JPS63221845A - Preparation of adsorbent - Google Patents
Preparation of adsorbentInfo
- Publication number
- JPS63221845A JPS63221845A JP5418487A JP5418487A JPS63221845A JP S63221845 A JPS63221845 A JP S63221845A JP 5418487 A JP5418487 A JP 5418487A JP 5418487 A JP5418487 A JP 5418487A JP S63221845 A JPS63221845 A JP S63221845A
- Authority
- JP
- Japan
- Prior art keywords
- adsorbent
- precipitate
- chlorine compound
- zro2
- washed
- 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.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000006228 supernatant Substances 0.000 abstract description 3
- 238000010908 decantation Methods 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 abstract description 2
- 229910011011 Ti(OH)4 Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010887 waste solvent Substances 0.000 description 2
- MQEMKUTWMALMCC-UHFFFAOYSA-N 1-nitrododecane Chemical compound CCCCCCCCCCCC[N+]([O-])=O MQEMKUTWMALMCC-UHFFFAOYSA-N 0.000 description 1
- LSKONYYRONEBKA-UHFFFAOYSA-N 2-Dodecanone Natural products CCCCCCCCCCC(C)=O LSKONYYRONEBKA-UHFFFAOYSA-N 0.000 description 1
- 241000269851 Sarda sarda Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、下水処理、核燃料廃棄物処理等の微量有害成
分吸着浄化装置に適用される吸着剤の調製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for preparing an adsorbent that is applied to a trace amount harmful component adsorption purification device for sewage treatment, nuclear fuel waste treatment, etc.
従来、上記の吸着剤としては５１０２が知られているが
、吸着容量は余り高くなく、またＢ ｉ Ｏ。Conventionally, 5102 has been known as the above-mentioned adsorbent, but its adsorption capacity is not very high, and B i O.
はアルカリ成分中では溶解する難点がある。has the disadvantage that it dissolves in alkaline components.
本発明は、従来の８１０２の吸着能に対比して１０倍以
上の吸着能を持ち、かつアルカリ、その他の薬品に対し
優れた耐性を有する吸着剤を安価に調製する方法を提供
するものである。The present invention provides a method for inexpensively preparing an adsorbent that has an adsorption capacity ten times higher than that of conventional 8102 and has excellent resistance to alkalis and other chemicals. .
本発明は、Ｔｉの塩素化合物とＺｒの塩素化合物を原料
としてＮＨ，法により Ｔｉの水酸化物とＺｒの水酸化
物を沈澱させ、該沈澱物を３５０〜４５０℃にて焼成し
、Ｚｒ０１／Ｔｉ０１のモル比が１．０±α３の吸着剤
を製造することを特徴とする吸着剤の調製法に関する。In the present invention, a hydroxide of Ti and a hydroxide of Zr are precipitated by the NH method using a chlorine compound of Ti and a chlorine compound of Zr as raw materials, and the precipitate is calcined at 350 to 450°C to form Zr01/ The present invention relates to a method for preparing an adsorbent, characterized in that the adsorbent has a Ti01 molar ratio of 1.0±α3.
本発明は、吸着剤の吸着能の向上を吸着剤の細孔構造の
改善、特に比表面積の増大により解決したものである。The present invention solves the problem of improving the adsorption capacity of an adsorbent by improving the pore structure of the adsorbent, particularly by increasing the specific surface area.
すなわち、本発明は、吸着剤の比表面積増大のため原料
の沈澱法の検討、沈澱物の焼成温度の検討を行ない、最
適値を見出したものである。That is, in the present invention, in order to increase the specific surface area of the adsorbent, the method of precipitation of raw materials and the firing temperature of the precipitate were investigated, and the optimum value was found.
先ず原料の沈澱法については、原則としてはアルカリに
よる沈澱法が採用されるが、ＮａＯＨやＫＯＨでは製品
吸着剤中に残存して吸着能に悪影響を及ぼすため、本発
明では焼成時に飛散するＮＨ，又は尿素を使用する沈澱
法によることとした。First, regarding the precipitation method of raw materials, in principle, alkali precipitation method is adopted, but since NaOH and KOH remain in the product adsorbent and have a negative effect on adsorption capacity, in the present invention, NH, which is scattered during calcination, Alternatively, a precipitation method using urea was used.
