JP4989015B2 - Method and apparatus for vacuum distillation of selenium - Google Patents
Method and apparatus for vacuum distillation of selenium Download PDFInfo
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- JP4989015B2 JP4989015B2 JP2003164529A JP2003164529A JP4989015B2 JP 4989015 B2 JP4989015 B2 JP 4989015B2 JP 2003164529 A JP2003164529 A JP 2003164529A JP 2003164529 A JP2003164529 A JP 2003164529A JP 4989015 B2 JP4989015 B2 JP 4989015B2
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Description
【0001】
【発明の属する技術分野】
本発明は、安価な方法により高純度セレンを真空蒸留により製造する方法に関する。
【0002】
【従来の技術】
従来のセレンの真空蒸留装置は、例えば高純度セレン製造装置(特公平1-4961:特許文献1)が提案されている。この技術は、セレンの精製原料となるセレンの不純物量が制限され、セレン品位99.9 mass %以上の原料セレンを用いて高純度セレンを製造する場合に用いられていた。
【0003】
また銅電解澱物湿式処理プロセス(特開2001-316735:特許文献2)に示すように、原料セレンを得る工程で不純物を制御する必要があり、不純物は1%以下にしなければ真空蒸留処理において、良好な成績は得られなかった。
【0004】
高純度セレンの製造方法及び製造装置(特開平10-324932:特許文献3)
において開示されている内容は、純度99.99 mass %の市販セレンを真空度1×10-2Torr電気炉温度300℃、5時間条件で精製する方法、さらに真空精製部が脱着可能であり、るつぼ、回収鋳型、冷却トラップ、水冷フランジから構成され、回収鋳型が耐熱材からなる二重の筒で封体される高純度セレン製造装置が開示されている。上記の文献では、セレンの精製原料となるセレンの不純物量が極めて、低くく維持されるように制限されている。
【0005】
即ち上記の処理法においても、セレン品位99.9 mass %以上の製品セレンを原料として高純度セレンを製造する場合に用いられたり、前記に示すように原料セレンを得る工程で不純物を制御する必要があり、不純物は1 mass %以下にしなければ良好な成績は得られなかった。またセレンよりも高融点、低蒸気圧である不純物は蒸留塔に残渣として残る。この残渣が多いと残渣抜出しラインを閉塵させ、操業継続を困難とする。
【0006】
【特許文献1】
特公平1-4961
【特許文献2】
特開2001-316735
【特許文献3】
特開平10-324932
【0007】
【発明が解決しようとする課題】
そこで、本発明においては、低コストで原料セレン中に高融点のPt、Pd等が、含んでいる物であっても処理が可能な方法及び装置を提供する。
【0008】
本発明に係るセレンの真空蒸留方法は、セレンを含有し、不純物としてテルル、白金、パラジウム、及び鉄を少なくとも含有する原料を希塩酸で洗浄し、テルルを除去し、更に純水にて塩酸を十分除去し、前記処理した原料を、予めプレ溶解炉において、400〜500℃にて溶解し、当該溶解により生じた残渣であって、白金、パラジウム、及び鉄を少なくとも含有する残渣を予め除去し、次いで前記プレ溶解炉から供給される前記原料を350〜400℃にて溶解する溶解釜を介して、当該溶解釜において白金、パラジウム、及び鉄を少なくとも含有する前記残渣を更に除去したうえで、真空蒸留装置において、前記セレンを精製する。水洗浄後の原料セレンを乾燥処理することが好ましい。
【0009】
本発明に係るセレンの真空蒸留装置は、希塩酸による洗浄によりテルルが除去され、更に純水にて塩酸が十分除去された原料であって、セレンを含有し、不純物として、少なくとも白金、パラジウム、及び鉄を含有する前記原料を400〜500℃にて溶解し、かつ白金、パラジウム、及び鉄を少なくとも含有する残渣を除去するプレ溶解炉と、前記プレ溶解炉から供給される前記原料を350〜400℃にて溶解し、白金、パラジウム、及び鉄を少なくとも含有する前記残渣を更に除去する溶解釜を真空蒸留装置の前処理装置として有する。
【0010】
【発明の実施の形態】
以下本発明に関して、詳細に説明する。
本発明の対象原料のセレンは、銅製錬の電解工程で発生する電解殿物から得られたセレン等であって、例えばPt<500mass ppm,Pd<1000mass ppm,Te<50mass ppm,Fe<50mass ppm,Pb<10mass ppm,As<50mass ppm,Cu<10mass ppm,Cl<10mass ppm,Sb<10mass ppm等の重金属を含み99.90mass%>Se>97.00mass%が含まれるものである。
【0011】
上記の原料セレンは、希塩酸(1.2〜2.0N)を用いて、予め洗浄することが望ましい。
パルプ濃度は、1000〜2000g/l程度で行う。この処理により予め原料セレン中のテルル、鉄、銅等を除去しておくことが望ましい。特にテルルは真空蒸留処理において、除去が困難であるためこの段階で除去することが好ましい。
また、鉄、銅等もセレンに較べ高融点のものであり、真空蒸留処理において残渣を形成する物でありこの段階でできるだけ除去しておくことが好ましい。
