JP2011079714A - Method for purifying tin-containing waste and tin oxide purified product - Google Patents
Method for purifying tin-containing waste and tin oxide purified product Download PDFInfo
- Publication number
- JP2011079714A JP2011079714A JP2009234537A JP2009234537A JP2011079714A JP 2011079714 A JP2011079714 A JP 2011079714A JP 2009234537 A JP2009234537 A JP 2009234537A JP 2009234537 A JP2009234537 A JP 2009234537A JP 2011079714 A JP2011079714 A JP 2011079714A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- tin oxide
- waste
- containing waste
- purifying
- 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 119
- 239000002699 waste material Substances 0.000 title claims abstract description 115
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000012264 purified product Substances 0.000 title claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 46
- 239000011521 glass Substances 0.000 claims abstract description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000460 chlorine Substances 0.000 claims abstract description 35
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000004090 dissolution Methods 0.000 claims abstract description 15
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 239000006228 supernatant Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 roof tiles Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、スズ（Ｓｎ）及びスズ酸化物（ＳｎＯ２等）の少なくともいずれかを含有するスズ含有廃棄物からガラスの澄泡剤として有用な酸化スズ精製物を精製することができるスズ含有廃棄物の精製方法及び該スズ含有廃棄物の精製方法により精製された酸化スズ精製物に関する。 INDUSTRIAL APPLICABILITY The present invention is a tin-containing waste that can purify a tin oxide purified product useful as a glass defoamer from a tin-containing waste containing at least one of tin (Sn) and tin oxide (SnO 2 or the like) The present invention relates to a purified product of tin oxide and a purified product of tin oxide purified by the method of purifying the waste containing tin.
金属スズは、鉱石から製錬することで得られる。即ち、金属スズの原鉱は、錫石であり、該錫石の精鉱を、溶鉱炉、反射炉、電気炉等で乾式法によって処理し、得られた粗錫を電解することにより得られる。また、スズ酸化物は、ガラス製造時の澄泡剤として広く用いられている（特許文献１参照）。このようなスズ酸化物の製造方法としては、下記化学式で示すように、金属スズを硝酸に溶解し、生成したメタスズ酸沈殿物を回収し、これを焼成する方法が提案されている（特許文献２参照）。
これに対し、本発明者らは、先に、スズ及びスズ酸化物を含有するスズ含有廃棄物を、水及び酸溶液の少なくともいずれかと混合してなるスラリー中のスズ及びスズ酸化物以外の成分を溶解する溶解工程と、スラリーを固液分離してスズ酸化物を精製する精製工程と、を含むスズ含有廃棄物の精製方法を提案している（特願２００８−２０７５７４号参照）。この提案によれば、低エネルギー、低コストでのスズ酸化物の精製が可能であり、得られた酸化スズ精製物はガラスの澄泡剤として利用できる。 On the other hand, the present inventors have previously made a component other than tin and tin oxide in a slurry obtained by mixing tin-containing waste containing tin and tin oxide with at least one of water and an acid solution. Has proposed a method for purifying tin-containing waste, which comprises a dissolution step for dissolving the slurry and a purification step for purifying tin oxide by solid-liquid separation of the slurry (see Japanese Patent Application No. 2008-207574). According to this proposal, it is possible to purify tin oxide with low energy and low cost, and the obtained tin oxide purified product can be used as a glass foaming agent.
しかし、スズ含有廃棄物中には、Ｃａ、塩素、カルシウム、塩素、フッ素、ケイ素、鉄、ナトリウム又はそれらの化合物などの様々な不純物が存在し、該不純物を除去できないとリサイクル品としての価値が低下してしまう。また、これらの不純物の残留量が多くなると、ガラス澄泡剤としての性能が低下してしまうという問題がある。 However, there are various impurities such as Ca, chlorine, calcium, chlorine, fluorine, silicon, iron, sodium, or their compounds in the tin-containing waste. It will decline. Moreover, when the residual amount of these impurities increases, there exists a problem that the performance as a glass fining agent will fall.