次に沈澱物の焼成温度については、常識的には、焼成温
度上昇は吸着剤の比表面積の低下につながるが、低温焼
成では製品吸着剤の使用中に水へ溶解したシ、耐薬品性
に劣る等の問題があシ、ある程度の高温での焼成か不可
欠である。Next, regarding the firing temperature of the precipitate, it is common sense that increasing the firing temperature will lead to a decrease in the specific surface area of the adsorbent, but low-temperature firing will reduce the chemical resistance of the product adsorbent that dissolves in water during use. There are problems such as inferiority, and firing at a certain high temperature is essential.
そこで本発明では製品吸着剤の吸着能が従来の８１０２
の１０倍程度となシ、しかも水に対して不溶性で、かつ
高い耐薬品性を示すものとすることを目標にして、沈澱
物の焼成温度を３５０〜４５０℃、好ましくは３５０〜
４００℃程度とすることセした。Therefore, in the present invention, the adsorption capacity of the product adsorbent is higher than that of the conventional 8102.
The firing temperature of the precipitate is set at 350 to 450°C, preferably 350 to 450°C, with the aim of making the precipitate about 10 times that of
It was decided to set the temperature to about 400°C.
また、安価に製造するためには、ＺｒＯ２／Ｔｉ０１の
比が小さいことが好ましいことから、本発明ではＺｒＯ
２／ Ｔｉ０１− ｔ Ｏ±α３（モル比）とすること
とした。In addition, in order to manufacture at low cost, it is preferable that the ratio of ZrO2/Ti01 is small, so in the present invention, ZrO2/Ti01 is preferably small.
2/Ti01-tO±α3 (molar ratio).
〔実施例〕
核燃料再生処理装置よシ発生する廃溶媒（ドデカン）の
劣化物を除去する吸着剤について本発明による製造実施
例を次に示す。[Example] The following is a manufacturing example of an adsorbent for removing degraded products of waste solvent (dodecane) generated from a nuclear fuel regeneration processing device according to the present invention.
Ｔｉ０／４５．２０４ ｍａｔを氷上に滴下し、水溶液
とした。次にＺｒ０Ｏｔ１６．３６１ ｍｏｔを常温で
水溶液としたものと混合して、Ｔｉｅ意対ＺｒＯ２のモ
ル比に換算して［１４５対α５５となり、また、Ｔｉ０
８とＺｒＯ２の合計濃度に換算して［１２ｍｏｂ／Ｌと
なるように調製した。てり後、これ等に対する反応当量
の１．１倍に当るＮＨ３量３６．Ｂ ９２ｒｒｏＬを、
１ ｍｏｂ／Ｌの濃度の水溶液として上記混合溶液に攪
拌しながら徐々に加えた。温度は室温のままとし、１０
０ｔのプラスチック容器を使用した。Ti0/45.204 mat was dropped onto ice to form an aqueous solution. Next, Zr0Ot16.361 mot was mixed with an aqueous solution at room temperature, and the molar ratio of Tie to ZrO2 was [145 to α55, and Ti0
The total concentration of ZrO2 and ZrO2 was adjusted to 12 mob/L. After sterilization, the amount of NH3 corresponding to 1.1 times the reaction equivalent for these is 36. B 92rroL,
An aqueous solution having a concentration of 1 mob/L was gradually added to the above mixed solution while stirring. Leave the temperature at room temperature, and
A 0 ton plastic container was used.
上記のようにしてＮＨ，を加えると、Ｔｉ（ＯＨ）４と
Ｚｒ（ＯＨ）ヰの白色沈澱物が生成した。沈澱物は凝集
しているものであり、沈降速度が非常に早いため、デカ
ンテーションで洗浄を繰り返して上筐液にａｔ−を検出
できなくなるまで完全に洗浄した。最後に上澄液を排出
した後、大型のヌツチェ濾過器で吸引ｒ過脱水を行なっ
た。When NH was added as described above, a white precipitate of Ti(OH) and Zr(OH) was formed. Since the precipitate was agglomerated and had a very fast sedimentation rate, it was thoroughly washed by repeated decantation until at- could no longer be detected in the supernatant liquid. Finally, after draining the supernatant liquid, suction filtration and dehydration were performed using a large Nutsche filter.
