JPH0575692B2 - - Google Patents
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- Publication number
- JPH0575692B2 JPH0575692B2 JP58129136A JP12913683A JPH0575692B2 JP H0575692 B2 JPH0575692 B2 JP H0575692B2 JP 58129136 A JP58129136 A JP 58129136A JP 12913683 A JP12913683 A JP 12913683A JP H0575692 B2 JPH0575692 B2 JP H0575692B2
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- Prior art keywords
- water glass
- silica sol
- diluted
- liquid
- acid
- Prior art date
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Description
【発明の詳細な説明】
本発明は、地盤改良を目的として地中に注入す
る水ガラス系注入薬液であるシリカゾルの製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing silica sol, which is a water glass-based injection chemical solution that is injected into the ground for the purpose of soil improvement.
土木建設分野においては、建設施工又は建設後
の地盤の改良若しくは止水を目的として薬液注入
による地盤強化が広く行われている。 In the field of civil engineering and construction, ground reinforcement by chemical injection is widely practiced for the purpose of improving the ground or stopping water during construction or after construction.
現在、薬液注入工法に用いる薬液を大別してア
ルカリ系と非アルカリ系とがあり、前者は水ガラ
スをアルカリ領域で固結させるものであり、後者
は水ガラス中のアルカリを取り除いて、中性−酸
性領域で固結させるものである。又、この非アル
カリ系には、水ガラスと酸性液剤を直接反応させ
て、中性−酸性領域で固結させる直接法と、水ガ
ラスを多量の酸性液剤で処理して強酸性（PH３程
度以下）のシリカゾルを作り、これにアルカリ剤
を加えて中性−酸性領域で固結させる間接法とが
ある。本発明はこの間接法に用いる強酸性のシリ
カゾルの製造方法に関するものである。 Currently, the chemical solutions used in the chemical injection method can be roughly divided into alkaline and non-alkaline systems.The former solidifies water glass in the alkaline region, while the latter removes the alkali in the water glass and neutralizes it. It solidifies in an acidic region. In addition, for this non-alkaline system, there is a direct method in which water glass and an acidic liquid are directly reacted and solidified in a neutral to acidic region, and a method in which water glass is treated with a large amount of an acidic liquid to form a strongly acidic (pH 3 or less) ) There is an indirect method in which a silica sol is prepared, an alkali agent is added to the silica sol, and the silica sol is solidified in a neutral to acidic region. The present invention relates to a method for producing a strongly acidic silica sol used in this indirect method.
シリカゾルの製造方法は化学反応の原理すなわ
ち、水ガラスと酸とのゲル化機構から「酸の中に
水ガラスを加える」方法が適しており、現在ほと
んどこの方法を利用してシリカゾルを製造してい
る。 The method for producing silica sol is based on the chemical reaction principle, i.e. the gelling mechanism of water glass and acid, and the method of "adding water glass to acid" is suitable.Currently, most silica sol is produced using this method. There is.
強酸性を示す酸には鉱酸（硫酸、りんさ、塩酸
等）があり、50〜75重量％程度の希硫酸が現在最
も多く用いられている。薬液に用いる水ガラスに
は、JIS3号けい酸ソーダ（水ガラス）（モル比３）
又はそれ以上のモル比の水ガラスが最も多く使用
されている。 Strongly acidic acids include mineral acids (sulfuric acid, phosphoric acid, hydrochloric acid, etc.), and dilute sulfuric acid of about 50 to 75% by weight is currently most commonly used. JIS No. 3 sodium silicate (water glass) (molar ratio 3) is used for water glass used for chemical solutions.
Water glass with a molar ratio of 1,000 or more is most commonly used.
この希硫酸例えば75重量％硫酸とJIS3号水ガラ
スより強酸性のシリカゾルを製造するには、従
来、一定容量の容器に最終所望珪酸含有率を達成
するために必要な希釈水の全量を希硫酸に加えた
液に、所定量のJIS3号品原液を加圧噴射すること
によつてバツチ方式で行われていた。 To produce a strongly acidic silica sol using dilute sulfuric acid, e.g. 75% sulfuric acid and JIS No. 3 water glass, conventionally, the entire amount of dilution water required to achieve the final desired silicic acid content is poured into a container of a certain volume using diluted sulfuric acid. This was done in batches by spraying a predetermined amount of JIS No. 3 stock solution under pressure into the solution added to the water.
