JP5024567B2 - Crystalline selenium powder and method for producing the same - Google Patents
Crystalline selenium powder and method for producing the same Download PDFInfo
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 72
- 239000011669 selenium Substances 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 238000010298 pulverizing process Methods 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000002178 crystalline material Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 8
- 230000004927 fusion Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940000207 selenious acid Drugs 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Description
本発明は、結晶質セレン粉末とその製造方法に関し、より詳しくは、非晶質セレンを結晶化して粉砕する結晶質セレン粉末とその製造方法に関する。
The present invention relates to crystalline selenium powder and a method for producing the same, and more particularly to crystalline selenium powder for crystallizing and pulverizing amorphous selenium and a method for producing the same .
高純度のセレンを製造する方法として蒸留法が知られている。例えば、特許第３８３８７４４号公報（特許文献１）には、原料ルツボに装入した原料セレンを真空蒸留し、蒸留されたセレンを凝縮させ、この凝縮液をルツボ下方の回収鋳型に流下させ、インゴットとして回収する方法が記載されている。あるいは、特開２００５−１９０６号公報（特許文献２）には、セレン含有原料を予めプレ溶解炉で加熱溶解し、残渣（Pt,Pd等）を除去した溶湯を溶解炉を通じて蒸留装置に導いて真空蒸留する方法が記載されている。 A distillation method is known as a method for producing high-purity selenium. For example, in Japanese Patent No. 3838744 (Patent Document 1), raw material selenium charged in a raw material crucible is vacuum distilled, condensed selenium is condensed, and this condensate is allowed to flow down to a recovery mold below the crucible. As a recovery method. Alternatively, Japanese Patent Laid-Open No. 2005-1906 (Patent Document 2) discloses that a selenium-containing raw material is heated and melted in a pre-melting furnace in advance and the molten metal from which residues (Pt, Pd, etc.) are removed is led to a distillation apparatus through the melting furnace. A method of vacuum distillation is described.
前者の蒸留法において、セレン蒸気は凝縮された後に鋳型に導かれてインゴットとして回収されるが、この他に、セレン凝縮液を鋳造ドラム上に連続的に滴下して粒子（乾式ショット粒）として回収する方法が知られている（特許文献３：特開２００１−３１６７３５号公報）。また、セレン蒸気の凝縮液を水中に導いて急冷し、水砕効果によって粒子化し、ショット粒として回収する方法も知られている。 In the former distillation method, selenium vapor is condensed and then led to a mold and recovered as an ingot. In addition to this, selenium condensate is continuously dropped onto a casting drum as particles (dry shot particles). A recovery method is known (Patent Document 3: Japanese Patent Laid-Open No. 2001-316735). Also known is a method in which a condensate of selenium vapor is introduced into water, rapidly cooled, granulated by a water granulation effect, and recovered as shot grains.
蒸留法によって回収したセレンのショットは非晶質であるため、４０℃以上で表面が軟化して互いに固着する。このため、取り扱い難くなる。また、非晶質セレンのショット粒を粉砕機に入れて粉砕すると、粉砕機内で融着を生じ、粉砕に支障をきたすと云う問題がある。 Since the shots of selenium recovered by the distillation method are amorphous, the surfaces soften at 40 ° C. or higher and adhere to each other. For this reason, it becomes difficult to handle. Further, when the amorphous selenium shot grains are put in a pulverizer and pulverized, there is a problem that fusion occurs in the pulverizer and hinders the pulverization.
本発明は、蒸留法などよって得た非晶質セレンについて、従来の上記問題を解決したものであり、非晶質セレンを結晶化して取扱性を高め、さらに、結晶化して粉砕することによって粉砕機内の融着などの問題を解消したものであり、高純度で結晶性の高いセレン粉末とその結晶化方法ないし粉末化方法を提供する。 The present invention solves the above-mentioned conventional problems with amorphous selenium obtained by distillation or the like, and crystallizes amorphous selenium to improve handling, and further, crystallizes and pulverizes it. A selenium powder having high purity and high crystallinity, and a crystallization method or a pulverization method thereof, which solves problems such as in-machine fusion.
本発明は、以下の構成を有する結晶質セレン粉末とその製造方法に関する。
〔１〕セレン蒸気を蒸留炉から抜き出して凝縮し、この凝縮液を水中に導入して水砕された非晶質セレン粒子にし、この非晶質セレン粒子を１００℃〜２１０℃に加熱して結晶化した後に、該結晶質セレン粒子を粉砕して粉末にすることを特徴とする結晶質セレン粉末の製造方法。
〔２〕結晶質セレン粒子を粉砕機で二段階に粉砕し、一段目の粉砕で粒径５〜１０mmに粉砕し、二段目の粉砕で粒径５０〜７０μmに粉砕する上記[１]に記載する結晶質セレン粉末の製造方法。
〔３〕上記[１]または上記[２]に記載する方法によって製造された結晶質セレン粉末であって、Ｘ線回折における最大回折ピークの半値幅が０.３°以下であり、硫黄含有量２０ppm以下、おおびナトリウム含有量１０ppm以下であることを特徴とする結晶質セレン粉末。
The present invention relates to crystalline selenium powder having the following constitution and a method for producing the same .
