JPH06233904A - Dissolution of raw material of silica type flocculating solution, method for producing silica type flocculating solution and apparatus therefor - Google Patents
Dissolution of raw material of silica type flocculating solution, method for producing silica type flocculating solution and apparatus thereforInfo
- Publication number
- JPH06233904A JPH06233904A JP4588593A JP4588593A JPH06233904A JP H06233904 A JPH06233904 A JP H06233904A JP 4588593 A JP4588593 A JP 4588593A JP 4588593 A JP4588593 A JP 4588593A JP H06233904 A JPH06233904 A JP H06233904A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- sulfuric acid
- liquid
- raw material
- tank
- 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 abstract description 359
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 179
- 238000004090 dissolution Methods 0.000 title claims abstract description 93
- 239000002994 raw material Substances 0.000 title claims abstract description 76
- 230000003311 flocculating effect Effects 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 210
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 149
- 230000001112 coagulating effect Effects 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 26
- 238000005345 coagulation Methods 0.000 claims description 25
- 230000015271 coagulation Effects 0.000 claims description 25
- 230000002776 aggregation Effects 0.000 claims description 12
- 238000004220 aggregation Methods 0.000 claims description 12
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
- 239000008399 tap water Substances 0.000 description 19
- 235000020679 tap water Nutrition 0.000 description 19
- 238000001879 gelation Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- 239000010802 sludge Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000012937 correction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水中に含有される溶解物
質、エマルジョン物質、拡散剤、油分、浮遊物質等の吸
着、凝集、排除に用いるシリカ系凝集液を製造するため
の原料となるシリカ系凝集液原料の溶解方法、シリカ系
凝集液の製造方法及び装置に関し、詳しくはモノマーシ
リカの含有割合の高いシリカ系凝集液を得るためのシリ
カ系凝集液原料の溶解方法、シリカ系凝集液の製造方法
並びにコンパクトな設計が可能なシリカ系凝集液の製造
装置に関する。FIELD OF THE INVENTION The present invention relates to silica as a raw material for producing a silica-based coagulating liquid used for adsorption, coagulation and elimination of dissolved substances, emulsion substances, diffusing agents, oils and suspended substances contained in water. Method of dissolving raw material of flocculant-based flocculating liquid, method and apparatus for producing flocculent of flocculating silica, and more specifically, method of dissolving raw material of flocculant of flocculating liquid for obtaining high-purity silica-based flocculating liquid containing silica, The present invention relates to a manufacturing method and a silica-based coagulating liquid manufacturing apparatus capable of being compactly designed.
【０００２】[0002]
【発明の背景】従来、汚水や各種廃水中の溶解物質（イ
オン類）や有機、無機の微粒子、浮遊物質等の抽出や凝
集、除去には主としてＡｌ系凝集液、Ｆｅ系凝集液、高
分子系凝集液が用いられている。BACKGROUND OF THE INVENTION Conventionally, Al-based flocculating liquids, Fe-based flocculating liquids, and polymers are mainly used for extraction, aggregation and removal of dissolved substances (ions), organic and inorganic fine particles, suspended substances, etc. in wastewater and various wastewaters. A system flocculant is used.
【０００３】かかる従来のＡｌ系、Ｆｅ系凝集液は、有
機化学物質や油分、油エマルジョン、界面活性剤等を吸
着したり、凝集する機能は極めて弱いため、実際に使用
するに際しては、大量のＡｌ系、Ｆｅ系凝集液を用い、
大量の水酸化アルミニウムや水酸化鉄の沈澱を生成させ
て（更にアルカリも添加し）、それらの沈澱物に物理的
に油分等を引っかけ、更に高分子凝集剤を投与してフロ
ック形状を大きくし、加圧浮上、又は沈降によりフロッ
クを水と分離する方法が採られている。Such conventional Al-based and Fe-based coagulating liquids have a very weak function of adsorbing or coagulating organic chemical substances, oils, oil emulsions, surfactants, etc. Using Al-based and Fe-based aggregation liquids,
A large amount of aluminum hydroxide or iron hydroxide precipitates are formed (addition of alkali), oils and the like are physically caught on these precipitates, and a polymer flocculant is further administered to increase the floc shape. The method of separating flocs from water by pressure floatation or sedimentation is adopted.
【０００４】かかる複雑な処理を行っても満足な結果を
得ることは難しく、更に投与した凝集剤に起因する大量
のスラッジが発生し、その処理コストも併せて負担せね
ばならない問題がある。It is difficult to obtain a satisfactory result even if such a complicated treatment is performed, and further, a large amount of sludge is generated due to the coagulant administered, and there is a problem that the treatment cost must be borne.
【０００５】かかる問題を解決するため、特願平１−２
９６３７１号明細書において、シリカ系凝集液が提案さ
れている。かかるシリカ系凝集液はそれらの有機化学物
質、油分、油エマルジョン、界面活性剤等を効果的に吸
着、凝集し、発生するスラッジも極度に少なくなるとい
う利益が得られる。To solve this problem, Japanese Patent Application No. 1-2
In the specification of 96371, a silica-based aggregation liquid is proposed. Such a silica-based flocculating liquid has the advantage that it effectively adsorbs and flocculates these organic chemicals, oils, oil emulsions, surfactants, etc., and the sludge generated is extremely reduced.
【０００６】従来のシリカ系凝集液はシリカ系凝集液原
料を中性酸又は還元酸、具体的には希硫酸に溶解して得
られるが、シリカ系凝集液原料を溶解する際に、水にシ
リカ系凝集液原料を溶解した後、希硫酸を添加する方法
ではシリカ系凝集液原料がゾル・ゲル状となってしま
い、モノマーシリカの割合が少なく安定性に欠ける欠点
があることがわかった。従来技術では希硫酸にシリカ系
凝集液原料を添加する旨の記載は認められるが、添加順
序がモノマーシリカの割合に大きく影響する旨の認識は
全く存在しない。The conventional silica-based flocculating liquid is obtained by dissolving the silica-based flocculating liquid raw material in a neutral acid or a reducing acid, specifically dilute sulfuric acid. When the silica-based flocculating liquid raw material is dissolved, it is dissolved in water. It was found that the method of adding dilute sulfuric acid after dissolving the silica-based flocculant raw material causes the silica-based flocculant raw material to be in a sol-gel state, which has a drawback that the ratio of the monomer silica is small and the stability is insufficient. Although there is a statement in the prior art that a silica-based flocculant raw material is added to dilute sulfuric acid, there is no recognition that the order of addition has a large effect on the proportion of monomer silica.
【０００７】また輸送の効率性等から２倍量の原料を溶
解したシリカ系凝集液が求められているが、製造法によ
っては、必要とされるモノマーシリカが少なくなってし
まうことがわかった。即ち、１Ｎの希硫酸１リットルに
シリカ系凝集液原料を溶解当量分溶解すると、１Ｎのシ
リカ系凝集液が得られるが、これと同じ様にして２Ｎの
シリカ系凝集液を得ようとして、２Ｎの希硫酸１リット
ルにシリカ系凝集液原料を溶解当量分（１Ｎの時の倍の
量）溶解すると、シリカ系凝集液原料の添加によって部
分的にｐＨの上昇するところではシリカの重合化が起こ
り、またｐＨの低いところでは無水シリカが生成された
りして、必要とされるモノマーシリカが少なくなってし
まうことがわかった。[0007] Further, a silica-based flocculating liquid in which twice as much raw material is dissolved is required in view of transportation efficiency and the like, but it has been found that the required monomer silica is reduced depending on the production method. That is, when the silica-based flocculant raw material is dissolved in 1 liter of 1N dilute sulfuric acid to dissolve the same amount, a 1N silica-based flocculation liquid can be obtained. When the silica-based flocculant raw material is dissolved in 1 liter of dilute sulfuric acid, the equivalent amount (double the amount when 1N) is dissolved, silica is polymerized where the pH is partially increased by the addition of the silica-based flocculant raw material. It was also found that anhydrous silica is produced at a low pH, so that less monomer silica is required.