この方式では、高濃度の水ガラスを加圧噴射す
るために、水ガラスと硫酸の反応時に亜硫酸ガス
の如き臭気ガスを発生するため、作業環境上好ま
しくない欠点がある。この原因は、水ガラス濃度
と加圧噴射に起因することが大きいことから、最
終所望珪酸含有率を達成するために必要な希釈水
を水ガラス及び硫酸にふり分ける方が望ましい。
しかしながら、現場での作業が繁雑となり、正確
なPH管理が難しい欠点がある。 This method has a disadvantage in that it is undesirable in terms of the working environment, since odor gas such as sulfur dioxide gas is generated during the reaction between water glass and sulfuric acid because highly concentrated water glass is sprayed under pressure. Since this is largely caused by the water glass concentration and pressurized injection, it is preferable to distribute the dilution water necessary to achieve the final desired silicic acid content into the water glass and sulfuric acid.
However, it has the disadvantage that on-site work is complicated and accurate pH control is difficult.
この問題を解決するため、発明者は最終所望珪
酸含有率を達成するために必要な希釈水の全量を
水ガラス原液に添加した希釈水ガラス液を高濃度
の強酸性液に添加することを主旨としたシリカゾ
ルの製造方法を発明し、特願昭53−22057号とし
て特許出願している。 In order to solve this problem, the inventor's idea is to add the diluted water glass solution, which is obtained by adding the entire amount of dilution water necessary to achieve the final desired silicic acid content to the highly concentrated strong acid solution. He invented a method for producing silica sol and filed a patent application as Japanese Patent Application No. 1983-22057.
この方法は、化学反応の原理から最も適したシ
リカゾルの製造方法であるが、実際現場で多量に
作るには次のような問題点がある。 Although this method is the most suitable method for producing silica sol based on the principle of chemical reaction, there are the following problems in producing it in large quantities on-site.
(イ) 攪拌機構を有した一定容器の中に水量に硫酸
を入れ、この中に多量の希釈水ガラス液を添加
することは、添加当初は液面が非常に低いため
飛び散る欠点がある。(b) When sulfuric acid is placed in a certain amount of water in a container equipped with a stirring mechanism, and a large amount of diluted water glass solution is added thereto, there is a drawback that the liquid level is very low at the beginning of addition, causing the solution to splatter.
(ロ) 一定容器の中に少量の硫酸を入れ、この中に
多量の希釈水ガラス液を加圧噴射注入すること
により、硫酸の攪拌を行う場合にも(イ)と同様な
液面が非常に低いため飛び散る欠点がある。(b) When stirring sulfuric acid by placing a small amount of sulfuric acid in a certain container and injecting a large amount of diluted water glass liquid into the container under pressure, the same liquid level as in (a) can be achieved. It has the disadvantage of scattering because it is low.
(ハ) また、上記(イ)、(ロ)はいずれもバツチ方式であ
るので、１回毎に製造することとなり、短時間
に多量のシリカゾルを製造できにない欠点があ
る。(c) In addition, since both (a) and (b) above are batch methods, they must be produced one time at a time, which has the disadvantage that a large amount of silica sol cannot be produced in a short period of time.
通常、強酸性のシリカゲルを製造するに使用す
る水ガラスのSiO2濃度は容量で10〜25％程度で
ある。この程度の水ガラスからPH１〜３程度のシ
リカゾルを作るには、75重量％硫酸を水ガラス量
（容量）の約1/5前後の量を加えれば充分である。
すなわち、３号水ガラス濃度（容量）10〜25％の
強酸性のシリカゾルを作るには、75重量％硫酸は
容量で２〜５％程度であり、希釈水を水ガラス側
に加えると、１m3のシリカゾルを作るのに980〜
950前後の希釈水ガラス液と20〜50程度の硫
酸となる。 Usually, the SiO 2 concentration of water glass used to produce strongly acidic silica gel is about 10 to 25% by volume. To make a silica sol with a pH of about 1 to 3 from this amount of water glass, it is sufficient to add 75% by weight sulfuric acid in an amount of about 1/5 of the amount (volume) of the water glass.
In other words, in order to make a strongly acidic silica sol with a No. 3 water glass concentration (volume) of 10 to 25%, 75% sulfuric acid is about 2 to 5% by volume, and when dilution water is added to the water glass side, 1 m 980 ~ to make silica sol 3
The result is a diluted water glass solution of about 950 and sulfuric acid of about 20 to 50.