[1] The selenium vapor is extracted from the distillation furnace and condensed, and the condensate is introduced into water to form crushed amorphous selenium particles. The amorphous selenium particles are heated to 100 ° C. to 210 ° C. A method for producing crystalline selenium powder, characterized by pulverizing the crystalline selenium particles into a powder after crystallization.
[2] The crystalline selenium particles are pulverized in two stages with a pulverizer, pulverized to a particle size of 5 to 10 mm by the first pulverization, and pulverized to a particle diameter of 50 to 70 μm by the second pulverization. Process for producing crystalline selenium powder to be described.
[3] Crystalline selenium powder produced by the method described in [1] or [2] above, wherein the half-value width of the maximum diffraction peak in X-ray diffraction is 0.3 ° or less, and the sulfur content Crystalline selenium powder characterized by being 20 ppm or less and a sodium content of 10 ppm or less.
本発明の結晶質セレン粉末は、蒸留法によって得た非晶質セレンを加熱処理して結晶化した乾式処理によるセレンであり、従来の湿式処理によって得た結晶質セレンに比べて、結晶性が高く、かつ高純度である。
The crystalline selenium powder of the present invention is selenium produced by a dry process in which amorphous selenium obtained by distillation is crystallized by heat treatment, and has a crystallinity as compared with crystalline selenium obtained by a conventional wet process. High and high purity.
また、本発明の製造方法は、セレン蒸気を蒸留炉から抜き出して凝縮し、この凝縮液を水中に導入して水砕された非晶質セレン粒子にし、この非晶質セレン粒子を１００℃〜２１０℃に加熱して結晶化した後に、該結晶質セレン粒子を粉砕して粉末にする方法であり、蒸留法によって回収した非晶質セレンを水砕した非晶質セレン粒子にし、この非晶質セレン粒子を加熱処理することによって容易に結晶化することができる。また、非晶質セレン粒子を結晶化して粉砕するので、粉砕機内で融着などを引き起こすことがなく、円滑に粉砕することができる。
Further, in the production method of the present invention, selenium vapor is extracted from the distillation furnace and condensed, and the condensed liquid is introduced into water to form crushed amorphous selenium particles. This is a method of pulverizing the crystalline selenium particles by heating to 210 ° C. and then pulverizing the crystalline selenium particles. The selenium particles can be easily crystallized by heat treatment . Further, since the amorphous selenium particles are crystallized and pulverized, they can be pulverized smoothly without causing fusion or the like in the pulverizer.
以下、本発明を実施形態に基づいて具体的に説明する。
本発明の製造方法は、セレン蒸気を蒸留炉から抜き出して凝縮し、この凝縮液を水中に導入して水砕された非晶質セレン粒子にし、この非晶質セレン粒子を１００℃〜２１０℃に加熱して結晶化した後に、該結晶質セレン粒子を粉砕して粉末にすることを特徴とする結晶質セレン粉末の製造方法である。
Hereinafter, the present invention will be specifically described based on embodiments.
In the production method of the present invention , selenium vapor is extracted from a distillation furnace and condensed, and this condensate is introduced into water to form crushed amorphous selenium particles. A method for producing crystalline selenium powder, characterized in that the crystalline selenium particles are pulverized into powder after being heated and crystallized.
蒸留法によって非晶質セレンを回収するには、例えば、蒸留炉の炉内温度を５００℃〜６００℃に保持してセレン含有原料を溶湯状態に維持し、このセレン含有原料の溶湯中に原料のセレン含有粉末を供給して溶融させる工程と、セレンの溶湯を沸点以上に加熱してセレンを蒸留する工程とを繰り返してセレンを半連続的にセレンを蒸留させて回収することができる。 In order to recover amorphous selenium by distillation, for example, the temperature in the distillation furnace is maintained at 500 ° C. to 600 ° C. to maintain the selenium-containing raw material in a molten state, and the raw material is contained in the molten selenium-containing raw material. The selenium-containing powder can be recovered by semi-continuously distilling selenium by repeating the step of supplying and melting the selenium-containing powder and the step of heating the molten selenium to a boiling point or higher to distill selenium.