【0012】
塩酸洗浄後は、工業用水等で十分洗浄することが望ましい。できれば、2回以上の洗浄が望ましい。塩酸が原料セレン中に残存すると、塩酸が装置を腐食するためである。
【0013】
また、工程中の装置からセレン中に不純物(鉄、クロム、ニッケル等)が、混入しないように、各工程における装置の内壁の材質をステンレス鋼またはアルマー処理鋼またはハステロイ(登録商標)としておくことが望ましい。
【0014】
洗浄を終了した原料セレンは、乾燥処理し、水分を除去する。乾燥は、100〜200℃において12時間以上行うことが好ましい。
【0015】
乾燥処理した原料セレンは、プレ溶解炉において、400〜500℃に昇温・溶解される。溶解された原料セレン中の高融点金属Pt、Pd等は、プレ溶解炉の残渣抜き出し口から効率的に除去される。
これにより、従来不可能であった純度の悪い例えば、97mass%程度の原料セレンであっても、真空蒸留炉での残渣抜き出しラインの閉塞を未然に防止できることを把握した。
400℃より低い温度では、原料の流動性が悪く効率的に残渣を抜き出すことが出来ないためである。また500℃より高い温度であると配管等の強度の低下および寿命の低下を来たす。
【0016】
次いで、残渣分を除去された熔融原料セレンは、溶解釜に入れられる。
溶解釜は、350〜400℃等で操業され、真空蒸留塔へは圧力差で供給される。
ここにおいても、一部残渣分を回収除去する。
なお従来法では、残渣の抜き出し配管が短期間で閉塞するため十分な除去が出来なかった。
【0017】
溶解釜の原料セレンは、真空蒸留炉が、真空に引かれると真空蒸留炉に吸引され真空蒸留処理が行われる。真空度は、0.1〜0.001Torrで行われる。
真空蒸留炉での温度は、350〜450℃において行われる。
通常連続運転で行われる。
【0018】
原料投入は、バッチ処理であっても、真空蒸留処理、鋳造は、連続で行われる。これは、残渣の除去と生産性を考慮した為である。
【0019】
上記処理の結果、例えばSe含有量が、97.00mass%と少ない原料であっても、Se純度99.99mass%、Te<5mass ppm、Pb<5mass ppm、Fe<5mass ppmの高純度のセレンが、得られる。
特に従来法では、例えばSe含有量が、99.00mass%と多い原料であっても、Te<50mass ppm、Fe<50mass ppmであったが、本願発明では純度の悪い原料であっても不純物の少ないセレンが容易に得られる。
また真空蒸留炉での残渣ラインにおいて、残渣に含有する鉄、パラジウム、白金等の高融点の金属に起因する目詰まりがなく、連続操業を容易にすることが出来る。
【実施例】
以下本発明に関して、図1にそって、具体的に説明する。
【0020】
表1の原料セレンを1.3N希塩酸で洗浄する。 原料セレン中にはPt、Pd、Teが多く、Se品位が低い値となっている。
また、本発明にかかかる高融点の不純物ではないが、Ru、Rh、更には、酸化物の酸素等が、2mass %前後存在すると考えられる。
【表1】
塩酸洗浄は、パルプ濃度1300g/lで、1回行った。この洗浄によりTeが、10ppmと低下した。
【0021】
塩酸洗浄後、塩素が原料中に残らないように水洗を行った。パルプ濃度を1200g/lで1回行った後、フィルタープレスで脱水し、さらにろ室内にケーキ体積の3倍量通水して洗浄した。その結果、塩素分のほとんどを除くことが出来た。これにより、装置の腐食を防止することが出来た。
【0022】
水洗後は、130℃15時間で乾燥を行った。乾燥後、プレ溶解炉へ原料セレンを投入した。プレ溶解炉では、430℃で20時間加熱溶解後、残渣抜き出し口から残渣を除去した。
この残渣の成分は、表2のようであった。
【0023】
【表2】
【0024】
高融点の白金、パラジウム、鉄、ニッケル等が良く除去されている。テルルもさらに除去されている。
プレ溶解炉で残渣を除去した後、原料セレンは溶解釜に供給する。
【0025】
溶解釜では、380〜400℃の温度で20時間保持し、プレ溶解炉で除去できなかった少量の残渣を除去する。この残渣は、プレ溶解炉での残渣量の10mass %であった。
残渣の成分は、表2とほぼ同等であるが、一緒に流出するセレンで薄まっている。
【0026】
溶解釜の溶湯は圧力差によって蒸留塔へ供給される。蒸留塔へ供給したセレンは0.02Torr、温度を400℃とし、20時間処理をした。
この結果表3のような高純度のセレンを得る事が出来た。
【0027】
【表3】
本願発明の方法により、不純物の除去が効率的に行われた。
原料のセレン品位が悪いものであっても、高純度のセレンを得られるようになった。
また一炉あたりの生産量も安定操業が可能になり、1.5〜2.0倍となった。
【0028】
(比較例)
プレ溶解炉の無い真空蒸留炉で、99.00 mass %の実施例より高品位の原料を処理したが、その製品の品位は、Te 38ppm、Fe 30ppmと不純物が高く、実施例のような高純度のセレンを得ることが出来なかった。
また、真空蒸留炉での残渣除去ラインでの目詰まりがあり、生産量も実施例の0.5倍と極めて少なかった。
【発明の効果】
(1)原料セレンの中に、高融点のもの(Pt、Pd、Fe等)が多くあっ
ても、効率よく高純度セレン(99.99mass %以上)を得ることが出来る。
(2)操業が安定するため一炉当りの生産量が、1.5〜2.0倍と飛躍的に伸
びた。
(3)装置内壁から原料への不純物(鉄、ニッケル、クロム等)の混入を効
率的に排除することが出来る。
【図面の簡単な説明】