このことは、硫酸の約20〜50倍前後の希釈水ガ
ラスを用いることになる。本来「何々の中に加え
る」とは加えるものが加えらるものより少である
べきものであり、これからも「多量の中に少量を
加える」べきものである。強酸性のシリカゾル液
の製造方法は化学的には「酸の中に水ガラスを加
える」であり、又、その作り易さは「できるだけ
水ガラスを希釈した水ガラス液」であり、この２
つの条件を満足してシリカゾル液を簡単で安価な
設備で多量に作るには多くの問題を含んでいる。 This means using diluted water glass that is about 20 to 50 times more diluted than sulfuric acid. Originally, ``adding to so-and-so'' meant that what was added should be less than what was added, and from now on, it should be ``adding a small amount to a large amount.'' Chemically speaking, the manufacturing method of strongly acidic silica sol liquid is ``adding water glass to acid'', and the ease of production is ``water glass liquid diluted as much as possible''.
There are many problems involved in producing a large amount of silica sol liquid using simple and inexpensive equipment while satisfying the following conditions.
本発明の目的は、製造が容易で、簡単な安価な
設備で連続して多量に製造することができるシリ
カゾルの製造方法を提供するにある。 An object of the present invention is to provide a method for producing silica sol that is easy to produce and can be produced continuously in large quantities using simple and inexpensive equipment.
本発明のシリカゾルの製造方法は、発明者が、
種々の実験をくり返した結果、強酸性のシリカゾ
ルの作り易さの条件は、第１に「酸の中に水ガラ
ス」よりも「できるだけ水ガラス濃度を希釈す
る」の方が大であることをつきとめ、「最終所望
珪酸含有率を達成するために必要な希釈水の全量
を水ガラス原液に添加した希釈水ガラス液を用い
る」こととし、また、第２に従来のバツチ方式で
シリカゾルを製造する方が、若干高濃度（SiO2
の含有量大の）シリカゾルができ易い利点がある
が、反面、装置費用が割高になることと、PH管理
が難しいという欠点を包含していたため、小規模
の設備で多量のシリカゲルを製造できる方法とし
て、「ポンプ等で希釈水ガラス液を連続的に移動
（液送）しながら、該移動中の希釈水ガラス液中
に垂直に高濃度の強酸性鉱酸液をノズルから連続
的に加圧噴射する」という連続混合方式とし、さ
らに、第３に希釈水ガラス液と強酸性鉱酸液とを
瞬時（ゲルタイムでいえば、１秒程度以下）に混
合しなければ均一なシリカゾル（溶液）が得られ
ないため、両液を混合させる混合装置として、上
端が密閉された円筒部と、この円筒部の下端に連
設され、下部に吐出口の設けた円錐部とからなる
ものを用い、円筒部内にその軸線に対して直角に
導入した多量の希釈水ガラス液を連続的に移動し
ながら、これに垂直に少量の強酸性鉱酸液を連続
的に加圧噴射することによつて両液を乱液状態で
旋回混合することとしたものである。 In the method for producing silica sol of the present invention, the inventors
After repeating various experiments, we found that the conditions for making a strongly acidic silica sol are, firstly, ``diluting the concentration of water glass as much as possible'' rather than ``water glass in acid''. They determined that ``a diluted water glass solution was added to the water glass stock solution by adding the entire amount of dilution water necessary to achieve the final desired silicic acid content,'' and secondly, a silica sol was produced using the conventional batch method. slightly higher concentration (SiO 2
Although it has the advantage of being able to easily produce silica sol (with a high content of ``While the diluted water glass liquid is continuously moved (liquid feeding) with a pump, etc., a highly concentrated strong acidic mineral acid liquid is continuously pressurized vertically into the moving diluted water glass liquid from a nozzle. Thirdly, if the diluted water glass solution and the strong mineral acid solution are not mixed instantaneously (about 1 second or less in terms of gel time), a uniform silica sol (solution) will not be produced. Therefore, as a mixing device for mixing both liquids, a device consisting of a cylindrical part whose upper end is sealed and a conical part connected to the lower end of this cylindrical part and has a discharge port at the bottom is used. While continuously moving a large amount of diluted water glass solution introduced perpendicularly to the axis of the chamber, a small amount of strong acidic mineral acid solution is continuously injected under pressure perpendicularly to the diluted water glass solution. The mixture was swirled and mixed in a turbulent state.