濾過ケーキは１００〜１１０℃で乾燥した後、更に４０
０℃で５時間焼成した。ここで得られた吸着剤の収量は
約１１００１Ｐであり、これは計算値目標量１２００ｆ
の９０係以上の高収率であった。After drying the filter cake at 100-110℃,
It was baked at 0°C for 5 hours. The yield of adsorbent obtained here was approximately 11001P, which corresponds to the calculated target amount of 1200f.
The yield was high, with a factor of 90 or higher.
上記のようにして得られた吸着剤につき、廃溶媒（ドデ
カン）の劣化物であるドデカノン、ドデカノール、ニト
ロドデカンに対する吸着性能を調べたところ、従来の代
表的なシリカゲル吸着剤より約１０倍優れていることを
確認した。We investigated the adsorption performance of the adsorbent obtained as described above for dodecanone, dodecanol, and nitrododecane, which are degraded products of waste solvent (dodecane), and found that it was about 10 times better than a typical conventional silica gel adsorbent. I confirmed that there is.
次に、焼成温度を種々変えた以外は上記と全く同様にし
て吸着剤を得、焼成温度と吸着剤の比表面積との関係を
調べ、この結果を＠１図の実線に示す。Next, an adsorbent was obtained in exactly the same manner as above except that the calcination temperature was varied, and the relationship between the calcination temperature and the specific surface area of the adsorbent was investigated, and the results are shown in the solid line in Figure @1.
本発明では、この第１図に基づいて焼成温度を４００℃
付近に限定したものである。その理由は次の実験事実に
基づくものである。In the present invention, the firing temperature is set at 400°C based on this Figure 1.
It is limited to the vicinity. The reason for this is based on the following experimental facts.
（１）本発明の製造法は、焼成温度対比表面積の定量的
な再現性が非常に優れ、信頼性の高いものである。(1) The manufacturing method of the present invention has excellent quantitative reproducibility of surface area versus firing temperature and is highly reliable.
（２）第１図の点線に示すように、洗浄不足により残留
するＮＨ４０１の分解温度は３３８℃であるから、もし
洗浄不足となっても４００℃で焼成すれば安全である。(2) As shown by the dotted line in FIG. 1, the decomposition temperature of NH401 remaining due to insufficient washing is 338°C, so even if washing is insufficient, it is safe to bake at 400°C.
（３）４！ｉｎ℃以上では急速に比表面積が減少する。(3)4! The specific surface area rapidly decreases at temperatures above in°C.
（４）ｌｉｏ℃以下では比表面積の増加は弱く、約３０
０℃以下では結晶水を含有したままであるから、不安定
であシ、処理液に溶解する可能性がある。(4) Below 10°C, the increase in specific surface area is weak, about 30°C.
At temperatures below 0°C, the crystal water remains contained, making it unstable and potentially dissolving in the processing solution.
また、前述の製造実施例において、ＺｒＯ２とＴｌＯ２
のモル比を種々変えた以外は全く同様にして吸着剤を得
、この比と吸着剤の比表面積との関係を調べ、この結果
を第２図の実線に示す。In addition, in the above manufacturing example, ZrO2 and TlO2
Adsorbents were obtained in exactly the same manner except that the molar ratio of .
なお、第２図の横軸はＺｒ０１ ／（ＺｒＯ２＋ＴｉＯ
２）ｍｏｔ／ｍ ｏ Ｌで示した。Note that the horizontal axis in Fig. 2 is Zr01/(ZrO2+TiO
2) Expressed in mot/m o L.
また、参考のために焼成温度を６００℃にした場合につ
いて第２図の点線に示す。For reference, the case where the firing temperature was 600° C. is shown by the dotted line in FIG.