【０００８】更に、従来のＡｌ系凝集液、Ｆｅ系凝集
液、高分子系凝集液を使用する際には、少なくとも２液
を必要とし、それだけでも装置の数が多くなり、装置の
コンパクト化を困難にしていた。また特願平１−２９６
３７１号の技術では、シリカ系凝集液の具体的な製造方
法及び装置は明らかでなく、実際の装置に適用できる製
造方法及び装置の開発が望まれていた。Furthermore, when using the conventional Al-based coagulating liquid, Fe-based coagulating liquid, and polymer-based coagulating liquid, at least two liquids are required, which alone increases the number of devices and makes the device compact. It was difficult. In addition, Japanese Patent Application No. 1-296
In the technology of No. 371, the specific method and apparatus for producing a silica-based coagulating liquid are not clear, and the development of a method and apparatus applicable to an actual apparatus has been desired.
【０００９】[0009]
【発明が解決しようとする課題】そこで、本発明の課題
は、第１にモノマーシリカの含有割合が多く安定性が高
いシリカ系凝集液が得られるシリカ系凝集液原料の溶解
方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is, firstly, to provide a method for dissolving a silica-based flocculant raw material which gives a silica-based flocculant having a high content of monomer silica and high stability. It is in.
【００１０】第２の課題は、輸送コストが低くて経済効
率が高くかつ原料を数倍量溶解できるシリカ系凝集液原
料の溶解方法を提供することにある。A second object of the present invention is to provide a method for dissolving a silica-based coagulating liquid raw material which has a low transportation cost, high economic efficiency, and can dissolve the raw material several times.
【００１１】第３の課題は、実際の装置に適用できるシ
リカ系凝集液の製造方法を提供することにある。A third object is to provide a method for producing a silica-based coagulating liquid which can be applied to an actual device.
【００１２】第４の課題は、コンパクトなシリカ系凝集
液の製造装置を提供することにある。A fourth object is to provide a compact silica-based flocculating liquid manufacturing apparatus.
【００１３】[0013]
【課題を解決するための手段】本発明者は上記課題を解
決すべく鋭意検討を重ねた結果、本発明に至ったもので
ある。The inventor of the present invention has come to the present invention as a result of extensive studies to solve the above problems.
【００１４】即ち、本発明に係るシリカ系凝集液原料の
溶解方法の第１は、シリカ系凝集液原料を希硫酸で溶解
してシリカ系凝集液を製造する際に、溶解槽に一定量の
水を供給し、該溶解槽内の水を撹拌しながら、硫酸を注
入して所定濃度の希硫酸を作成した後、該溶解槽内に特
定のＣａ塩基度を有するシリカ系凝集液原料を前記希硫
酸で溶解できる溶解平衡量を投入することを特徴とす
る。That is, the first method of dissolving the silica-based flocculating liquid raw material according to the present invention is to dissolve a fixed amount of the silica-based flocculating liquid raw material in a dissolving tank when the silica-based flocculating liquid raw material is dissolved with dilute sulfuric acid. While supplying water and stirring the water in the dissolution tank, sulfuric acid was injected to prepare dilute sulfuric acid having a predetermined concentration, and then the silica-based coagulation liquid raw material having a specific Ca basicity was added to the dissolution tank. It is characterized in that a dissolution equilibrium amount that can be dissolved in diluted sulfuric acid is added.
【００１５】また本発明に係るシリカ系凝集液原料の溶
解方法の第２は、モノマーシリカの含有割合が高く、か
つ高濃度シリカ系凝集液が得られるシリカ系凝集液原料
の溶解方法において、上記第１の方法によってシリカ系
凝集液を得、次いで硫酸を前記希硫酸と同じ当量分だけ
添加し、再度前記シリカ系凝集液原料を該希硫酸で溶解
できる溶解平衡量を投入し、必要によりこの操作を繰り
返すことを特徴とする。The second method of dissolving the silica-based flocculating liquid raw material according to the present invention is the method for dissolving the silica-based flocculating liquid raw material having a high content of monomer silica and capable of obtaining a high-concentration silica-based flocculating liquid raw material. A silica-based coagulating liquid is obtained by the first method, sulfuric acid is added in the same amount as the dilute sulfuric acid, and a dissolution equilibrium amount capable of dissolving the silica-based coagulating liquid raw material in the dilute sulfuric acid is added again. Characterized by repeating the operation.
【００１６】更に、本発明に係るシリカ系凝集液の製造
方法は、特定のＣａ塩基度を有するシリカ系凝集液原料
を希硫酸で溶解してシリカ系凝集液を製造するシリカ系
凝集液の製造方法において、溶解槽に一定量の水を供給
し、該溶解槽内の水を撹拌しながら、硫酸を注入して所
定濃度の希硫酸を作成した後、該溶解槽内にシリカ系凝
集液原料を投入し、次いで溶解平衡に達するまで保持し
た後、次に必要により該溶解槽内のｐＨが２．５を越え
ているかいないかを判断し、該ｐＨが２．５未満である
場合にはｐＨが２．５を越えるまで数分間保持し、一方
ｐＨが２．５以上である場合には次に濾過するか否かを
判断し、濾過しない場合にはそのままシリカ系凝集液と
し、また濾過する場合には濾液をシリカ系凝集液とする
ことを特徴とする。Further, the production of the silica-based flocculating liquid according to the present invention
The method is a silica-based aggregate liquid raw material having a specific Ca basicity.
Silica-based method for producing silica-based coagulation liquid by dissolving dilute sulfuric acid with dilute sulfuric acid
Supplying a fixed amount of water to the dissolution tank in the method of producing a coagulation liquid
Then, while stirring the water in the dissolution tank, add sulfuric acid.
After preparing dilute sulfuric acid with a constant concentration, the silica-based coagulum is placed in the dissolution tank.
Add the material to be collected, and then hold it until the dissolution equilibrium is reached.
Then, if necessary, the pH in the dissolution tank exceeds 2.5
The pH is less than 2.5.
In some cases, hold for several minutes until pH exceeds 2.5, while
If the pH is above 2.5, ask whether to filter next.
Judge and if not filtered, use silica-based coagulation liquid as it is.
In addition, when filtering, use the filtrate as a silica-based coagulation liquid
It is characterized by
【００１７】更に、本発明に係るシリカ系凝集液の製造
装置は、溶解槽と、該溶解槽に一定量の水を供給する水
供給手段と、該溶解槽内の液を撹拌する撹拌手段と、前
記水供給手段から水が供給された溶解槽に硫酸を注入す
るための硫酸注入手段と、該溶解槽にシリカ系凝集液原
料を供給する手段と、該溶解槽内のｐＨが２．５以上で
ありかつ該溶解槽内の溶液を濾過しない場合にシリカ系
凝集液を受け入れるための凝集液タンクとを有すること
を特徴とする。Further, the apparatus for producing a silica-based coagulating liquid according to the present invention comprises a dissolution tank, water supply means for supplying a fixed amount of water to the dissolution tank, and stirring means for stirring the liquid in the dissolution tank. A sulfuric acid injecting means for injecting sulfuric acid into a dissolution tank to which water has been supplied from the water supply means; a means for supplying a silica-based flocculant raw material into the dissolution tank; and a pH in the dissolution tank of 2.5. It is characterized in that it has a flocculating liquid tank for receiving the silica-based flocculating liquid when the solution in the dissolution tank is not filtered.