すなわち、本発明による強酸性のシリカゾルの
製造方法は、酸の中に水ガスを加えて強酸性のシ
リカゾルを得るシリカゾルの製造方法において、
最終所望珪酸含有率を達成するために必要な希釈
水の全量を水ガラス原液に添加して希釈した希釈
水ガラス液を調製した後、上端が密閉された円筒
部と、この円筒部の下端に連設され、下部に吐出
口を設けた円錐部とからなる混合装置の円筒部内
にその軸線に対して直角に導入した多量の希釈水
ガラス液を連続的に移動しながら、これに垂直に
少量の強酸性鉱酸液を連続的に加圧噴射しかつ両
液を乱流状態で旋回混合することを特徴とする。 That is, the method for producing a strongly acidic silica sol according to the present invention is a method for producing a silica sol in which a strongly acidic silica sol is obtained by adding water gas to an acid.
After preparing a diluted water glass liquid by adding the entire amount of dilution water required to achieve the final desired silicic acid content to the water glass stock solution, a cylindrical part with a sealed upper end and a lower end of this cylindrical part are While continuously moving a large amount of diluted water glass liquid introduced perpendicularly to the axis of the cylindrical part of the mixing device, which consists of a conical part and a conical part with a discharge port at the bottom, a small amount of diluted water glass is introduced perpendicularly to the cylindrical part of the mixing device. The method is characterized by continuously injecting a strongly acidic mineral acid solution under pressure and swirling and mixing both solutions in a turbulent state.
本発明のシリカゾル液の製造に用いる水ガラス
は、JIS3号品（モル比3.0）又は、それ以上のモ
ル比の水ガラスである。又、酸は硫酸、塩酸、リ
ン酸等の強酸性の鉱酸が好ましい。 The water glass used in the production of the silica sol liquid of the present invention is JIS No. 3 (molar ratio 3.0) or water glass with a molar ratio higher than that. Further, the acid is preferably a strongly acidic mineral acid such as sulfuric acid, hydrochloric acid, or phosphoric acid.
本発明の方法によつて製造される強酸性のシリ
カゾル濃度は、SiO2が10〜４重量％程度であり、
好ましくは８−４重量％であるが、その濃度は水
ガラスのモル比、鉱酸の種類や連続的に加圧噴射
圧等により変動するものであることは言うまでも
ない。 The concentration of the strongly acidic silica sol produced by the method of the present invention is approximately 10 to 4% by weight of SiO2 ,
It is preferably 8-4% by weight, but it goes without saying that the concentration varies depending on the molar ratio of water glass, the type of mineral acid, the continuous pressurizing injection pressure, etc.
第１図に本発明の強酸性のシリカゾルの製造方
法を実施する装置の一実施例を示す。 FIG. 1 shows an embodiment of an apparatus for carrying out the method for producing a strongly acidic silica sol of the present invention.
図１において、１は希釈ガラス液槽、４は高濃
度の高酸液槽である。希釈水ガラス液槽１中の希
釈水ガラス及び鉱酸液槽４中の高濃度鉱酸液は、
それぞれ圧送ポンプ３により圧送管２を通つて混
合装置５に圧送される。混合装置５は、上端が密
閉された円筒部と、この円周部の下端に連接さ
れ、下部に吐出口を設けた円錐部とからなり、円
筒部内にその軸線に対して直角に導入した多量希
水ガラス液を連続的に移動しながら、この希釈水
ガラス液流中に垂直に高濃度の少量の鉱酸液を加
圧噴射ノズル６により連続的に加圧噴射しかつ両
者は乱流状態で旋回混合することによつて、瞬時
に混合され、瞬結ゲルを析出させることなく、均
一な強酸性のシリカゲルが生成する。生成したシ
リカゾルはシリカゾル貯槽７内に落下する。 In FIG. 1, 1 is a dilution glass liquid tank, and 4 is a high concentration high acid liquid tank. The diluted water glass in the diluted water glass liquid tank 1 and the highly concentrated mineral acid liquid in the mineral acid liquid tank 4 are as follows:
Each of them is pumped by a pressure pump 3 through a pressure feed pipe 2 to a mixing device 5 . The mixing device 5 consists of a cylindrical part whose upper end is sealed and a conical part connected to the lower end of this circumferential part and provided with a discharge port at the bottom. While continuously moving the diluted water glass liquid, a small amount of highly concentrated mineral acid liquid is vertically injected vertically into the diluted water glass liquid flow using a pressurized injection nozzle 6, and both are in a turbulent flow state. By swirling the silica gel, the mixture is instantaneously mixed, and a uniform strongly acidic silica gel is produced without precipitation of flash-setting gel. The generated silica sol falls into the silica sol storage tank 7.
