid is carried out in a closed system, and the addition of concentrated sulfuric acid is carried out in a closed system. Because of the ejection force, it became possible to use concentrated sulfuric acid.
この場合、本反応をより円滑に行わせるため、循環ポン
プ（３）の所要エネルギーはＳｈｏｗとして７重量％の
濃度の反応系１餉コ当り１ＫＷＨ以上の動力で稼動させ
ることが必要である。In this case, in order to carry out the reaction more smoothly, the circulation pump (3) needs to be operated at a power of 1 KWH or more per reaction system with a concentration of 7% by weight as a show.
また上記のように、循環流の吐出口付近下に副撹拌機（
５）を付設して高速撹拌させることがより効果的で好ま
しい。In addition, as mentioned above, there is a sub-stirrer (
It is more effective and preferable to add 5) and stir at high speed.
しかして、濃硫酸の添加は上記反応式（１）にあるよう
に反応に必要な全量の酸量を連続的に添加するのではな
く、少なくとも２回に分けて断続的に添加することが必
要であり、これが第３の特徴となっている。Therefore, when adding concentrated sulfuric acid, it is necessary to add it intermittently in at least two parts, rather than continuously adding the entire amount of acid required for the reaction as shown in reaction formula (1) above. This is the third feature.
このような断続的な酸の添加は本反応においては公知で
あり、本発明においても必要であり、その理由も上記公
知文献に充分説明されているが、特に濃硫酸を用いる場
合には、この断続的添加はより欠くことができないもの
となる。Such intermittent addition of acid is known in the present reaction and is also necessary in the present invention, and the reason for this is fully explained in the above-mentioned known literature, but especially when concentrated sulfuric acid is used, this Intermittent addition becomes more essential.
この場合、濃硫酸の添加量は上記反応式（１）により求
められるが、原料の珪酸ソーダについて言えば、Ｓ ｉ
ｏ ２／ Ｎ ａ２０モル比をＭ、Ｒ１中和に要する酸
の全量に対する酸の添加量の割合をＸ重量％および、こ
のときの反応系内のモル比（ＳｉＯ２と未反応のＮａ２
Ｏのモル比Ｓ ； Ｏｘ／ Ｎ ａ２０ ）をｍ、ｒと
すると、
となる。In this case, the amount of concentrated sulfuric acid added is determined by the above reaction formula (1), but regarding the raw material sodium silicate, Si
o2/Na20 molar ratio is M, the ratio of the amount of acid added to the total amount of acid required for R1 neutralization is X% by weight, and the molar ratio in the reaction system at this time (SiO2 and unreacted Na2
If the molar ratio of O (S; Ox/N a20 ) is m and r, then the following equation is obtained.
本発明においては、第１回目の濃硫酸の添加量（Ｘ）は
２０〜５０重景％、特に３０〜４５重量％が好適であり
、第２回目の濃硫酸の添加量は３０〜５５重景％、特に
４０〜５０重量％が好適であり、第２回目で実質的に反
応させ、更に第３回目は残量を反応系のｐＨ調整として
ｐＨが５前後になるまで添加して反応を終了させる。In the present invention, the amount (X) of concentrated sulfuric acid added in the first addition is preferably 20 to 50% by weight, particularly 30 to 45% by weight, and the amount of concentrated sulfuric acid added in the second addition is 30 to 55% by weight. %, particularly 40 to 50% by weight, is preferable, and the reaction is substantially carried out in the second reaction, and the remaining amount is added in the third reaction to adjust the pH of the reaction system until the pH becomes around 5. Terminate it.
なお、多くの場合、上記のように３回に分けて濃硫酸を
断続的に添加するが、他の添加態様として３回以上に分
けて添加することもできる。In many cases, concentrated sulfuric acid is added intermittently in three portions as described above, but as another addition mode, concentrated sulfuric acid may be added in three or more portions.
各回の濃硫酸添加後には熟成を行なうが、本発明におい
ては第１回目の添加終了後、反応系は青味を滞びた乳光
色から白濁液と変化してゆく状態で温度７０℃１ツ、上
、特に８５〜９５℃の温度で、０．５〜３時間、特に１
〜２時間熟成を行なう。Aging is performed after each addition of concentrated sulfuric acid, but in the present invention, after the first addition, the reaction system changes from an opalescent color with a stagnant bluish color to a cloudy liquid at a temperature of 70°C. at a temperature of 85-95°C for 0.5-3 hours, especially 1
Aging is performed for ~2 hours.