【００１８】更に又、本発明に係るシリカ系凝集液の製
造装置は、溶解槽と、該溶解槽に一定量の水を供給する
水供給手段と、該溶解槽内の液を撹拌する撹拌手段と、
前記水供給手段から水が供給された溶解槽に硫酸を注入
するための硫酸注入手段と、該溶解槽にシリカ系凝集液
原料を供給する手段と、該溶解槽内のｐＨが２．５以上
でありかつ該溶解槽内の溶液を濾過する場合に該濾液で
あるシリカ系凝集液を受け入れるための凝集液タンクと
を有することを特徴とする。Furthermore, the apparatus for producing a silica-based coagulating liquid according to the present invention comprises a dissolution tank, water supply means for supplying a fixed amount of water to the dissolution tank, and stirring means for stirring the liquid in the dissolution tank. When,
Sulfuric acid injecting means for injecting sulfuric acid into the dissolution tank to which water is supplied from the water supply means, means for supplying the silica-based flocculant raw material to the dissolution tank, and pH in the dissolution tank of 2.5 or more. And a flocculating liquid tank for receiving the silica-based flocculating liquid which is the filtrate when the solution in the dissolving tank is filtered.
【００１９】以下、本発明について詳細に説明する。The present invention will be described in detail below.
【００２０】シリカ系凝集液原料の溶解方法の第１の特
徴は、溶解槽に一定量の水を供給し、該溶解槽内の液を
撹拌しながら、硫酸を注入して所定濃度の希硫酸を作成
した後、該溶解槽内に特定のＣａ塩基度を有するシリカ
系凝集液原料を前記希硫酸で溶解できる溶解平衡量を投
入することである。即ち、希硫酸の希釈水溶液を作成し
た後、シリカ系凝集液原料を投入するのが本質であり、
この逆にシリカ系凝集液原料の水溶液を作成した後、硫
酸を添加した場合には、シリカ系凝集液原料がゾル・ゲ
ル状となってしまい、モノマーシリカの割合が少なくな
ってしまい、本発明の目的を達成できない。The first characteristic of the method for dissolving the silica-based coagulating liquid raw material is to supply a fixed amount of water to the dissolving tank, and while stirring the solution in the dissolving tank, inject sulfuric acid to dilute sulfuric acid having a predetermined concentration. After preparing the above, a dissolution equilibrium amount capable of dissolving the silica-based flocculating liquid raw material having a specific Ca basicity in the dilute sulfuric acid is charged into the dissolution tank. That is, it is essential to add a silica-based flocculant raw material after preparing a diluted aqueous solution of dilute sulfuric acid.
On the contrary, when sulfuric acid is added after the aqueous solution of the silica-based coagulating liquid raw material is prepared, the silica-based coagulating liquid raw material becomes a sol-gel state, and the ratio of the monomer silica is reduced. Can not achieve the purpose of.
【００２１】またシリカ系凝集液原料の溶解方法の第２
の特徴は、溶解槽に一定量の水を供給し、該溶解槽内の
液を撹拌しながら、硫酸を注入して所定濃度の希硫酸を
作成した後、該溶解槽内に特定のＣａ塩基度を有するシ
リカ系凝集液原料を前記希硫酸で溶解できる溶解平衡量
を投入してシリカ系凝集液を得、次いで硫酸を前記希硫
酸と同じ当量分だけ添加し、更に前記シリカ系凝集液原
料を該希硫酸で溶解できる溶解平衡量を投入して高濃度
のシリカ系凝集液を得る方法である。The second method of dissolving the silica-based flocculant raw material
The feature is that a certain amount of water is supplied to the dissolution tank, sulfuric acid is injected while stirring the liquid in the dissolution tank to create dilute sulfuric acid with a predetermined concentration, and then a specific Ca base is added to the dissolution tank. The silica-based flocculant liquid raw material having a degree of dissolution is added with a dissolution equilibrium amount capable of being dissolved in the dilute sulfuric acid to obtain a silica-based flocculent liquid, and then sulfuric acid is added in the same amount as the dilute sulfuric acid. Is a method for obtaining a high-concentration silica-based coagulating liquid by adding a dissolution equilibrium amount capable of dissolving the above with dilute sulfuric acid.
【００２２】この高濃度のシリカ系凝集液を得る方法を
具体的に説明すると、例えば、溶解槽に水を供給し、該
溶解槽内の液を撹拌しながら、ｃｏｎｃ硫酸を注入して
１Ｎ濃度の希硫酸１リットルを作成した後、該溶解槽内
にＣａ塩基度１．１５を有するシリカ系凝集液原料を前
記１Ｎ濃度の希硫酸で溶解できる溶解平衡量４２．５ｇ
を投入してシリカ系凝集液を得、次いで硫酸を前記希硫
酸と同じ当量分（Ｈ2ＳＯ4 ＝４９ｇ）だけ添加し、更
に前記シリカ系凝集液原料を該希硫酸で溶解できる溶解
平衡量４２．５ｇを投入して、いわゆる２Ｎの高濃度シ
リカ系凝集液を得ることができる。尚、３Ｎ、４Ｎ、５
Ｎについても同様にこの操作を繰り返すことにより得ら
れる。The method for obtaining this high-concentration silica-based coagulating liquid will be specifically described. For example, water is supplied to the dissolution tank, and while concentrating the liquid in the dissolution tank, conc sulfuric acid is injected to obtain a 1N concentration. 1 liter of diluted sulfuric acid is prepared, and then a dissolution equilibrium amount of 42.5 g capable of dissolving the silica-based flocculant raw material having Ca basicity of 1.15 in the dissolution tank with the 1N concentration of diluted sulfuric acid.
Is added to obtain a silica-based coagulation liquid, and then sulfuric acid is added in an amount equivalent to that of the dilute sulfuric acid (H 2 SO 4 = 49 g). Further, a dissolution equilibrium amount capable of dissolving the silica-based coagulation liquid raw material in the dilute sulfuric acid is added. By charging 42.5 g, a so-called 2N high-concentration silica-based aggregation liquid can be obtained. 3N, 4N, 5
Similarly, N can be obtained by repeating this operation.
【００２３】これに対し、溶解槽に水を供給し、該溶解
槽内の液を撹拌しながら、ｃｏｎｃ硫酸を注入して２Ｎ
濃度の希硫酸１リットルを作成した後、該溶解槽内にＣ
ａ塩基度１．１５を有するシリカ系凝集液原料を前記２
Ｎ濃度の希硫酸で溶解できる溶解平衡量８５ｇを投入し
てシリカ系凝集液を得ると、やはり見掛け上はいわゆる
２Ｎの高濃度シリカ系凝集液を得ることができるように
考えられるが、このようにして得られたシリカ系凝集液
は、シリカ系凝集液原料の添加によって部分的にｐＨの
上昇するところではシリカの重合化が起こり、またｐＨ
の低いところでは無水シリカが生成されたりして、必要
とされるモノマーシリカが少なくなってしまうという問
題があり、本発明の目的を達成できない。On the other hand, water is supplied to the dissolution tank, and while stirring the liquid in the dissolution tank, conc sulfuric acid is injected to obtain 2N.
After preparing 1 liter of dilute sulfuric acid having a concentration, C in the dissolution tank
a The silica-based flocculating liquid raw material having a basicity of 1.15 is added to
When a dissolution equilibrium amount of 85 g capable of being dissolved in dilute sulfuric acid having an N concentration is added to obtain a silica-based coagulation liquid, it is considered that a so-called 2N high-concentration silica-based coagulation liquid can be apparently obtained. The silica-based flocculant obtained in step (1) has a pH value that is partially polymerized by the addition of the silica-based flocculant raw material.
In the case where the temperature is low, there is a problem that anhydrous silica is produced and the amount of required monomer silica is reduced, and the object of the present invention cannot be achieved.
【００２４】[0024]
【実施例】次に、本発明に係るシリカ系凝集液の製造方
法の実施例を図面に基いて説明する。EXAMPLES Next, examples of the method for producing a silica-based coagulating liquid according to the present invention will be described with reference to the drawings.
【００２５】図１は、シリカ系凝集液の製造システムフ
ロー図である。FIG. 1 is a flow chart of a silica-based coagulating liquid manufacturing system.