本発明は、従来における諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、スズ及び酸化スズの少なくともいずれかを含有するスズ含有廃棄物から酸化スズを精製し、塩素含有量が少なく、ガラスの澄泡剤として再利用が可能な酸化スズ精製物を効率よく精製できるスズ含有廃棄物の精製方法及び酸化スズ精製物を提供することを目的とする。 An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention purifies tin oxide from a tin-containing waste containing at least one of tin and tin oxide, and provides a purified tin oxide that has a low chlorine content and can be reused as a glass defattant. It is an object to provide a method for purifying tin-containing waste that can be purified efficiently and a tin oxide purified product.
前記課題を解決するため本発明者らが鋭意検討を重ねた結果、酸化スズ精製物中に塩素が多く含有されていると、ガラス消泡剤としての特性の低下が見られ、塩素が他の不純物よりもガラス消泡剤としての特性に悪影響を及ぼすことを知見した。 As a result of intensive studies by the present inventors in order to solve the above problems, when a large amount of chlorine is contained in the tin oxide refined product, the properties as a glass antifoaming agent are deteriorated. It has been found that the properties as a glass defoamer are adversely affected rather than impurities.
本発明は、本発明者らによる前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ スズ及びスズ酸化物の少なくともいずれかを含有するスズ含有廃棄物に、水及び酸溶液の少なくともいずれかを添加して廃棄物スラリーを調製するリパルプ工程と、
前記廃棄物スラリーと酸溶液を混合してスズ及びスズ酸化物以外の成分を溶解する溶解工程と、
スズ及びスズ酸化物以外の成分を溶解した後の廃棄物スラリーを固液分離してスズ酸化物を精製する精製工程と、
前記固液分離した固形分を洗浄して酸化スズ精製物を得る洗浄工程と、を含み、
前記酸化スズ精製物中の塩素含有量が、２質量％以下であることを特徴とするスズ含有廃棄物の精製方法である。
＜２＞ 溶解工程により、スズ及びスズ酸化物以外の成分を溶解した後の廃棄物スラリーを静置し、上澄みを除去した後、水を添加する上澄み置換工程を含む前記＜１＞に記載のスズ含有廃棄物の精製方法である。
＜３＞ 塩素含有量が、１質量％以下である前記＜１＞から＜２＞のいずれかに記載のスズ含有廃棄物の精製方法である。
＜４＞ 酸溶液が塩酸である前記＜１＞から＜３＞のいずれかに記載のスズ含有廃棄物の精製方法である。
＜５＞ スズ含有廃棄物が、太陽電池基板を製造する際の酸化スズを蒸着する工程で発生する廃棄物である前記＜１＞から＜４＞のいずれかに記載のスズ含有廃棄物の精製方法である。
＜６＞ スズ含有廃棄物が、太陽電池基板を製造する際の酸化スズの被覆工程、表面処理工程、真空蒸着工程、及び薄膜スパッタリング工程のいずれかで発生する廃棄物であり、かつ該廃棄物がアルカリ土類金属又はアルカリ金属を含有している前記＜１＞から＜４＞のいずれかに記載のスズ含有廃棄物の精製方法である。
＜７＞ スズ含有廃棄物が、太陽電池基板を製造する際の酸化スズを蒸着する工程で排出される排ガスをアルカリ土類金属化合物又はアルカリ金属化合物によって中和して得られる粉状乃至スラリー状の廃棄物であり、かつ該廃棄物がカルシウムを５質量％〜６０質量％含有している前記＜１＞から＜４＞のいずれかに記載のスズ含有廃棄物の精製方法である。
＜８＞ 前記＜１＞から＜７＞のいずれかに記載のスズ含有廃棄物の精製方法により精製されたことを特徴とする酸化スズ精製物である。
＜９＞ 酸化スズ精製物中の塩素含有量が、２質量％以下である前記＜８＞に記載の酸化スズ精製物である。
＜１０＞ ガラスの澄泡剤として再利用される前記＜８＞から＜９＞のいずれかに記載の酸化スズ精製物である。
＜１１＞ ガラス澄泡性評価試験における泡数が、５個／ｃｍ３以下である前記＜１０＞に記載の酸化スズ精製物である。
The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A repulping step of preparing a waste slurry by adding at least one of water and an acid solution to a tin-containing waste containing at least one of tin and tin oxide;
A dissolution step of mixing the waste slurry and the acid solution to dissolve components other than tin and tin oxide;
A purification step of refining tin oxide by solid-liquid separation of the waste slurry after dissolving components other than tin and tin oxide;
Washing the solid-liquid separated solid content to obtain a tin oxide purified product,
The method for purifying tin-containing waste, wherein a chlorine content in the tin oxide purified product is 2% by mass or less.