以下、本発明の実施例及び比較例を挙げて、本
発明は更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples of the present invention.
実施例 １
添付の図面の装置を用いて、連続混合方式によ
るシリカゾルの製造を行つた。Example 1 Silica sol was produced by a continuous mixing method using the apparatus shown in the attached drawings.
200入りのポリエチレン製容器にモル比3.4、
比重1.32、SiO224.1重量％の水ガラス37.5と希
釈水107.2を入れ良く混合した。 Molar ratio 3.4 in a polyethylene container containing 200,
37.5 of water glass with a specific gravity of 1.32 and 24.1% by weight of SiO 2 and 107.2 of dilution water were added and mixed well.
得られた希釈水ガラス液を圧送ポンプで20／
分の吐出量で液送（移動）させながら、該移動中
の希釈水ガラス液に75重量％工業用硫酸7.5を
5.3／分の吐出量でノズルより0.5Kgｆ／cm2の圧
力で噴射したところ瞬結ゲルを生成することなく
完全なシリカゾル液（PH＝2.2）を製造すること
ができた。 The obtained diluted water glass liquid was pumped with a pressure pump for 20/20 minutes.
While transporting (moving) the liquid at a discharge rate of
When sprayed from the nozzle at a pressure of 0.5 Kgf/cm 2 at a discharge rate of 5.3/min, a complete silica sol solution (PH = 2.2) could be produced without generating flash gel.
比較例 １
実施例１と同じ連続混合方式によつてシリカゾ
ルの製造を行つた。Comparative Example 1 A silica sol was produced using the same continuous mixing method as in Example 1.
200ｇ入りのポリエチレン製容器に、実施例１
と同じ水ガラス37.5ｇと希釈水37.5を入れ良く
混合した。 Example 1 in a 200g polyethylene container
Add 37.5 g of the same water glass and 37.5 g of dilution water and mix well.
得られた希釈水ガラス液を圧送ポンプ20／分
の吐出量で放送（移動）させながら、該移動中の
希釈水ガラス液に、実施例１と同じ硫酸7.3に
水67.7を加えた希釈硫酸を20ｇ／分の吐出量で
ノズルより、0.5Kgｆ／cm2の圧力で噴射したとこ
ろ、多量の瞬結ゲルを生じ、実用に耐えるシリカ
ゾル液は得られなかつた。 While broadcasting (moving) the obtained diluted water glass liquid with a pressure pump at a discharge rate of 20/min, diluted sulfuric acid, which is the same as in Example 1, in which 7.3 parts of sulfuric acid and 67.7 parts of water were added, was added to the moving diluted water glass liquid. When the silica sol was sprayed from a nozzle at a pressure of 0.5 Kgf/cm 2 at a discharge rate of 20 g/min, a large amount of instantaneous gel was produced, and a silica sol liquid suitable for practical use could not be obtained.
なお、ノズル径は、20／分の吐出量で0.5Kg
ｆ／cm2の噴射圧となるよう調製した。 The nozzle diameter is 0.5Kg at a discharge rate of 20/min.
The injection pressure was adjusted to be f/cm 2 .
以上説明したように、本発明のシリカゾルの製
造方法によれば、上端が密閉された円筒部と、こ
の円筒部の下端が連設され、下部の吐出口を設け
た円錐部とからなる混合装置を用い、円筒部内に
その軸線に対して直角に導入した多量の希釈水ガ
ラス液を連続的に移動しながら、これに垂直に少
量の強酸性鉱酸液を連続的に加圧噴射しかつ両液
を乱流状態で旋回混合することによつて、両液が
瞬時に混合されるので、瞬結ゲルを析出すること
なく、均一な強酸性のシリカゾルを従来のバツチ
方式に比して容易に、簡単で安価な設備で連続し
て多量に製造することができる。 As explained above, according to the silica sol manufacturing method of the present invention, the mixing device includes a cylindrical part whose upper end is sealed, and a conical part which is connected to the lower end of the cylindrical part and has a lower discharge port. While continuously moving a large amount of diluted water glass liquid introduced perpendicularly to the axis of the cylinder using a By swirling and mixing the liquids in a turbulent state, both liquids are instantly mixed, making it easier to produce a uniform strongly acidic silica sol without precipitating an instant gel than with the conventional batch method. It can be manufactured continuously in large quantities using simple and inexpensive equipment.