【００２６】スイッチを入れてシステムをスタートさ
せ、始めに溶解槽に一定量の水を供給する。この水は通
常水道水が用いられるが、格別限定されない。但し、Ｆ
ｅイオン、Ａｌイオン等金属イオンを数ＰＰＭ以上を含
む水はシリカとインターアクションを起こし好ましくな
い。The system is started by turning on the switch, and first, a fixed amount of water is supplied to the dissolving tank. This water is usually tap water, but is not particularly limited. However, F
Water containing several PPM or more of metal ions such as e ions and Al ions is not preferable because it causes interaction with silica.
【００２７】次に、水の量が一定になったら、溶解槽内
の水を撹拌する。Next, when the amount of water becomes constant, the water in the dissolution tank is stirred.
【００２８】次に硫酸を注入して所定濃度の希硫酸を作
成する。希硫酸濃度はモノマーシリカのゲル化を防止す
る意味で２Ｎ以下が好ましく、より好ましくは１Ｎ以下
である。本例では１Ｎ希硫酸とする。Next, sulfuric acid is injected to prepare dilute sulfuric acid having a predetermined concentration. The dilute sulfuric acid concentration is preferably 2N or less, more preferably 1N or less, in order to prevent gelation of the monomer silica. In this example, 1N dilute sulfuric acid is used.
【００２９】注入する硫酸は濃硫酸が用いられ、受け入
れ設備等を考慮すると、６４％濃度で受け入れることが
好ましい。なお既設に９８％濃硫酸設備（消防法完備）
がある場合にはそれを利用することもできる。Concentrated sulfuric acid is used as the sulfuric acid to be injected, and it is preferable to accept it at a concentration of 64% in consideration of the receiving equipment. In addition, 98% concentrated sulfuric acid equipment (completely equipped with Fire Defense Law)
If there is, it can be used.
【００３０】次に、数分間保持（撹拌下で放置）する。
均一な１Ｎ希硫酸を得るためである。保持時間は３分程
度あれば良い。Next, it is held for several minutes (leaved under stirring).
This is to obtain uniform 1N dilute sulfuric acid. The holding time may be about 3 minutes.
【００３１】次に、溶解槽内にシリカ系凝集液原料を投
入する。本発明において、シリカ系凝集液原料の「溶解
平衡量」というのは、与えた硫酸量で溶解できるシリカ
系凝集液原料の量を意味する。本例では１Ｎ希硫酸１リ
ットルで溶解できるＣａ塩基度１．１５のシリカ系凝集
液原料の量は４２．５ｇである。Next, the silica-based coagulating liquid raw material is put into the dissolution tank. In the present invention, the “dissolution equilibrium amount” of the silica-based aggregation liquid raw material means the amount of the silica-based aggregation liquid raw material that can be dissolved with the given amount of sulfuric acid. In this example, the amount of the silica-based flocculant raw material having a Ca basicity of 1.15 which can be dissolved in 1 liter of 1N dilute sulfuric acid is 42.5 g.
【００３２】次に、溶解平衡に達するまで保持する。保
持時間は５分程度でよいが、より確実に溶解平衡に達す
るまでには１５分間が好ましい。Next, the solution is held until the dissolution equilibrium is reached. The holding time may be about 5 minutes, but it is preferably 15 minutes to more surely reach the dissolution equilibrium.
【００３３】次に、必要により溶解槽内のｐＨが２．５
を越えているかいないかを判断する。希硫酸と原料の反
応が進行すれば溶解槽内のｐＨが上昇してくる。そして
ｐＨが２．５未満である場合にはいまだ反応が溶解平衡
まで進行していないのでｐＨが２．５を越えるまで数分
間保持する。この保持によって反応が進行し、ｐＨが上
昇する。反応を継続させればｐＨが収れんするため、そ
の反応時間とｐＨの収れん関係をつかめばあえてかかる
ｐＨ判断は必要ない。設備面で低コスト化を図る上では
かかるｐＨ判断をしない方法をとることが好ましい。Next, if necessary, the pH in the dissolution tank is adjusted to 2.5.
Judge whether or not it exceeds. If the reaction between the dilute sulfuric acid and the raw material proceeds, the pH in the dissolution tank will rise. When the pH is less than 2.5, the reaction has not yet reached the dissolution equilibrium, and therefore the pH is maintained for several minutes until it exceeds 2.5. By this retention, the reaction proceeds and the pH rises. Since the pH converges when the reaction is continued, it is not necessary to make a pH judgment if the relationship between the reaction time and the pH convergence is grasped. In terms of equipment cost reduction, it is preferable to adopt a method that does not make such pH judgment.
【００３４】一方、ｐＨが２．５以上である場合には反
応が進行し溶解平衡に達したと判断できるので、次に濾
過するか否かを判断する。On the other hand, when the pH is 2.5 or more, it can be judged that the reaction has proceeded and the dissolution equilibrium has been reached, and therefore, it is judged whether or not to carry out filtration.
【００３５】そして、濾過しない場合にはスラッジを含
めたまま凝集液タンクに受け入れる。これによって本発
明のシリカ系凝集液を得ることができる。When not filtered, the sludge containing the sludge is received in the flocculating liquid tank. As a result, the silica-based aggregation liquid of the present invention can be obtained.
【００３６】また濾過する場合には濾過機で濾液とスラ
ッジに分離し、濾液を凝集液タンクに受け入れる。これ
によって本発明のシリカ系凝集液を得ることができる。In the case of filtration, the filtrate and sludge are separated by a filter and the filtrate is received in a flocculating liquid tank. As a result, the silica-based aggregation liquid of the present invention can be obtained.
【００３７】尚、濾過する場合の溶解槽内での最終ｐＨ
はｐＨ≒３．０となるようシリカ系凝集液原料の量を増
して調節することも好ましい。The final pH in the dissolution tank when filtering
Is also preferably adjusted by increasing the amount of the silica-based coagulating liquid raw material so that the pH becomes approximately 3.0.
【００３８】更にスラッジはＣａＳＯ4 ・２Ｈ2 Ｏ（石
膏）であり、これを例えばスラッジピットに受け入れ
る。Further, the sludge is CaSO 4 .2H 2 O (gypsum), which is received in, for example, a sludge pit.
【００３９】凝集液タンク内の本発明のシリカ系凝集液
が使用されて減少し、レベルセンサーで検出されたとき
には、スタートに戻って再度上記の方法を繰り返す。When the silica-based flocculating liquid of the present invention in the flocculating liquid tank is used and reduced, and when it is detected by the level sensor, the process is returned to the start and the above method is repeated again.
【００４０】上記のシステムは自動化されていることが
好ましく、具体的連動関係は以下の装置例で明らかにす
る。The above system is preferably automated, and the specific interlocking relationship will be clarified in the following apparatus example.
【００４１】本発明のシリカ系凝集液の製造方法に用い
られるシリカ系凝集液原料は、シリカの複合結晶鉱物・
非結晶鉱物であり、例えば天然クリストバル石、高炉ス
ラグ等が用いられる。具体的には、酸化処理等の改質処
理されたシリカ系凝集液原料、即ちシリカの複合結晶鉱
物・非結晶鉱物の未酸化硫黄成分が除去されたシリカ系
凝集液原料が好ましいが、特願平１−２９６３７１号に
記載されたシリカ系凝集液原料を用いることもできる。The raw material of the silica-based flocculating liquid used in the method for producing the silica-based flocculating liquid of the present invention is a composite crystal mineral of silica.
Amorphous minerals such as natural cristobalite and blast furnace slag are used. Specifically, it is preferable to use a silica-based flocculant raw material that has been subjected to a modification treatment such as oxidation treatment, that is, a silica-based flocculent fluid raw material from which the unoxidized sulfur component of the silica composite crystalline mineral / amorphous mineral has been removed. It is also possible to use the silica-based flocculating liquid raw material described in JP-A 1-296371.
【００４２】次に、本発明に係るシリカ系凝集液の製造
装置の実施例を図２に基いて説明する。Next, an embodiment of the apparatus for producing a silica-based coagulating liquid according to the present invention will be described with reference to FIG.