<2> The waste slurry after dissolving components other than tin and tin oxide in the dissolution step is allowed to stand, and after removing the supernatant, the supernatant replacement step of adding water is included. This is a method for purifying tin-containing waste.
<3> The method for purifying a tin-containing waste according to any one of <1> to <2>, wherein the chlorine content is 1% by mass or less.
<4> The method for purifying a tin-containing waste according to any one of <1> to <3>, wherein the acid solution is hydrochloric acid.
<5> Purification of tin-containing waste according to any one of <1> to <4>, wherein the tin-containing waste is a waste generated in a step of depositing tin oxide when manufacturing a solar cell substrate. Is the method.
<6> The tin-containing waste is a waste generated in any of a tin oxide coating process, a surface treatment process, a vacuum deposition process, and a thin film sputtering process when manufacturing a solar cell substrate, and the waste Is a method for purifying a tin-containing waste according to any one of <1> to <4>, which contains an alkaline earth metal or an alkali metal.
<7> Powder or slurry obtained by neutralizing exhaust gas discharged in the step of depositing tin oxide when producing a solar cell substrate with tin-containing waste with an alkaline earth metal compound or alkali metal compound The method for purifying a tin-containing waste according to any one of <1> to <4>, wherein the waste contains 5% by mass to 60% by mass of calcium.
<8> A purified tin oxide product purified by the method for purifying tin-containing waste according to any one of <1> to <7>.
<9> The purified tin oxide according to <8>, wherein the chlorine content in the purified tin oxide is 2% by mass or less.
<10> The purified tin oxide according to any one of <8> to <9>, which is reused as a clearing agent for glass.
<11> The tin oxide purified product according to <10>, wherein the number of bubbles in the glass clear foam property evaluation test is 5 / cm 3 or less.
本発明によると、従来における問題を解決することができ、スズ及び酸化スズの少なくともいずれかを含有するスズ含有廃棄物から酸化スズを精製し、塩素含有量が少なく、ガラスの澄泡剤として再利用が可能な酸化スズ精製物を効率よく精製できるスズ含有廃棄物の精製方法及び酸化スズ精製物を提供することができる。 According to the present invention, conventional problems can be solved, and tin oxide is purified from a tin-containing waste containing at least one of tin and tin oxide, and the chlorine content is low. It is possible to provide a method for purifying tin-containing waste and a tin oxide refined product that can efficiently purify a tin oxide refined product that can be used.
（スズ含有廃棄物の精製方法）
本発明のスズ含有廃棄物の精製方法は、リパルプ工程と、溶解工程と、精製工程と、酸化スズ精製物を得る洗浄工程とを少なくとも含み、上澄み置換工程、乾燥工程、更に必要に応じてその他の工程を含んでなる。
(Method for purifying tin-containing waste)
The method for refining a tin-containing waste of the present invention includes at least a repulping step, a dissolving step, a refining step, and a washing step for obtaining a tin oxide refined product, a supernatant replacement step, a drying step, and, if necessary, other The process is comprised.