第１図は本発明の方法を実施する装置の実施例
の配置図である。
１……希釈水ガラス槽、２……圧送管、３……
圧送ポンプ、４……高濃度鉱酸液槽、５……混合
装置、６……加圧噴射ノズル、７……シリカゾル
槽。
FIG. 1 is a layout diagram of an embodiment of an apparatus for carrying out the method of the invention. 1... Dilution water glass tank, 2... Pressure feeding pipe, 3...
Pressure pump, 4... High concentration mineral acid liquid tank, 5... Mixing device, 6... Pressurized injection nozzle, 7... Silica sol tank.
Claims (1)
ルを得るシリカゾルの製造方法において、最終所
望珪酸含有率を達成するために必要な希釈水の全
量を水ガラス原液に添加して、希釈した希釈水ガ
ラス液を調製した後、上端が密閉された円筒部
と、この円筒部の下端に連設され、下部に吐出口
を設けた円錐部とからなる混合装置の円筒部内に
その軸線に対して直角に導入した多量の希釈水ガ
ラス液を連続的に移動しながら、これに垂直に少
量の強酸性鉱酸液を連続的に加圧噴射しかつ両液
を乱流状態で旋回混合することを特徴とするシリ
カゾルの製造方法。1. In a silica sol production method in which a strongly acidic silica sol is obtained by adding water glass to an acid, the entire amount of dilution water necessary to achieve the final desired silicic acid content is added to the water glass stock solution to obtain a diluted diluted silica sol. After preparing the water glass liquid, it is placed along its axis into a cylindrical part of a mixing device consisting of a cylindrical part whose upper end is sealed and a conical part connected to the lower end of this cylindrical part and has a discharge port at the bottom. While continuously moving a large amount of diluted water glass liquid introduced at right angles, a small amount of strong acidic mineral acid liquid is continuously injected under pressure perpendicularly to this, and both liquids are swirled and mixed in a turbulent state. Characteristic method for producing silica sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12913683A JPS6021811A (en) | 1983-07-15 | 1983-07-15 | Preparation of silica sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12913683A JPS6021811A (en) | 1983-07-15 | 1983-07-15 | Preparation of silica sol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6021811A JPS6021811A (en) | 1985-02-04 |
| JPH0575692B2 true JPH0575692B2 (en) | 1993-10-21 |
Family
ID=15002001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12913683A Granted JPS6021811A (en) | 1983-07-15 | 1983-07-15 | Preparation of silica sol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010087262A1 (en) | 2009-01-30 | 2010-08-05 | 旭化成ケミカルズ株式会社 | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0620270U (en) * | 1992-05-15 | 1994-03-15 | 冨士シール工業株式会社 | Heat shrinkable sleeve body |
| DE19515316C1 (en) * | 1995-04-19 | 1996-08-29 | Mannesmann Ag | Method for operating a mold |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5134244A (en) * | 1974-09-17 | 1976-03-23 | Asahi Chemical Ind | SANHENSEIKE ISANENSETSUCHAKUZAI |
| JPS5952247B2 (en) * | 1977-04-11 | 1984-12-19 | 三信建設工業株式会社 | Grout injection method |
| JPS6057476B2 (en) * | 1977-05-20 | 1985-12-14 | 強化土エンジニヤリング株式会社 | Ground injection method |
| JPS5827779A (en) * | 1981-08-10 | 1983-02-18 | Kyokado Eng Co Ltd | Injection method of stratum |
-
1983
- 1983-07-15 JP JP12913683A patent/JPS6021811A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010087262A1 (en) | 2009-01-30 | 2010-08-05 | 旭化成ケミカルズ株式会社 | Method for producing silica-supported catalyst, and method for producing unsaturated carboxylic acid or unsaturated nitrile |
| EP3466533A1 (en) | 2009-01-30 | 2019-04-10 | Asahi Kasei Kabushiki Kaisha | Methods for the oxidation or ammoxydation of propane characterized by the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6021811A (en) | 1985-02-04 |
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