【００４３】図２において、１は硫酸注入手段であり、
例えば６４％硫酸として受け入れる硫酸タンク１０１
と、硫酸ポンプ１０２と、ピペット状の硫酸定量容器１
０３と、硫酸注入バルブ１０４とで構成されている。硫
酸ポンプ１０２には耐食性のポンプが用いられる。ピペ
ット状の硫酸定量容器１０３は、硫酸ポンプ１０２から
送られた硫酸を硫酸定量容器１０３の細管部に設けられ
たオーバーフロー管１０５からオーバーフローさせて定
量可能に構成されている。In FIG. 2, 1 is a sulfuric acid injection means,
For example, a sulfuric acid tank 101 that accepts as 64% sulfuric acid
, Sulfuric acid pump 102, and pipette-shaped sulfuric acid quantitative container 1
03 and a sulfuric acid injection valve 104. As the sulfuric acid pump 102, a corrosion resistant pump is used. The pipette-shaped sulfuric acid quantitative container 103 is configured to allow quantitative determination by overflowing the sulfuric acid sent from the sulfuric acid pump 102 from an overflow pipe 105 provided in a thin tube portion of the sulfuric acid quantitative container 103.
【００４４】２は溶解槽であり、樹脂製又は耐食性金属
で形成される。２０１は溶解槽２内の液を撹拌するため
の撹拌機であり、３は水道水注入手段を構成する水道水
注入バルブである。Reference numeral 2 denotes a melting tank, which is made of a resin or a corrosion resistant metal. Reference numeral 201 is a stirrer for stirring the liquid in the dissolution tank 2, and 3 is a tap water injection valve constituting a tap water injection means.
【００４５】溶解槽２内には、ハイレベルセンサー２０
２とローレベルセンサー２０３が設けられている。ハイ
レベルセンサー２０２は硫酸ポンプ１０２、硫酸注入バ
ルブ１０４、撹拌機２０１と各々連動しており、ローレ
ベルセンサー２０３は硫酸注入バルブ１０４、撹拌機２
０１、水道水注入バルブ３と各々連動している。In the melting tank 2, a high level sensor 20
2 and a low level sensor 203 are provided. The high level sensor 202 is interlocked with the sulfuric acid pump 102, the sulfuric acid injection valve 104, and the agitator 201, and the low level sensor 203 is the sulfuric acid injection valve 104 and the agitator 2.
01, the tap water injection valve 3 is interlocked with each.
【００４６】２０４は溶解槽２内に必要により設けられ
るｐＨメーターであり、ｐＨが２．５を越えているかい
ないかを判断する指標とする。ただし前述のように硫酸
と原料の反応時間によってｐＨ値は収れんするので、タ
イマーによってシーケンスを組むこともできる。Reference numeral 204 is a pH meter provided in the dissolution tank 2 as required, and is used as an index for judging whether or not the pH exceeds 2.5. However, as described above, since the pH value converges depending on the reaction time of the sulfuric acid and the raw material, the sequence can be set up by the timer.
【００４７】４は溶解槽２にシリカ系凝集液原料４０１
を供給する手段であり、ホッパー４０２と自動供給する
場合に設けられる原料供給フィーダー４０３とによって
構成される。なお自動供給しない場合には原料供給フィ
ーダー４０３は必要ない。ホッパー４０２内にはシリカ
系凝集液原料４０１をホッパー内で酸化するためのエア
ー供給手段を有していてもよい。4 is a silica-based coagulating liquid raw material 401 in the dissolution tank 2.
And a raw material supply feeder 403 provided in the case of automatic supply. The raw material supply feeder 403 is not necessary when the automatic supply is not used. The hopper 402 may have an air supply means for oxidizing the silica-based flocculant raw material 401 in the hopper.
【００４８】５はシリカ系凝集液を受け入れるための凝
集液タンクである。Reference numeral 5 is a flocculating liquid tank for receiving the silica flocculating liquid.
【００４９】溶解槽２内で得られた溶液はｐＨが２．５
以上であり、濾過しない場合には、送液ポンプ５０１に
よって直接凝集液タンク５に送られる。５０２は撹拌
機、５０３はバルブである。The solution obtained in the dissolution tank 2 has a pH of 2.5.
When the filtration is not performed, the liquid is fed directly to the flocculating liquid tank 5 by the liquid feeding pump 501. 502 is a stirrer and 503 is a valve.
【００５０】一方、溶解槽２内で得られた溶液は、ｐＨ
が２．５以上でありかつ溶液を濾過する場合には、送液
ポンプ５０１によって濾過機６に送られる。濾過機６で
は濾液とスラッジに分離され、濾液は凝集液タンク５に
送られる。またスラッジはスラッジピット６０１に貯留
される。On the other hand, the pH of the solution obtained in the dissolution tank 2 is
Is 2.5 or more and the solution is filtered, the solution is sent to the filter 6 by the solution sending pump 501. In the filter 6, the filtrate and sludge are separated, and the filtrate is sent to the flocculating liquid tank 5. The sludge is stored in the sludge pit 601.
【００５１】凝集液タンク５内のシリカ系凝集液は処理
水ポンプ７によって各種排水処理に供される。処理水ポ
ンプ７はローレベルセンサー５０４の検知で停止する。The silica-based aggregating liquid in the aggregating liquid tank 5 is subjected to various wastewater treatments by the treated water pump 7. The treated water pump 7 stops when the low level sensor 504 detects it.
【００５２】なお前述の溶解槽２内で得られた溶液がｐ
Ｈが２．５以上であり、濾過しない場合には、送液ポン
プ５０１によってライン５０５を介して直接各種排水処
理に供することもできる。The solution obtained in the above-mentioned dissolution tank 2 is p
When H is 2.5 or more and is not filtered, it can be directly subjected to various wastewater treatments by the liquid feed pump 501 via the line 505.
【００５３】次に、本発明の溶解方法並びにシリカ系凝
集液の製造方法、装置に好ましく採用される主なシーケ
ンスを説明するが、必ずしも限定されない。Next, the main sequence preferably employed in the dissolving method, the method for producing a silica-based coagulating liquid, and the apparatus of the present invention will be described, but the present invention is not necessarily limited thereto.
【００５４】硫酸注入手段１に６４％硫酸が受け入れら
れ、硫酸定量容器１０３に所定量計量しておく。また水
道水注入バルブ３を開いて溶解槽２内に水を所定量満た
しておく。64% sulfuric acid is received by the sulfuric acid injecting means 1, and a predetermined amount is weighed in the sulfuric acid quantitative container 103. Further, the tap water injection valve 3 is opened to fill the dissolution tank 2 with a predetermined amount of water.
【００５５】この状態で撹拌機２１０を起動する。次い
で硫酸注入バルブ１０４を開いて所定量を注入する。In this state, the stirrer 210 is started. Then, the sulfuric acid injection valve 104 is opened to inject a predetermined amount.
【００５６】時間差５分間を設けて、原料供給フィーダ
ー４０３を起動し、所定量供給したら停止する。The material supply feeder 403 is started with a time difference of 5 minutes, and when a predetermined amount is supplied, it is stopped.
【００５７】時間差１５分間を設けて、バルブ５０３を
開いて、送液ポンプ５０１を起動する。この送液ポンプ
５０１の運転は濾過機６と連動させる（但し、濾過を必
要とする場合）。従って、送液ポンプ５０１の起動と同
時に濾過機６も起動する。With a time difference of 15 minutes, the valve 503 is opened and the liquid feed pump 501 is started. The operation of the liquid feed pump 501 is linked with the filter 6 (provided that filtration is required). Therefore, the filter 6 is activated at the same time when the liquid delivery pump 501 is activated.
【００５８】ローレベルセンサー２０３の検知によって
送液ポンプ５０１を停止し、バルブ５０３を閉じ、濾過
機６の運転を停止する。Upon detection by the low level sensor 203, the liquid feed pump 501 is stopped, the valve 503 is closed, and the operation of the filter 6 is stopped.