セレン含有原料としては、市販の金属セレン粉末、銅製錬の電解工程で発生する電解澱物から得られた粉末状のセレン含有物などを用いることができる。セレンの融点は約２２０℃であるので、例えば、蒸留炉を５００℃〜６００℃に保持すると、セレン含有粉末原料は溶解してセレン溶湯となる。炉内を密閉にしてセレン溶湯を沸点以上、例えば約６７０℃〜７５０℃に加熱するとセレンが蒸留する。 As the selenium-containing raw material, commercially available metal selenium powder, powdered selenium-containing material obtained from an electrolytic starch generated in an electrolytic process of copper smelting, or the like can be used. Since the melting point of selenium is about 220 ° C., for example, when the distillation furnace is maintained at 500 ° C. to 600 ° C., the selenium-containing powder raw material is melted to become a molten selenium. When the furnace is sealed and the molten selenium is heated to the boiling point or higher, for example, about 670 ° C. to 750 ° C., selenium is distilled.
このセレン蒸気を蒸留炉から抜き出して凝縮し、この凝縮液を水中に導入すると、セレンは急冷されて金属化すると共に水砕作用を受けて粒径が数ミリの非晶質セレン粒子になる。 When this selenium vapor is extracted from the distillation furnace and condensed, and this condensate is introduced into water, the selenium is rapidly cooled to be metallized and subjected to a water crushing action to become amorphous selenium particles having a particle size of several millimeters.
この非晶質セレン粒子を加熱容器に入れ、１００℃〜２１０℃に加熱して結晶化する。加熱温度が１００℃未満であると結晶化しない。また加熱温度が２１０℃を上回ると融解が始まるので好ましくない。 The amorphous selenium particles are put in a heating container and heated to 100 ° C. to 210 ° C. for crystallization. If the heating temperature is less than 100 ° C, crystallization will not occur. On the other hand, if the heating temperature exceeds 210 ° C, melting starts, which is not preferable.
加熱時間は３０-〜６０分であれば良い。加熱雰囲気は非酸化性が好ましいが、空気中でもよい。 The heating time may be 30--60 minutes. The heating atmosphere is preferably non-oxidizing, but may be in air.
上記加熱処理によって結晶性の高いセレン粒子になる。具体的には、例えば、Ｘ線回折における最大回折ピークの相対強度が１０００以上であって、該最大ピークの半値幅が０.３°以下であるシャープな回折ピークを有するセレン粒子を得ることができる。
By the heat treatment, selenium particles having high crystallinity are obtained. Specifically, for example, it is possible to obtain a selenium particle having a sharp diffraction peak in which the relative intensity of the maximum diffraction peak in X-ray diffraction is 1000 or more and the half width of the maximum peak is 0.3 ° or less. it can.
また、この結晶質セレンは蒸留法によって回収した非晶質セレンを結晶化したものであるので、高純度であり、例えば、硫黄含有量２０ppm以下、ナトリウム含有量１０ppm以下である。 Further, since this crystalline selenium is obtained by crystallizing amorphous selenium recovered by a distillation method, it has high purity, for example, a sulfur content of 20 ppm or less and a sodium content of 10 ppm or less.
上記結晶質セレンを粉砕機に入れ、目的の粒度になるように粉砕する。粉砕は二段階に行うとよく、例えば一段目の粉砕で粒径５〜１０mmに粉砕し、二段目の粉砕で粒径５０〜７０μmまで粉砕すると良い。 The crystalline selenium is put in a pulverizer and pulverized to a target particle size. The pulverization may be performed in two stages. For example, the pulverization may be performed to a particle size of 5 to 10 mm by the first pulverization and the particle size may be pulverized to 50 to 70 μm by the second pulverization.
上記結晶質セレンは結晶性が高いので、粉砕機の内部で非晶質セレンのような融着を引き起こさず、良好に粉砕することができる。 Since the crystalline selenium has high crystallinity, it can be pulverized well without causing fusion like amorphous selenium inside the pulverizer.
以下に本発明の実施例を比較例と共に示す。なお、Ｘ線回折の測定条件は次のとおりである。
装置：理学電気社製（ＲＩＮＴ２０００／ＵＬＴＩＭＡ＋）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査範囲（２θ）：５°〜９０°
スリットサイズ：発散（ＤＳ）１度、散乱（ＳＳ）１度、受光（ＲＳ）０.３mm
測定ステップ幅：２θで０.０２度
Examples of the present invention are shown below together with comparative examples. The X-ray diffraction measurement conditions are as follows.