なお、熟成時間はセン断力が強い程短かくすることがで
きる。Note that the aging time can be made shorter as the shearing force becomes stronger.
この最初の熟成の間は濃硫酸の添加のみを中断するだけ
でポンプ循環や主副撹拌機の稼動は必ずしも中止する必
要はない。During this initial ripening, only the addition of concentrated sulfuric acid is interrupted, and the circulation of the pump and the operation of the main and sub stirrers do not necessarily need to be stopped.
次いで、この熟成終了後再び濃硫酸の２回目の添加を前
記の条件で行ない、添加終了後第２回目の熟成を行なう
。Next, after the completion of this ripening, concentrated sulfuric acid is added again under the above-mentioned conditions, and after the addition is finished, the second ripening is carried out.
この間の熟成は先のそれよりも短時間でよく、多くの場
合０．２〜１時間である。この熟成の際にはポンプ循環
の能力を低下させた状態で主撹拌機による熟成を行なう
ことが重要で本発明の特徴の１つとなっている。ここで
ポンプ循環の能力の低下とは、その稼動を停止させるか
、またはインバーターによりポンプの回転数を下げて実
質的にセン断力のかからない状態にすることを言う０通
常は循環ポンプの稼動停止が好ましい、なお、副撹拌機
が付設されている場合には、その稼動も同様に能力低下
を行なう。この理由は第２回目の硫酸の添加で反応が実
質的に行なわれて生成する珪酸に対し、この時点におけ
る熟成下にポンプ循環や高速撹拌を続けると、得られた
高構造性の活性な珪酸粒子が強力セン断作用により破壊
されて、殆んど目的とする品質が得られないからである
。This period of aging may be shorter than the previous one, and in most cases is 0.2 to 1 hour. During this ripening, it is important to carry out the ripening using the main stirrer while the pump circulation capacity is reduced, and this is one of the features of the present invention. Here, reducing the pump circulation capacity means stopping its operation or lowering the pump rotation speed using an inverter so that no shearing force is applied to it.Normally, the circulation pump stops operating. is preferable; however, if an auxiliary stirrer is attached, its operation capacity is similarly reduced. The reason for this is that when the silicic acid is substantially reacted and produced by the second addition of sulfuric acid, if pump circulation and high-speed stirring are continued during aging at this point, the resulting highly structured active silicic acid This is because the particles are destroyed by the strong shearing action, making it almost impossible to obtain the desired quality.
更に、上記熟成終了後、インバーターにて循環ポンプの
回転数を下げて循環流量を少なくした条件で′ａ硫酸の
残量を添加してｐＨ５前後に調整して反応を終了させ、
暫時熟成する。Furthermore, after the completion of the above-mentioned ripening, the remaining amount of sulfuric acid was added to adjust the pH to around 5, and the reaction was terminated by lowering the rotation speed of the circulation pump using an inverter and reducing the circulation flow rate.
Maturing for a while.
なお、この時の熟成においては、必ずしもポンプ循環の
停止をする必要はない。Note that during this ripening, it is not necessarily necessary to stop pump circulation.
以下は、常法により母液を分離し、要すれば、この母液
を硫酸ソーダとして回収し他方、−過ケーキは洗浄後含
水珪酸スラリーまたは粉体として得ることができる。゛
本発明にかかる方法で得られる含水珪酸は、２００メツ
シュ篩残分が多くとも３重量％、通常２重量％以下の極
めて粗粒分の少ない微細な粒子である。In the following, the mother liquor is separated by a conventional method, and if necessary, the mother liquor is recovered as sodium sulfate, and the filtrate cake can be obtained as a hydrous silicic acid slurry or powder after washing. The hydrated silicic acid obtained by the method of the present invention is fine particles with an extremely small amount of coarse particles, with a 200 mesh sieve residue of at most 3% by weight, and usually 2% by weight or less.
他方、本発明にかかる方法によれば、濃硫酸を直接原料
として安全に使用できるので、工業的に有利に実施する
ことができる。On the other hand, according to the method according to the present invention, concentrated sulfuric acid can be safely used directly as a raw material, so that it can be carried out industrially advantageously.
［実 施 例］
夾Ｗ二」ユ
図に示すような主撹拌機（４）及び副撹拌機（５）を付
設した反応槽（３）にＪＩＳＢ号珪酸ソーダ（ＭＲ：
３．１５）６３５ｋｆＩを珪酸ソーダ仕込ポンプ（２）
より仕込み、次いで水１９９０ｋｇを仕込んだ後、主撹
拌機（４）による撹拌下８５°Ｃに加温した。[Example] JISB sodium silicate (MR:
3.15) 635kfI using sodium silicate charging pump (2)
After charging 1,990 kg of water, the mixture was heated to 85°C while being stirred by the main stirrer (4).