【００５９】濾液は凝集液タンク５に受け入れられ、こ
の時撹拌機５０２は連続運転している。The filtrate is received in the flocculating liquid tank 5, and the agitator 502 is continuously operating at this time.
【００６０】処理水ポンプ７が作動し、凝集液タンク５
内の液面が低下し、ローレベルセンサー５０４が検知し
たら、処理水ポンプ７が停止すると共に水道水注入バル
ブ３が開いて、水道水を溶解槽２に供給する。水道水注
入バルブ３はハイレベルセンサー２０２の検知によって
閉じる。The treated water pump 7 operates and the flocculating liquid tank 5
When the liquid level inside is lowered and detected by the low level sensor 504, the treated water pump 7 is stopped and the tap water injection valve 3 is opened to supply tap water to the dissolution tank 2. The tap water injection valve 3 is closed by the detection of the high level sensor 202.
【００６１】またローレベルセンサー２０３の検知によ
って水道水注入バルブ３を開いて、水道水を溶解槽２に
供給するようにすることもできる。The tap water injection valve 3 may be opened by the detection of the low level sensor 203 to supply tap water to the dissolving tank 2.
【００６２】[0062]
実験例１ 図２に示す装置を用いて実験を行なった。はじめに１５
０リットルの溶解槽２に水道水注入バルブ３を開いて水
道水を１００リットル供給した。Experimental Example 1 An experiment was conducted using the apparatus shown in FIG. Introduction 15
The tap water injection valve 3 was opened in the 0 liter dissolution tank 2 to supply 100 liters of tap water.
【００６３】該溶解槽２内の液を撹拌機２０１で撹拌し
ながら、硫酸注入バルブ１０４を開いて６４％硫酸４．
３４リットルを注入して１Ｎ濃度の希硫酸となるように
した。While stirring the liquid in the dissolution tank 2 with the stirrer 201, the sulfuric acid injection valve 104 was opened to give 64% sulfuric acid.
34 liters were injected so as to obtain 1N concentration of dilute sulfuric acid.
【００６４】次いで、該溶解槽２内にＣａ塩基度１．１
５を有するシリカ系凝集液原料を４．２５ｋｇを投入し
た。Then, Ca basicity of 1.1 is added in the dissolution tank 2.
4.25 kg of the silica-based aggregate liquid raw material having No. 5 was added.
【００６５】１５分間撹拌を続け保持して、シリカ系凝
集液を得た。By continuously stirring for 15 minutes, a silica-based coagulating liquid was obtained.
【００６６】このシリカ系凝集液の粘度を指標として測
定して、重合ゲル化状態を調べた。又静置してゾルゲル
化進行状態を調べた。The state of polymerization and gelation was examined by measuring the viscosity of this silica-based coagulating liquid as an index. Further, it was left to stand and the progress of sol-gelation was examined.
【００６７】粘度の測定は粘度計により行った。The viscosity was measured with a viscometer.
【００６８】測定結果を表１に示す。The measurement results are shown in Table 1.
【００６９】比較実験例１ 実験例１と同様に図２に示す装置を用いて実験を行なっ
た。はじめに１５０リットルの溶解槽２に水道水注入バ
ルブ３を開いて水道水を１００リットル供給した。Comparative Experimental Example 1 Similar to Experimental Example 1, an experiment was conducted using the apparatus shown in FIG. First, the tap water injection valve 3 was opened in the dissolution tank 2 of 150 liters to supply 100 liters of tap water.
【００７０】次いで、溶解槽２内の液を撹拌機２０１で
撹拌しながら、溶解槽２内にＣａ塩基度１．１５を有す
るシリカ系凝集液原料を４．２５ｋｇを投入した。Next, while stirring the liquid in the dissolution tank 2 with the stirrer 201, 4.25 kg of the silica-based aggregate liquid raw material having a Ca basicity of 1.15 was charged into the dissolution tank 2.
【００７１】次いで、硫酸注入バルブ１０４を開いて６
４％硫酸４．３４リットルを注入して１Ｎ濃度の希硫酸
となるようにした。Then, the sulfuric acid injection valve 104 is opened to 6
4.34 liters of 4% sulfuric acid was injected so that the diluted sulfuric acid had a concentration of 1N.
【００７２】１５分間撹拌を続け保持して、シリカ系凝
集液を得た。By continuously stirring for 15 minutes, a silica-based coagulating liquid was obtained.
【００７３】このシリカ系凝集液の粘度を指標として測
定して、重合、ゲル化状態を調べた。The viscosity of this silica-based coagulating liquid was measured as an index to examine the polymerization and gelation state.
【００７４】粘度の測定は実験例１と同様にした。The viscosity was measured in the same manner as in Experimental Example 1.
【００７５】測定結果を表１に示す。The measurement results are shown in Table 1.
【００７６】[0076]
【表１】 表１から明らかなように、本発明のシリカ系凝集液はシ
リカの重合、ゲル化が進んでいないことがわかる。又、
比較実験例１では２４時間後にゾルゲル化が認められ、
４８時間後にはゲル化したが、実験例１は安定してい
た。[Table 1] As is clear from Table 1, the silica-based aggregation liquid of the present invention does not undergo silica polymerization and gelation. or,
In Comparative Experimental Example 1, sol-gelation was observed after 24 hours,
Although it gelled after 48 hours, Experimental Example 1 was stable.
【００７７】実験例２ 図２に示す装置を用いて実験を行なった。はじめに１５
０リットルの溶解槽２に水道水注入バルブ３を開いて水
道水を１００リットル供給した。Experimental Example 2 An experiment was conducted using the apparatus shown in FIG. Introduction 15
The tap water injection valve 3 was opened in the 0 liter dissolution tank 2 to supply 100 liters of tap water.
【００７８】該溶解槽２内の水を撹拌機２０１で撹拌し
ながら、硫酸注入バルブ１０４を開いて６４％硫酸４．
３４リットルを注入して１Ｎ濃度の希硫酸となるように
した。While stirring the water in the dissolution tank 2 with the stirrer 201, the sulfuric acid injection valve 104 is opened to make 64% sulfuric acid.
34 liters were injected so as to obtain 1N concentration of dilute sulfuric acid.
【００７９】次いで、該溶解槽２内にＣａ塩基度１．１
５を有するシリカ系凝集液原料を４．２５ｋｇを投入し
た。攪拌を１５分間継続して１Ｎ希硫酸溶解のシリカ系
凝集液を得た。Then, the basicity of Ca in the dissolution tank 2 is 1.1.
4.25 kg of the silica-based aggregate liquid raw material having No. 5 was added. Stirring was continued for 15 minutes to obtain a silica-based coagulation liquid in which 1N dilute sulfuric acid was dissolved.
【００８０】更に、６４％硫酸を４．３４リットルを加
え、これにＣａ塩基度１．１５を有するシリカ系凝集液
原料を４．２５ｋｇを投入した。Further, 4.34 liters of 64% sulfuric acid was added, and 4.25 kg of a silica-based flocculant raw material having a Ca basicity of 1.15 was added thereto.
【００８１】１５分間撹拌を続け保持して、高濃度のシ
リカ系凝集液を得た。By continuously stirring for 15 minutes, a high-concentration silica-based aggregate liquid was obtained.
【００８２】このシリカ系凝集液の粘度を指標として測
定して、重合、ゲル化状態を調べ、静置してゾルゲル化
の進行状態を調べた。The viscosity of the silica-based coagulating liquid was measured as an index to examine the polymerization and gelation state, and the sol-gelation progress state was examined by standing.
【００８３】粘度の測定は実験例１と同様にした。The viscosity was measured in the same manner as in Experimental Example 1.
【００８４】測定結果を表２に示す。The measurement results are shown in Table 2.
【００８５】比較実験例２ 実験例２と同様に図２に示す装置を用いて実験を行なっ
た。はじめに１５０リットルの溶解槽２に水道水注入バ
ルブ３を開いて水道水を１００リットル供給した。Comparative Experimental Example 2 An experiment was conducted using the apparatus shown in FIG. First, the tap water injection valve 3 was opened in the dissolution tank 2 of 150 liters to supply 100 liters of tap water.