Equipment: Rigaku Denki Co. (RINT2000 / ULTIMA +)
Tube: Cu
Tube voltage: 40 kV
Tube current: 40 mA
Scanning range (2θ): 5 ° to 90 °
Slit size: Divergence (DS) 1 degree, Scattering (SS) 1 degree, Received light (RS) 0.3mm
Measurement step width: 0.02 degrees at 2θ
〔実施例１〜２〕
蒸留法によって得た非晶質セレン粒子を加熱容器に入れ、２００℃、３０分加熱した。この加熱処理されたセレン粒子の結晶性をＸ線回折によって測定した。この結果を表１に示した。また、Ｘ線回折による最大ピーク付近の回折グラフを図１に示した。さらに、この結晶質セレンについて、不純物量として硫黄およびナトリウムの含有量を測定した、この結果を表１に示した。
[Examples 1-2]
The amorphous selenium particles obtained by the distillation method were put in a heating container and heated at 200 ° C. for 30 minutes. The crystallinity of the heat-treated selenium particles was measured by X-ray diffraction. The results are shown in Table 1. A diffraction graph near the maximum peak by X-ray diffraction is shown in FIG. Further, for this crystalline selenium, the contents of sulfur and sodium were measured as impurities, and the results are shown in Table 1.
実施例１および２におい得たセレン粒子を粉砕機に入れて１０分間粉砕したところ、粉砕機内の融着は発生せず、均一なセレン粉末を回収した。 When the selenium particles obtained in Examples 1 and 2 were put into a pulverizer and pulverized for 10 minutes, no fusion in the pulverizer occurred and a uniform selenium powder was recovered.
〔比較例１〜２〕
湿式法によって得たセレンを加熱して結晶化した。まず、亜セレン酸を含有する水溶液に塩化物イオンの存在下で還元剤を添加してセレン沈澱（赤色セレン）を生成させ、この赤色セレンを分離回収して水中に入れ、６０℃以上に加熱し、さらに空気中で１４０℃以上に加熱して結晶化した。このセレン粒子について、結晶性をＸ線回折によって測定した。この結果を表１に示した。また、Ｘ線回折による最大ピーク付近の回折グラフを図１に示した。さらに、この結晶質セレンについて、不純物量として硫黄およびナトリウムの含有量を測定した、この結果を表１に示した。
[Comparative Examples 1-2]
Selenium obtained by the wet method was heated and crystallized. First, a reducing agent is added to an aqueous solution containing selenious acid in the presence of chloride ions to form a selenium precipitate (red selenium). This red selenium is separated and recovered, put into water, and heated to 60 ° C. or higher. Further, it was crystallized by heating to 140 ° C. or higher in air. The selenium particles were measured for crystallinity by X-ray diffraction. The results are shown in Table 1. A diffraction graph near the maximum peak by X-ray diffraction is shown in FIG. Further, for this crystalline selenium, the contents of sulfur and sodium were measured as impurities, and the results are shown in Table 1.
表１および図１に示すように、実施例１〜２のセレンは、Ｘ線回折における最大回折ピークの相対強度が１０００以上であって、該最大ピークの半値幅が０.３以下であるシャープな回折ピークを有している。また、硫黄含有量２０ppm以下、ナトリウム含有量１０ppm以下であり、不純物量が大幅に少ない。 As shown in Table 1 and FIG. 1, the selenium of Examples 1 and 2 has a sharpness in which the relative intensity of the maximum diffraction peak in X-ray diffraction is 1000 or more and the half-value width of the maximum peak is 0.3 or less. Has a good diffraction peak. In addition, the sulfur content is 20 ppm or less, the sodium content is 10 ppm or less, and the amount of impurities is significantly small.
一方、比較例１−２のセレンは、、Ｘ線回折における最大回折ピークの相対強度が実施例１〜２の半分以下、その半値幅は実施例１〜２の２倍以上であり、結晶性が実施例１〜２よりも格段に低い。また、硫黄含有量は４００ppm台、ナトリウム含有量３００ppm台であり、不純物量が格段に多い。 On the other hand, the selenium of Comparative Example 1-2 has a relative intensity of the maximum diffraction peak in X-ray diffraction that is not more than half that of Examples 1-2, and its half-value width is not less than twice that of Examples 1-2. However, it is much lower than Examples 1-2. Further, the sulfur content is in the 400 ppm range and the sodium content is in the 300 ppm range, and the amount of impurities is remarkably large.
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| GB1603468A (en) * | 1977-09-14 | 1981-11-25 | Xerox Corp | Electrophotographic member |
| JPS54120228A (en) * | 1978-03-13 | 1979-09-18 | Ricoh Co Ltd | Production of metallic selenium |
| JPS5518606A (en) * | 1978-07-25 | 1980-02-08 | Ricoh Co Ltd | Production of selenium material for electrophotography |
| JPS5832004A (en) * | 1981-08-20 | 1983-02-24 | Ricoh Co Ltd | Preparation of selenium for vacuum evaporation |
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| JPS6117404A (en) * | 1984-07-04 | 1986-01-25 | Fuji Xerox Co Ltd | Production of selenium |
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| JP3838744B2 (en) * | 1997-05-26 | 2006-10-25 | 同和鉱業株式会社 | Method for producing high purity selenium |
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