第２図から明らかなように、ＺｒＯ２／ＴｉＯ２の比率
は、１：１よシややＺｒＯ２が多い側に吸着性能にピー
クが見られる。しかし、ＺｒＯ２はＴｌＯ２よシも高価
であるから、これを考慮すればＺｒＯ２／ＴｌＯ２のモ
ル比は１．０±α２の範囲が最適である。As is clear from FIG. 2, when the ZrO2/TiO2 ratio is slightly higher than 1:1, a peak in adsorption performance can be seen on the side with more ZrO2. However, since ZrO2 is more expensive than TlO2, taking this into consideration, the optimum molar ratio of ZrO2/TlO2 is in the range of 1.0±α2.
更に、第１図、第２図のデータを得るのに調裏した各種
比表面積を有する吸着剤の吸着性能をドデカツノの吸着
量で調べ、この結果を第３図に示す。Furthermore, the adsorption performance of adsorbents having various specific surface areas, which were used to obtain the data shown in FIGS. 1 and 2, was investigated based on the adsorption amount of dode bonito, and the results are shown in FIG. 3.
第３図から明らかなように、比表面積が大であれば高Ａ
＠着性能を示す。As is clear from Figure 3, the larger the specific surface area, the higher the A
@ Indicates adhesion performance.
なお、本発明のＮＨ３法を、加熱分解を要する尿素法と
も比較したか、吸着性能に大差なく加熱手段の不要な本
発明のＮＨ３法に利点があることが明らかとなった。The NH3 method of the present invention was also compared with the urea method, which requires thermal decomposition, and it became clear that the NH3 method of the present invention, which does not require a heating means, has an advantage as there is no significant difference in adsorption performance.
本発明によれば、従来の代表的吸着剤であるＳ ｉ ｏ
、に比し約１０倍も高い吸着性能を有し、しかも水に対
する水溶性と辷高い耐薬品性とを有する吸着剤を安価に
製造することができる。According to the present invention, S i o which is a typical conventional adsorbent
It is possible to produce an adsorbent at a low cost, which has an adsorption performance that is about 10 times higher than that of , and also has water solubility and high chemical resistance.
第１図は吸着剤の焼成温度と比表面積との関係を示す図
表、第２図は吸着剤のＺｒＯ２／（ＺｒＯ２十ＴｉＯ，
） Ｃモル比）と比表面積との関係を示す図表、第３図
は吸着剤の比表面積とドデカツノ吸着量との関係を示す
図表である。Figure 1 is a chart showing the relationship between the calcination temperature and specific surface area of the adsorbent, and Figure 2 is the graph showing the relationship between the adsorbent's calcination temperature and specific surface area.
Figure 3 is a diagram showing the relationship between the specific surface area (C molar ratio) and the specific surface area.
Claims (1)
＿３法によりＴｉの水酸化物とＺｒの水酸化物を沈澱さ
せ、該沈澱物を３５０〜４５０℃にて焼成し、ＺｒＯ＿
２／ＴｉＯ＿２のモル比が１．０±０．３の吸着剤を製
造することを特徴とする吸着剤の調製法。NH using Ti chlorine compound and Zr chlorine compound as raw materials
Ti hydroxide and Zr hydroxide are precipitated by method _3, and the precipitate is calcined at 350 to 450°C to form ZrO_
A method for preparing an adsorbent, the method comprising producing an adsorbent having a molar ratio of 2/TiO_2 of 1.0±0.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5418487A JPS63221845A (en) | 1987-03-11 | 1987-03-11 | Preparation of adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5418487A JPS63221845A (en) | 1987-03-11 | 1987-03-11 | Preparation of adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63221845A true JPS63221845A (en) | 1988-09-14 |
Family
ID=12963459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5418487A Pending JPS63221845A (en) | 1987-03-11 | 1987-03-11 | Preparation of adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63221845A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990014885A1 (en) * | 1989-05-29 | 1990-12-13 | Leonid Mikhailovich Sharygin | Granulated inorganic sorbent and method of obtaining it |
-
1987
- 1987-03-11 JP JP5418487A patent/JPS63221845A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990014885A1 (en) * | 1989-05-29 | 1990-12-13 | Leonid Mikhailovich Sharygin | Granulated inorganic sorbent and method of obtaining it |
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