【００８６】該溶解槽２内の液を撹拌機２０１で撹拌し
ながら、硫酸注入バルブ１０４を開いて６４％硫酸８．
６８リットルを注入して２Ｎ濃度の希硫酸となるように
した。While stirring the liquid in the dissolution tank 2 with the stirrer 201, the sulfuric acid injection valve 104 was opened to give 64% sulfuric acid 8.
68 liters were injected to obtain a 2N concentration of dilute sulfuric acid.
【００８７】次いで、該溶解槽２内にＣａ塩基度１．１
５を有するシリカ系凝集液原料を８．５ｋｇを投入し
た。Then, Ca basicity of 1.1 is added to the dissolution tank 2.
8.5 kg of the silica-based aggregate liquid raw material having No. 5 was charged.
【００８８】１５分間撹拌を続け保持して、高濃度のシ
リカ系凝集液を得た。By continuously stirring for 15 minutes, a high-concentration silica-based coagulating liquid was obtained.
【００８９】このシリカ系凝集液の粘度を指標として測
定して、重合、ゲル化状態を調べ、静置してゾルゲル化
の進行状態を調べた。The viscosity of this silica-based coagulating liquid was measured as an index to examine the polymerization and gelation state, and the standing state was examined for the progress state of sol-gelation.
【００９０】粘度の測定は実験例１と同様にした。The viscosity was measured in the same manner as in Experimental Example 1.
【００９１】測定結果を表２に示す。The measurement results are shown in Table 2.
【００９２】[0092]
【表２】 表２から明らかなように、本発明のシリカ系凝集液は高
濃度であるにもかかわらず明らかにモノマーシリカの含
量が高く、モノマーシリカの安定性も高いことがわか
る。[Table 2] As is clear from Table 2, the silica-based coagulation liquid of the present invention has a high content of monomer silica and a high stability of monomer silica, despite its high concentration.
【００９３】比較のシリカ系凝集液のモノマーシリカ含
量が少なく、モノマーシリカの安定性に欠けるのは、シ
リカ系凝集液原料の添加によって部分的にｐＨの上昇す
るところではシリカの重合化が起こり、またｐＨの低い
ところでは無水シリカが生成されたりしていることに起
因しているものと考えられる。尚、シリカの重合、ゾル
ゲル化が認められると急速にゲル化が進行してゼリー状
固形物となる。The comparative silica-based coagulation liquid has a low content of monomer silica and lacks stability of the monomer silica because the polymerization of silica occurs at a point where the pH is partially increased by the addition of the silica-based coagulation liquid raw material. It is also considered that anhydrous silica is generated at low pH. When polymerization of silica and sol-gelation are observed, gelation proceeds rapidly to form a jelly-like solid.
【００９４】[0094]
【発明の効果】以上の説明から明らかなように、本発明
によれば、第１にモノマーシリカの含有割合が高くか
つ、安定性の高いシリカ系凝集液が得られるシリカ系凝
集液原料の溶解方法を提供することができ、第２に、輸
送コストが低くて経済効率が高くかつ原料を数倍量溶解
できるシリカ系凝集液原料の溶解方法を提供することが
できる。As is apparent from the above description, according to the present invention, firstly, the dissolution of the raw material of the silica-based flocculating liquid which gives a highly stable silica-based flocculating liquid having a high content ratio of the monomer silica. It is possible to provide a method, and secondly, to provide a method for dissolving a silica-based coagulating liquid raw material, which has low transportation cost, high economic efficiency, and can dissolve the raw material several times.
【００９５】第３に実際の装置に適用できるシリカ系凝
集液の製造方法を提供でき、第４にコンパクトなシリカ
系凝集液の製造装置を提供することができる。Thirdly, it is possible to provide a method for producing a silica-based coagulating liquid which can be applied to an actual device, and fourthly, it is possible to provide a compact silica-based coagulating liquid producing device.
【００９６】なお本発明によって得られたシリカ系凝集
液は、水中に含有される溶解物質やエマルジョン物質、
拡散剤、油分、浮遊物質等の吸着、凝集、排除に用いら
れ、現在、特に困難とされる油（動物油、植物油、鉱物
油）含有排水の油水分離に極めて有効である。このよう
な作用はモノマー・シリカの影響によるものと考えられ
る。即ちモノマー・シリカは有機物質、界面活性剤やそ
の他の有機物、無機イオン、プランクトンやバクテリ
ア、浮遊物質を吸着したり、凝集する機能を持ってい
る。この機能はＡｌ系、Ｆｅ系、高分子系凝集剤には見
られないものである。これらはモノマー・シリカのもつ
特性であり、即ちモノマー・シリカが重合し、ゲル化す
る過程で水中の有機物等との間にミセルを速やかに形成
し、無機イオンとの間にインター・アクションを起こし
て結合し、シリカのゲル化反応を急速に促進することに
よる。The silica-based coagulation liquid obtained by the present invention is a dissolved substance or emulsion substance contained in water,
It is used for adsorption, aggregation and elimination of diffusing agents, oils, suspended solids, etc., and is extremely effective for oil-water separation of wastewater containing oil (animal oil, vegetable oil, mineral oil), which is currently particularly difficult. Such an effect is considered to be due to the influence of the monomer / silica. That is, the monomer / silica has a function of adsorbing or aggregating organic substances, surfactants and other organic substances, inorganic ions, plankton, bacteria and suspended substances. This function is not found in Al-based, Fe-based, and polymer-based coagulants. These are the characteristics of the monomer / silica, that is, during the process of polymerization and gelation of the monomer / silica, micelles are rapidly formed with the organic substances in the water, etc., and the interaction with inorganic ions occurs. By rapidly accelerating the gelation reaction of silica.
【図１】シリカ系凝集液の製造システムフロー図[Figure 1] Silica-based flocculant manufacturing system flow diagram
【図２】本発明に係るシリカ系凝集液の製造装置の一実
施例を示す説明図FIG. 2 is an explanatory view showing an embodiment of the apparatus for producing a silica-based coagulating liquid according to the present invention.
１：硫酸注入手段 １０１：硫酸タンク １０２：硫酸ポンプ １０３：硫酸定量容器 １０４：硫酸注入バルブ １０５：オーバーフロー管 ２：溶解槽 ２０１：撹拌機 ２０２：ハイレベルセンサー ２０３：ローレベルセンサー ２０４：ｐＨメーター ３：水道水注入バルブ ４：シリカ系凝集液原料供給手段 ４０１：シリカ系凝集液原料 ４０２：ホッパー ４０３：原料供給フィーダー ５：凝集液タンク ５０１：送液ポンプ ５０２：撹拌機 ５０３：バルブ ５０４：ローレベルセンサー ５０５：ライン ６：濾過機 ６０１：スラッジピット 1: Sulfuric acid injection means 101: Sulfuric acid tank 102: Sulfuric acid pump 103: Sulfuric acid metering vessel 104: Sulfuric acid injection valve 105: Overflow pipe 2: Dissolution tank 201: Stirrer 202: High level sensor 203: Low level sensor 204: pH meter 3 : Tap water injection valve 4: Silica-based flocculating liquid raw material supply means 401: Silica-based flocculating liquid raw material 402: Hopper 403: Raw material supply feeder 5: Flocculant liquid tank 501: Liquid feeding pump 502: Stirrer 503: Valve 504: Low level Sensor 505: Line 6: Filter 601: Sludge pit
【手続補正書】[Procedure amendment]
【提出日】平成５年８月１２日[Submission date] August 12, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００７６[Correction target item name] 0076
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００７６】[0076]
【表１】 表１から明らかなように、本発明のシリカ系凝集液はシ
リカの重合、ゲル化が進んでいないことがわかる。又、
比較実験例１では２４時間後にゾルゲル化が認められ、
４８時間後にはゲル化したが、実験例１は安定してい
た。[Table 1] As is clear from Table 1, the silica-based aggregation liquid of the present invention does not undergo silica polymerization and gelation. or,
In Comparative Experimental Example 1, sol-gelation was observed after 24 hours,
Although it gelled after 48 hours, Experimental Example 1 was stable.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００９２[Correction target item name] 0092
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００９２】[0092]
【表２】 表２から明らかなように、本発明のシリカ系凝集液は高
濃度であるにもかかわらず明らかにモノマーシリカの含
量が高く、モノマーシリカの安定性も高いことがわか
る。[Table 2] As is clear from Table 2, the silica-based coagulation liquid of the present invention has a high content of monomer silica and a high stability of monomer silica, despite its high concentration.