【図1】 本発明の一態様である真空処理装置を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing high-purity selenium by vacuum distillation by an inexpensive method.
[0002]
[Prior art]
As a conventional vacuum distillation apparatus for selenium, for example, a high-purity selenium production apparatus (Japanese Patent Publication No. 1-4961: Patent Document 1) has been proposed. This technique has been used in the case of producing high-purity selenium using raw material selenium having a selenium quality of 99.9 mass% or more because the amount of impurities of selenium as a refined raw material of selenium is limited.
[0003]
Moreover, as shown in a copper electrolytic starch wet processing process (Japanese Patent Laid-Open No. 2001-316735: Patent Document 2), it is necessary to control impurities in the step of obtaining raw material selenium. Good results were not obtained.
[0004]
Method and apparatus for producing high purity selenium (JP-A-10-324932: Patent Document 3)
Is disclosed in US Pat. No. 6,057,089, a method of purifying commercially available selenium having a purity of 99.99 mass% under conditions of a vacuum degree of 1 × 10 −2 Torr electric furnace temperature of 300 ° C. for 5 hours, and a vacuum purification section can be detached. An apparatus for producing high-purity selenium, which is composed of a crucible, a recovery mold, a cooling trap, and a water-cooled flange and is sealed with a double cylinder made of a heat-resistant material, is disclosed. In the above-mentioned document, the amount of impurities of selenium used as a selenium refining material is limited so as to be kept extremely low.
[0005]
That is, even in the above-described treatment method, it is necessary to control impurities in the process of obtaining raw selenium as described above, or when producing high-purity selenium using selenium grade 99.9 mass% or more as raw material. Good results could not be obtained unless the impurity content was 1 mass% or less. Impurities having a higher melting point and lower vapor pressure than selenium remain as residues in the distillation column. If this residue is large, the residue extraction line is closed, making it difficult to continue operation.
[0006]
[Patent Document 1]
JP 1-4961
[Patent Document 2]
JP 2001-316735 A
[Patent Document 3]
JP-A-10-324932
[0007]
[Problems to be solved by the invention]
Therefore, the present invention provides a method and an apparatus capable of processing even low-cost raw material selenium containing high melting point Pt, Pd or the like.