次いで、８５℃の昇温後、所要エネルギー１ 、５ Ｋ
Ｗ Ｈ／ ｖａ”にて循環ポンプ（６）を稼動させ、
吐出型を２０＋ｎ’／時間として同時に副撹拌機（５）
を稼動させた。Then, after increasing the temperature to 85°C, the required energy is 1.5 K.
Operate the circulation pump (6) at W H/va”,
The discharge type is set to 20+n'/hour and the sub-stirrer (5) is used at the same time.
was put into operation.
次いで、９８重量％濃硫酸を、以下の第１表に示す条件
で添加及び熟成して中和反応を行ない、それぞれの微細
な含水珪酸を得た。この反応操作はいずれもの場合にも
安全に操業できた。Next, 98% by weight concentrated sulfuric acid was added and aged under the conditions shown in Table 1 below to carry out a neutralization reaction to obtain each fine hydrated silicic acid. This reaction operation could be operated safely in all cases.
次いで、得られた含水珪酸のスラリーについて２００メ
ツシユ篩を通して粒度をみたところ２００メツシュ篩残
分（篩残分／全固形分）は第１表に記載する結果の通り
であり、いずれも微細な含水珪酸であった。Next, the obtained slurry of hydrous silicic acid was passed through a 200 mesh sieve to check the particle size. It was silicic acid.
また、同時にその乾燥品についてＢＥＴ法で比表面積も
測定した。得られた結果を第１表に併記する。At the same time, the specific surface area of the dried product was also measured using the BET method. The obtained results are also listed in Table 1.
実施例５
実施例３において、循環ポンプ（６）の所要エネルギー
を２．３ＫＷＨ／ｍ’に変えた以外は、全く同様の条件
で反応及び熟成を行ない微細な含水珪酸を得た。得られ
た含水珪酸の粒径は２００メ・・Ｉシュ篩残分０．１重
量％であり、また、ＢＥＴ比表面積は２４３ｍ”ｙｅで
あった。Example 5 Fine hydrated silicic acid was obtained by carrying out the reaction and ripening under exactly the same conditions as in Example 3, except that the required energy of the circulation pump (6) was changed to 2.3 KWH/m'. The particle size of the obtained hydrated silicic acid was 0.1% by weight of the residue on the 200 mm sieve, and the BET specific surface area was 243 m"ye.
と１１Ｌ
実施例３において、循環ポンプ（６）の所要エネルギー
を０ 、５ Ｋ Ｗ Ｈ／ Ｉ１１’にて稼動させ、吐
出量を１０Ｉ１３／時間とした以外は、全く同様の条件
で反応及び熟成を行ない含水珪酸を得た。and 11L In Example 3, the reaction and aging were carried out under exactly the same conditions except that the required energy of the circulation pump (6) was 0. Hydrous silicic acid was obtained.
このとき得られた含水珪酸の２００メツシュ篩残分は８
重量％あり、極めて粗粒部分の多いものであった。The residue of the hydrated silicic acid obtained at this time through the 200 mesh sieve was 8
% by weight, and contained extremely large portions of coarse particles.
！ｆＪヱしし
実施例１〜４で用いたものと同様の図に示す反応系を循
環系にしたが、濃硫酸（９８重量％Ｈ，Ｓ○４）の添加
をポンプ循環系の反応槽への戻り口付近の循環パイプ内
ではなく、別のパイプ（水の注入に用いたと同じ）で３
回に分けて行ない、熟成を試みたところ、濃硫酸の添加
に際して激しい突沸が生じ、操作が極めて危険を伴って
きたので操作を中止せざるを得なかった。なお、反応系
は著しい極部的にゲルが生じていた。! The reaction system shown in the figure similar to that used in Examples 1 to 4 was made into a circulation system, but concentrated sulfuric acid (98% by weight H, SO4) was added to the reaction tank of the pump circulation system. 3 in a separate pipe (the same one used for water injection) rather than in the circulation pipe near the return port of the
When attempts were made to ripen the mixture in batches, severe bumping occurred when concentrated sulfuric acid was added, making the operation extremely dangerous and the operation had to be discontinued. It should be noted that a gel was formed in the reaction system in significant local areas.