本発明においては、前記洗浄工程後の酸化スズ精製物中の塩素含有量は、２質量％以下であり、１質量％以下が好ましく、０．７質量％以下がより好ましい。前記塩素含有量が、２質量％を超えると、脱泡の効果が不十分となり、ガラス製品の品質の低下を招くことがある。
前記塩素含有量は、例えば波長分散型Ｘ線装置、イオンクロマト分析装置などにより測定することができる。
本発明において、酸化スズ精製物中の塩素含有量を２質量％以下にする方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば廃棄物スラリーに塩酸を添加し、反応を終えた後、反応液を静置し、上澄み水を除去し、新しく水を投入して塩素を含有する上澄みを除去する方法（上澄み置換工程）、塩酸使用量を過剰としないこと、固液分離を繰り返す方法、リパルプを繰り返す方法などが挙げられる。これらの中でも、上澄み置換工程が経済的観点から特に好ましい。
In the present invention, the chlorine content in the tin oxide purified product after the washing step is 2% by mass or less, preferably 1% by mass or less, and more preferably 0.7% by mass or less. When the chlorine content exceeds 2% by mass, the effect of defoaming becomes insufficient and the quality of the glass product may be deteriorated.
The chlorine content can be measured by, for example, a wavelength dispersive X-ray apparatus or an ion chromatograph analyzer.
In the present invention, the method for reducing the chlorine content in the purified tin oxide to 2% by mass or less is not particularly limited and can be appropriately selected according to the purpose. For example, hydrochloric acid is added to the waste slurry, After the reaction is completed, the reaction solution is allowed to stand, the supernatant water is removed, and water is added to remove the supernatant containing chlorine (supernatant replacement step). The amount of hydrochloric acid used should not be excessive. Examples thereof include a method of repeating liquid separation and a method of repeating repulping. Among these, the supernatant replacement step is particularly preferable from the economical viewpoint.
＜リパルプ工程＞
前記リパルプ工程は、スズ、スズ酸化物のいずれか一方又は双方を含有するスズ含有廃棄物に、水及び酸溶液の少なくともいずれかを添加して廃棄物スラリーを調製する工程であり、処理量に見合った投入口と攪拌機を有するリパルプ装置を用いて行うことができる。
<Repulping process>
The repulping step is a step of preparing a waste slurry by adding at least one of water and an acid solution to a tin-containing waste containing either one or both of tin and tin oxide. It can be carried out using a repulp apparatus having a suitable inlet and stirrer.
前記リパルプ工程においては、スズ及びスズ酸化物の少なくともいずれかを含有するスズ含有廃棄物と水を混合してスズ含有廃棄物の塊をほぐし、スラリー状とすることが好ましい。
前記水としては、特に制限はなく、目的に応じて適宜選択することができ、例えば水道水、イオン交換水、限外濾過水、逆浸透水、蒸留水等の純水、又は超純水を用いることができる。
In the repulping step, it is preferable that a tin-containing waste containing at least one of tin and tin oxide is mixed with water to loosen a lump of the tin-containing waste to form a slurry.
The water is not particularly limited and may be appropriately selected depending on the intended purpose.For example, tap water, ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or other pure water, or ultrapure water. Can be used.
前記リパルプ工程においては、前記スズ含有廃棄物の塊がもともとほぐし易い場合、又は処理系内の使用水量を制限したい場合は、スズ含有廃棄物に酸溶液を加え、酸溶液とスズ含有廃棄物との廃棄物スラリーとしてもよい。
前記酸溶液としては、特に制限はなく、目的に応じて適宜選択することができ、例えば塩酸、硫酸、硝酸、などが挙げられる。これらの中でも、塩酸が特に好ましい。
In the repulping step, when the tin-containing waste lump is originally easily loosened, or when it is desired to limit the amount of water used in the treatment system, an acid solution is added to the tin-containing waste, and the acid solution and the tin-containing waste It is good also as a waste slurry.
There is no restriction | limiting in particular as said acid solution, According to the objective, it can select suitably, For example, hydrochloric acid, a sulfuric acid, nitric acid etc. are mentioned. Among these, hydrochloric acid is particularly preferable.