[0008]
Vacuum distillation process selenium according to the present invention contains selenium, and an impurity Te Lulu, platinum, palladium, and raw material containing at least the iron is washed with dilute hydrochloric acid to remove tellurium, hydrochloric further with pure water Is removed in advance in a pre-melting furnace at 400 to 500 ° C., and the residue generated by the dissolution is previously removed at least containing platinum, palladium, and iron. Then , after further removing the residue containing at least platinum, palladium, and iron in the melting pot through a melting pot for melting the raw material supplied from the pre-melting furnace at 350 to 400 ° C. The selenium is purified in a vacuum distillation apparatus . The raw selenium after washing with water is preferably dried .
[0009]
The vacuum distillation apparatus for selenium according to the present invention is a raw material from which tellurium has been removed by washing with dilute hydrochloric acid and from which hydrochloric acid has been sufficiently removed with pure water, containing selenium, and as impurities, at least platinum, palladium, and A pre-melting furnace that melts the raw material containing iron at 400 to 500 ° C. and removes a residue containing at least platinum, palladium, and iron, and the raw material supplied from the pre-melting furnace is 350 to 400 ℃ and dissolved at, that Yusuke platinum, palladium, and a dissolving tank to further remove said residue containing at least iron as a pretreatment device of a vacuum distillation unit.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The target raw material selenium of the present invention is selenium or the like obtained from an electrolytic product generated in an electrolytic process of copper smelting, for example, Pt <500 mass ppm, Pd <1000 mass ppm, Te <50 mass ppm, Fe <50 mass ppm. , Pb <10 mass ppm, As <50 mass ppm, Cu <10 mass ppm, Cl <10 mass ppm, Sb <10 mass ppm, and the like, and 99.90 mass%>Se> 9.70 mass%.
[0011]
The raw material selenium is desirably washed in advance using dilute hydrochloric acid (1.2 to 2.0 N).
The pulp concentration is about 1000 to 2000 g / l. It is desirable to previously remove tellurium, iron, copper and the like in the raw material selenium by this treatment. In particular, tellurium is preferably removed at this stage because it is difficult to remove in vacuum distillation.
Moreover, iron, copper, and the like have a higher melting point than selenium, and form a residue in the vacuum distillation treatment, and are preferably removed as much as possible at this stage.
[0012]
After washing with hydrochloric acid, it is desirable to wash thoroughly with industrial water or the like. If possible, two or more washes are desirable. This is because if hydrochloric acid remains in the raw material selenium, the hydrochloric acid corrodes the apparatus.
[0013]
In order to prevent impurities (iron, chromium, nickel, etc.) from entering the selenium from the equipment in the process, the material of the inner wall of the equipment in each process should be stainless steel, alumer-treated steel or Hastelloy (registered trademark). Is desirable.
[0014]
The raw selenium that has been washed is dried to remove moisture. The drying is preferably performed at 100 to 200 ° C. for 12 hours or more.
[0015]
The raw material selenium that has been dried is heated and melted to 400 to 500 ° C. in a premelting furnace. The high melting point metals Pt, Pd and the like in the melted raw material selenium are efficiently removed from the residue outlet of the premelting furnace.
As a result, it was grasped that the residue extraction line in the vacuum distillation furnace can be prevented from being obstructed even if the raw material selenium having a low purity, for example, about 97 mass%, which has been impossible in the past, is used.
This is because at a temperature lower than 400 ° C., the flowability of the raw material is poor and the residue cannot be extracted efficiently. On the other hand, if the temperature is higher than 500 ° C., the strength of pipes and the like are lowered and the life is shortened.
[0016]
Next, the molten raw material selenium from which the residue has been removed is placed in a melting pot.
The melting kettle is operated at 350 to 400 ° C. or the like, and is supplied to the vacuum distillation tower with a pressure difference.
Also in this case, a part of the residue is recovered and removed.
In addition, in the conventional method, since the residue extraction piping was blocked in a short period of time, it could not be removed sufficiently.
[0017]
When the vacuum distillation furnace is evacuated, the raw material selenium of the melting pot is sucked into the vacuum distillation furnace and subjected to vacuum distillation treatment. The degree of vacuum is 0.1 to 0.001 Torr.
The temperature in a vacuum distillation furnace is 350-450 degreeC.
Usually performed continuously.
[0018]
Even if the raw material is charged in batch processing, vacuum distillation processing and casting are performed continuously. This is because residue removal and productivity are taken into consideration.