雌１乱と
ＪＩＳＢ号珪酸ソーダ６３５重量部に水１９９０重量部
を添加した珪酸ソーダ水溶液を撹拌型反応槽に仕込み、
９８重量％濃硫酸を徐々に激しい撹拌下で添加したとこ
ろ比較例２と同様に激しい飛散が音を立てて生じて危険
な現象を呈した。 なお添加を続けたところ、添加濃硫
酸の液滴にゲル化が生じ、反応系は不均質となり、危険
性も増大して実質的に本反応方式は実施を中止せざるを
得なかった。A sodium silicate aqueous solution prepared by adding 1990 parts by weight of water to 635 parts by weight of JISB sodium silicate was charged into a stirring type reaction tank.
When 98% by weight concentrated sulfuric acid was gradually added under vigorous stirring, similar to Comparative Example 2, violent scattering occurred with a loud noise, presenting a dangerous phenomenon. As the addition continued, gelation occurred in the droplets of the added concentrated sulfuric acid, the reaction system became heterogeneous, and the danger increased, so the implementation of this reaction method had to be discontinued.
［発明の効果］
本発明にかかる方法によれば、珪酸アルカリ水溶液の中
和反応による含水珪酸の製造において、９８重量％の濃
硫酸でも直接原料として安全に使用することができ、し
かも、２００メツシュ篩残分が多くとも３％、通常２％
以下という粗粒子部分が極めて少ない微細な含水珪酸を
得ることができる。すなわち、従来は微細な含水珪酸を
得るために例えば充分な湿式粉砕処理を必要とするが、
本発明によれば、かかる処理を格別に採ることなく、直
接的に微細な含水珪酸を得ることができる。[Effects of the Invention] According to the method of the present invention, even 98% by weight concentrated sulfuric acid can be safely used directly as a raw material in the production of hydrated silicic acid by the neutralization reaction of an aqueous alkali silicate solution. Sieve residue is at most 3%, usually 2%
It is possible to obtain fine hydrated silicic acid having an extremely small amount of coarse particles as follows. That is, conventionally, sufficient wet pulverization is required to obtain fine hydrated silicic acid, but
According to the present invention, fine hydrated silicic acid can be directly obtained without any special treatment.
この含水珪酸は各種プラスチック、ゴム等の充填剤、あ
るいは製紙用充填剤等に利用することができる。This hydrated silicic acid can be used as a filler for various plastics, rubbers, etc., or as a filler for paper manufacturing.
上述のように、：ａ硫酸が使用可能であることは、熱監
が効果的に利用できるので省エネルギーであると共に、
稀硫酸よりも純分当りのコストが安いこともあって、非
常に工業的に有利な製造ということができる。As mentioned above, the fact that sulfuric acid can be used means that thermal monitoring can be used effectively, which saves energy.
Since the cost per pure component is lower than that of dilute sulfuric acid, it can be said to be a very industrially advantageous production method.
図は本発明の１実施態様を示す工程図である。
図中・ １・・・珪酸ソーダ計量槽、２・・・珪酸ソー
ダ仕込ポンプ、３・・反応槽、４・・・主撹拌機、５・
・・副撹拌機、６・・・循環ポンプ、７・・・流量計、
８・・・濃硫酸計量槽、９・・・濃硫酸仕込ポンプ、１
０・・・蒸気加熱ジャケット。
特許出願人 日本化学工業株式会社
手続補正書く自発）
昭和６１年１１月４日The figure is a process diagram showing one embodiment of the present invention. In the diagram: 1... Sodium silicate measuring tank, 2... Sodium silicate charging pump, 3... Reaction tank, 4... Main stirrer, 5...