−スズ含有廃棄物の組成−
前記スズ含有廃棄物は、スズ、スズ酸化物のいずれか一方又は双方を含有する廃棄物であれば特に制限はなく、目的に応じて適宜選択することができ、例えば（１）太陽電池基板を製造する際の酸化スズを蒸着する工程で発生する廃棄物、（２）太陽電池基板を製造する際の酸化スズの被覆工程、表面処理工程、真空蒸着工程、及び薄膜スパッタリング工程のいずれかで発生する廃棄物であり、かつ該廃棄物がアルカリ土類金属又はアルカリ金属を含有しているもの、（３）酸化スズの蒸着工程から排出される排ガスをアルカリ土類金属化合物又はアルカリ金属化合物によって中和して得られた粉状乃至スラリー状の廃棄物であり、かつ該廃棄物がカルシウムを５質量％〜６０質量％含有しているもの、などが挙げられる。前記スズ含有廃棄物は、アルカリ性であることが好ましい。
なお、前記スズ含有廃棄物の組成としては、精製目的であるスズ及びスズ酸化物以外の不純物の含有量は少ない方が好ましい。
-Composition of tin-containing waste-
The tin-containing waste is not particularly limited as long as it is a waste containing one or both of tin and tin oxide, and can be appropriately selected according to the purpose. For example, (1) a solar cell substrate Waste generated in the process of depositing tin oxide during manufacturing, (2) Generated in any of the tin oxide coating process, surface treatment process, vacuum deposition process, and thin film sputtering process when manufacturing solar cell substrates Waste that contains alkaline earth metal or alkali metal, and (3) exhaust gas discharged from the deposition process of tin oxide is mixed with alkaline earth metal compound or alkali metal compound. Examples thereof include powdery or slurry-like waste obtained by summing, and the waste contains 5% by mass to 60% by mass of calcium. The tin-containing waste is preferably alkaline.
In addition, as a composition of the said tin containing waste material, it is preferable that there is little content of impurities other than the tin and tin oxide which are the objectives of refinement | purification.
＜溶解工程＞
前記溶解工程は、前記廃棄物スラリーと酸溶液を混合してスズ及びスズ酸化物以外の成分を溶解する工程である。
<Dissolution process>
The dissolution step is a step of mixing the waste slurry and the acid solution to dissolve components other than tin and tin oxide.
前記溶解工程においては、廃棄物スラリーのｐＨが１０〜１４の範囲から酸溶液の添加によってｐＨが１〜７の範囲まで低下させることでスズ及びスズ酸化物以外の成分を溶解させることが好ましい。 In the dissolution step, it is preferable to dissolve components other than tin and tin oxide by lowering the pH of the waste slurry from the range of 10 to 14 to the range of 1 to 7 by addition of an acid solution.
前記酸溶液としては、特に制限はなく、目的に応じて適宜選択することができ、例えば塩酸、硫酸、硝酸、などが挙げられる。これらの中でも、カルシウムを除去する点で塩酸が特に好ましい。また、排水処理の観点からも塩酸が好ましい。
前記酸溶液の添加量は、スズ含有廃棄物１ｇに対し０．１ｇ〜３．０ｇが好ましく、０．５ｇ〜２．０ｇがより好ましい。
There is no restriction | limiting in particular as said acid solution, According to the objective, it can select suitably, For example, hydrochloric acid, a sulfuric acid, nitric acid etc. are mentioned. Among these, hydrochloric acid is particularly preferable in terms of removing calcium. Also, hydrochloric acid is preferable from the viewpoint of wastewater treatment.
The amount of the acid solution added is preferably 0.1 g to 3.0 g, more preferably 0.5 g to 2.0 g, with respect to 1 g of tin-containing waste.
前記スズ及びスズ酸化物以外の成分としては、例えばナトリウム、マグネシウム、カルシウム、リン酸、硫黄、フッ素、などが挙げられる。
前記溶解工程における酸添加後の廃棄物スラリーのｐＨは、７以下が好ましく、０．５〜４．５がより好ましい。前記ｐＨが、０．５未満であると、排水の中和にコストがかかる上に、酸化スズ精製物中の塩素濃度が上昇することがある。一方、前記ｐＨが７を超えると、スズ含有廃棄物中の酸化スズ以外の成分、特に消石灰などの溶解効率が極端に低下することがある。
Examples of components other than tin and tin oxide include sodium, magnesium, calcium, phosphoric acid, sulfur, and fluorine.