[0019]
As a result of the above treatment, for example, even if the Se content is as low as 97.00 mass%, high purity selenium with Se purity 99.99 mass%, Te <5 mass ppm, Pb <5 mass ppm, Fe <5 mass ppm is obtained. ,can get.
In particular, in the conventional method, for example, even if the raw material has a high Se content of 99.00 mass%, Te <50 mass ppm and Fe <50 mass ppm. Less selenium is easily obtained.
Further, in a residue line in a vacuum distillation furnace, there is no clogging due to a high melting point metal such as iron, palladium, platinum contained in the residue, and continuous operation can be facilitated.
【Example】
Hereinafter, the present invention will be described in detail with reference to FIG.
[0020]
The raw selenium in Table 1 is washed with 1.3N dilute hydrochloric acid. The raw material selenium contains a large amount of Pt, Pd, and Te, and has a low Se quality.
Further, although it is not a high melting point impurity according to the present invention, it is considered that Ru, Rh, oxide oxygen and the like are present at about 2 mass%.
[Table 1]
Hydrochloric acid washing was performed once at a pulp concentration of 1300 g / l. This washing decreased Te to 10 ppm.
[0021]
After washing with hydrochloric acid, it was washed with water so that no chlorine remained in the raw material. The pulp concentration was 1200 g / l once, followed by dewatering with a filter press, and further washing by passing 3 times the cake volume through the filter chamber. As a result, most of the chlorine content could be removed. Thereby, corrosion of the apparatus was able to be prevented.
[0022]
After washing with water, drying was performed at 130 ° C. for 15 hours. After drying, raw material selenium was charged into a premelting furnace. In the pre-melting furnace, after heating and melting at 430 ° C. for 20 hours, the residue was removed from the residue outlet.
The components of this residue were as shown in Table 2.
[0023]
[Table 2]
[0024]
High melting point platinum, palladium, iron, nickel, etc. are well removed. Tellurium has also been removed.
After removing the residue in the premelting furnace, the raw material selenium is supplied to the melting pot.
[0025]
In the melting pot, hold at a temperature of 380 to 400 ° C. for 20 hours to remove a small amount of residue that could not be removed in the pre-melting furnace. This residue was 10 mass% of the amount of residue in the premelting furnace.
The components of the residue are almost the same as in Table 2, but are diluted with selenium flowing out together.
[0026]
The molten metal in the melting kettle is supplied to the distillation tower by the pressure difference. The selenium supplied to the distillation column was 0.02 Torr, the temperature was 400 ° C., and treated for 20 hours.
As a result, high purity selenium as shown in Table 3 was obtained.
[0027]
[Table 3]
Impurities were efficiently removed by the method of the present invention.
Even if the selenium quality of the raw material is poor, high-purity selenium can be obtained.
In addition, the amount of production per furnace has become stable, and has increased 1.5 to 2.0 times.
[0028]
(Comparative example)
In the vacuum distillation furnace without pre-melting furnace, high quality raw materials were processed compared to the example of 99.00 mass%, but the quality of the product is as high as 38 ppm Te and 30 ppm Fe, which is as high as in the examples. It was not possible to obtain pure selenium.
Moreover, there was clogging in the residue removal line in the vacuum distillation furnace, and the production amount was extremely small, 0.5 times that of the example.
【Effect of the invention】
(1) Even if the raw material selenium has a high melting point (Pt, Pd, Fe, etc.), high-purity selenium (99.99 mass% or more) can be obtained efficiently.
(2) Since the operation is stable, the production amount per furnace has increased dramatically by 1.5 to 2.0 times.
(3) It is possible to efficiently exclude impurities (iron, nickel, chromium, etc.) from the inner wall of the apparatus to the raw material.
[Brief description of the drawings]
FIG. 1 shows a vacuum processing apparatus which is one embodiment of the present invention.
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JP4957909B2 (en) * | 2007-12-25 | 2012-06-20 | 三菱マテリアル株式会社 | Selenium distillation method and distillation apparatus |
CN110894065B (en) * | 2019-12-18 | 2023-04-07 | 中南大学 | Equipment and method for preparing high-purity tellurium |
JP7325363B2 (en) * | 2020-03-12 | 2023-08-14 | Jx金属株式会社 | Method for treating mixtures containing selenium and tellurium |
CN114180536A (en) * | 2022-01-05 | 2022-03-15 | 昆明理工大学 | Crude selenium slag purification device and method |
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