Claims (5)
リカ系凝集液を製造する際に、溶解槽に一定量の水を供
給し、該溶解槽内の水を撹拌しながら、硫酸を注入して
所定濃度の希硫酸を作成した後、該溶解槽内に特定のＣ
ａ塩基度を有するシリカ系凝集液原料を前記希硫酸で溶
解できる溶解平衡量を投入することを特徴とするシリカ
系凝集液原料の溶解方法。1. When a silica-based flocculant raw material is dissolved in dilute sulfuric acid to produce a silica-based flocculant, a certain amount of water is supplied to the dissolution tank, and the sulfuric acid is stirred while stirring the water in the dissolution tank. Is injected to prepare a dilute sulfuric acid having a predetermined concentration, and then a specific C is put in the dissolution tank.
(a) A method for dissolving a silica-based flocculant raw material, which comprises adding a dissolution equilibrium amount capable of dissolving the silica-based flocculant raw material having a basicity with the dilute sulfuric acid.
濃度シリカ系凝集液が得られるシリカ系凝集液原料の溶
解方法において、請求項１記載の方法によってシリカ系
凝集液を得、次いで硫酸を前記希硫酸と同じ当量分だけ
添加し、再度前記シリカ系凝集液原料を該希硫酸で溶解
できる溶解平衡量を投入し、必要によりこの操作を繰り
返すことを特徴とするシリカ系凝集液原料の溶解方法。2. A method for dissolving a silica-based flocculant raw material, which has a high content ratio of monomer silica and is capable of obtaining a high-concentration silica-based flocculate, wherein a silica-based flocculate is obtained by the method according to claim 1, and then sulfuric acid is added. The same amount as the dilute sulfuric acid is added, and a dissolution equilibrium amount capable of dissolving the silica-based coagulation liquid raw material is again added, and this operation is repeated if necessary. Method.
原料を希硫酸で溶解してシリカ系凝集液を製造するシリ
カ系凝集液の製造方法において、 溶解槽に一定量の水を供給し、該溶解槽内の水を撹拌し
ながら、硫酸を注入して所定濃度の希硫酸を作成した
後、該溶解槽内にシリカ系凝集液原料を投入し、次いで
溶解平衡に達するまで保持した後、 次に必要により該溶解槽内のｐＨが２．５を越えている
かいないかを判断し、該ｐＨが２．５未満である場合に
はｐＨが２．５を越えるまで数分間保持し、 一方ｐＨが２．５以上である場合には次に濾過するか否
かを判断し、 濾過しない場合にはそのままシリカ系凝集液とし、また
濾過する場合には濾液をシリカ系凝集液とすることを特
徴とするシリカ系凝集液の製造方法。3. A method for producing a silica-based flocculating liquid, which comprises dissolving a raw material for a silica-based flocculating liquid having a specific Ca basicity with dilute sulfuric acid to produce a silica-based flocculating liquid, and supplying a fixed amount of water to a dissolving tank. After stirring the water in the dissolution tank to inject sulfuric acid to prepare a dilute sulfuric acid having a predetermined concentration, after introducing the silica-based flocculant raw material into the dissolution tank and then holding it until the dissolution equilibrium is reached. Next, if necessary, it is judged whether or not the pH in the dissolution tank exceeds 2.5, and if the pH is less than 2.5, hold for several minutes until the pH exceeds 2.5, On the other hand, if the pH is 2.5 or more, determine whether or not to filter next. If not, use silica-based coagulation liquid as it is, and if filtration, use the filtrate as silica-based coagulation liquid. A method for producing a silica-based aggregation liquid, which comprises:
る水供給手段と、該溶解槽内の液を撹拌する撹拌手段
と、前記水供給手段から水が供給された溶解槽に硫酸を
注入するための硫酸注入手段と、該溶解槽にシリカ系凝
集液原料を供給する手段と、該溶解槽内のｐＨが２．５
以上でありかつ該溶解槽内の溶液を濾過しない場合にシ
リカ系凝集液を受け入れるための凝集液タンクとを有す
ることを特徴とするシリカ系凝集液の製造装置。4. A dissolution tank, water supply means for supplying a fixed amount of water to the dissolution tank, stirring means for stirring the liquid in the dissolution tank, and a dissolution tank to which water is supplied from the water supply means. Sulfuric acid injecting means for injecting sulfuric acid into the solution, means for supplying the silica-based coagulating liquid raw material to the dissolving tank, and pH in the dissolving tank is 2.5.
An apparatus for producing a silica-based coagulation liquid, comprising: a coagulation liquid tank for receiving the silica-based coagulation liquid when the solution in the dissolution tank is not filtered.
る水供給手段と、該溶解槽内の液を撹拌する撹拌手段
と、前記水供給手段から水が供給された溶解槽に硫酸を
注入するための硫酸注入手段と、該溶解槽にシリカ系凝
集液原料を供給する手段と、該溶解槽内のｐＨが２．５
以上でありかつ該溶解槽内の溶液を濾過する場合に該濾
液であるシリカ系凝集液を受け入れるための凝集液タン
クとを有することを特徴とするシリカ系凝集液の製造装
置。5. A dissolution tank, water supply means for supplying a fixed amount of water to the dissolution tank, stirring means for stirring the liquid in the dissolution tank, and a dissolution tank to which water is supplied from the water supply means. Sulfuric acid injecting means for injecting sulfuric acid into the solution, means for supplying the silica-based coagulating liquid raw material to the dissolving tank, and pH in the dissolving tank is 2.5.
An apparatus for producing a silica-based coagulation liquid, which is the above and has a coagulation liquid tank for receiving the silica-based coagulation liquid that is the filtrate when the solution in the dissolution tank is filtered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5045885A JP2558591B2 (en) | 1993-02-10 | 1993-02-10 | Method for dissolving silica-based flocculant raw material, method and apparatus for producing silica-based flocculate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5045885A JP2558591B2 (en) | 1993-02-10 | 1993-02-10 | Method for dissolving silica-based flocculant raw material, method and apparatus for producing silica-based flocculate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06233904A true JPH06233904A (en) | 1994-08-23 |
| JP2558591B2 JP2558591B2 (en) | 1996-11-27 |
Family
ID=12731698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5045885A Expired - Lifetime JP2558591B2 (en) | 1993-02-10 | 1993-02-10 | Method for dissolving silica-based flocculant raw material, method and apparatus for producing silica-based flocculate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2558591B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005009586A1 (en) * | 2003-07-25 | 2005-02-03 | Keiichiro Asaoka | Coagulant, process for producing the same, and method of coagulation with the coagulant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03157107A (en) * | 1989-11-15 | 1991-07-05 | Tsutomu Nishimura | Silica-based liquid flocculant and its production |
-
1993
- 1993-02-10 JP JP5045885A patent/JP2558591B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03157107A (en) * | 1989-11-15 | 1991-07-05 | Tsutomu Nishimura | Silica-based liquid flocculant and its production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005009586A1 (en) * | 2003-07-25 | 2005-02-03 | Keiichiro Asaoka | Coagulant, process for producing the same, and method of coagulation with the coagulant |
| US7666916B2 (en) | 2003-07-25 | 2010-02-23 | Keiichiro Asaoka | Flocculant, manufacturing method therefor, and flocculation method using the flocculant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2558591B2 (en) | 1996-11-27 |
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