...Sub-stirrer, 6...Circulation pump, 7...Flowmeter,
8... Concentrated sulfuric acid measuring tank, 9... Concentrated sulfuric acid charging pump, 1
0...Steam heating jacket. Patent applicant Nippon Kagaku Kogyo Co., Ltd. (Volunteer to write procedural amendments) November 4, 1986
Claims (1)
の製造方法において、 （ａ）反応系を７０℃以上の温度条件下でポンプ循環し
； （ｂ）酸が濃硫酸であり、この濃硫酸をポンプ循環系の
反応槽への戻り口付近の循環パイプ内に添加し； （ｃ）濃硫酸の添加を少なくとも２回に分けて断続的に
行ない；且つ （ｄ）濃硫酸の添加を中断する際、ポンプ循環の能力を
低下して熟成する、 ことを特徴とする含水珪酸の製造方法。 ２、ポンプ循環はＳｉＯ＿２として７重量％の濃度の反
応系１ｍ＾３当り１ＫＷＨ以上の所要エネルギーで行な
う特許請求の範囲第１項記載の含水珪酸の製造方法。 ３、反応槽内の反応系が主撹拌機及び副撹拌機で分散状
態にある特許請求の範囲第１項記載の含水珪酸の製造方
法。 ４、濃硫酸の第１回目の添加を珪酸アルカリを中和する
に要する酸全量の２５〜５０重量％に相当する量で珪酸
粒子が実質的に沈澱しない間に行ない、第２回目の添加
を酸全量の３０〜５５重量％に相当する量で行ない且つ
第３回目の添加を残量で行なって反応系のｐＨ調整し、
且つその間の熟成において、第２回目の熟成はポンプ循
環を、第３回目の最終熟成は撹拌をそれぞれ停止状態で
行なう特許請求の範囲第１項記載の含水珪酸の製造方法
。[Claims] 1. A method for producing hydrated silicic acid by neutralizing an aqueous aqueous silicate solution and an acid, in which (a) the reaction system is pump-circulated at a temperature of 70°C or higher; (b) the acid is concentrated sulfuric acid. The concentrated sulfuric acid is added to the circulation pipe near the return port of the pump circulation system to the reaction tank; (c) the concentrated sulfuric acid is added intermittently in at least two times; A method for producing hydrated silicic acid, characterized in that when the addition of sulfuric acid is interrupted, the ability of pump circulation is reduced to allow ripening. 2. The method for producing hydrated silicic acid according to claim 1, wherein the pump circulation is performed with a required energy of 1 KWH or more per 1 m^3 of the reaction system having a concentration of 7% by weight as SiO_2. 3. The method for producing hydrated silicic acid according to claim 1, wherein the reaction system in the reaction tank is dispersed by a main stirrer and a sub-stirrer. 4. The first addition of concentrated sulfuric acid is carried out in an amount equivalent to 25 to 50% by weight of the total amount of acid required to neutralize the alkali silicate, while the silicic acid particles are not substantially precipitated, and the second addition is carried out. Adjust the pH of the reaction system by adding the acid in an amount corresponding to 30 to 55% by weight of the total amount of acid, and making the third addition with the remaining amount,
The method for producing hydrated silicic acid according to claim 1, wherein during the aging, the second aging is performed with pump circulation, and the third and final aging is performed with stirring stopped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9466586A JPS62252312A (en) | 1986-04-25 | 1986-04-25 | Production of hydrous silicic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9466586A JPS62252312A (en) | 1986-04-25 | 1986-04-25 | Production of hydrous silicic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62252312A true JPS62252312A (en) | 1987-11-04 |
| JPH0465009B2 JPH0465009B2 (en) | 1992-10-16 |
Family
ID=14116543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9466586A Granted JPS62252312A (en) | 1986-04-25 | 1986-04-25 | Production of hydrous silicic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62252312A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0341383A2 (en) * | 1988-05-07 | 1989-11-15 | Degussa Aktiengesellschaft | Finely divided precipitated silicas with a high structure, process for their preparation and their use |
| JP2004506782A (en) * | 2000-08-18 | 2004-03-04 | ジェイ・エム・ヒューバー・コーポレーション | Abrasive composition and method for producing the same |
| JP2004506671A (en) * | 2000-08-18 | 2004-03-04 | ジェイ・エム・ヒューバー・コーポレーション | Method for producing dentifrice composition and product thereof |
| JP2015129082A (en) * | 2010-02-24 | 2015-07-16 | ジェイ・エム・フーバー・コーポレーション | Continuous silica production process and silica product prepared from the same |
-
1986
- 1986-04-25 JP JP9466586A patent/JPS62252312A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0341383A2 (en) * | 1988-05-07 | 1989-11-15 | Degussa Aktiengesellschaft | Finely divided precipitated silicas with a high structure, process for their preparation and their use |
| JP2004506782A (en) * | 2000-08-18 | 2004-03-04 | ジェイ・エム・ヒューバー・コーポレーション | Abrasive composition and method for producing the same |
| JP2004506671A (en) * | 2000-08-18 | 2004-03-04 | ジェイ・エム・ヒューバー・コーポレーション | Method for producing dentifrice composition and product thereof |
| JP2015129082A (en) * | 2010-02-24 | 2015-07-16 | ジェイ・エム・フーバー・コーポレーション | Continuous silica production process and silica product prepared from the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0465009B2 (en) | 1992-10-16 |
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