The pH of the waste slurry after the acid addition in the dissolution step is preferably 7 or less, and more preferably 0.5 to 4.5. When the pH is less than 0.5, it is costly to neutralize wastewater, and the chlorine concentration in the purified tin oxide may increase. On the other hand, when the pH exceeds 7, the dissolution efficiency of components other than tin oxide in the tin-containing waste, particularly slaked lime, may be extremely lowered.
前記廃棄物スラリーと前記酸溶液との混合方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば粉体の廃棄物の場合、投入口からリパルプ槽内に直接投入し、攪拌によるせん断によりリパルプする方法、塊状の廃棄物であれば、グリズリフィーダなどの破砕機によりあらかじめ破砕した後にリパルプする方法、などが挙げられる。
前記溶解工程における反応時間は、長いほどよく、例えば０．５時間〜６時間が好ましい。
前記溶解工程は、反応温度による酸化スズ精製物の品位に大きな違いはないが、中和熱が発生するため、冷却設備を設けることが好ましい。
The mixing method of the waste slurry and the acid solution is not particularly limited and can be appropriately selected depending on the purpose. For example, in the case of powdered waste, the waste slurry and the acid solution are directly input into the repulp tank. In addition, a method of repulping by shearing by stirring, and a method of repulping after crushing in advance with a crusher such as a grizzly feeder in the case of massive waste are included.
The longer the reaction time in the dissolution step, the better. For example, 0.5 to 6 hours is preferable.
In the dissolution step, there is no significant difference in the quality of the tin oxide purified product depending on the reaction temperature, but it is preferable to provide cooling equipment because heat of neutralization is generated.
前記廃棄物スラリーと酸溶液を混合する際の廃棄物スラリーの濃度は、５質量％〜５０質量％が好ましく、１０質量％〜３０質量％がより好ましい。前記廃棄物スラリーの濃度による酸化スズ精製物の品位に大きな違いはないが、前記廃棄物スラリーの濃度が、５質量％未満であると、生産効率が低下することがあり、５０質量％を超えると、酸化スズ精製物の品位や攪拌操作、濾過操作に影響を与えることがある。また、必要に応じて反応槽へ廃棄物スラリーを直接投入して、廃棄物スラリー濃度を調整することも可能である。 The concentration of the waste slurry when mixing the waste slurry and the acid solution is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 30% by mass. There is no significant difference in the quality of the tin oxide refined product depending on the concentration of the waste slurry, but if the concentration of the waste slurry is less than 5% by mass, the production efficiency may be reduced and exceeds 50% by mass. This may affect the quality of the tin oxide refined product, the stirring operation, and the filtration operation. Moreover, it is also possible to adjust the waste slurry concentration by directly feeding the waste slurry into the reaction vessel as necessary.
＜上澄み置換工程＞
前記上澄み置換工程は、前記溶解工程により、スズ及びスズ酸化物以外の成分を溶解した後の廃棄物スラリーを静置し、上澄みを除去した後、水を添加する工程である。
前記上澄みの除去は、例えば吸引ポンプなどを用いて行うことができる。
前記水の添加は、前記上澄みの除去量と同じ量を添加することが好ましい。
前記上澄み置換工程は、１回以上行うことが好ましく、２回以上行うことが、より塩素含有量を低減できる点でより好ましい。
<Supernatant replacement step>
The supernatant replacement step is a step of adding water after leaving the waste slurry after dissolving components other than tin and tin oxide in the dissolution step and removing the supernatant.
The removal of the supernatant can be performed using, for example, a suction pump.
It is preferable to add the same amount of water as the amount of the supernatant removed.
The supernatant replacement step is preferably performed once or more, and more preferably twice or more in that the chlorine content can be further reduced.
＜精製工程＞
前記精製工程は、スズ及びスズ酸化物以外の成分を溶解した廃棄物スラリーを固液分離して酸化スズを精製する工程である。
前記固液分離としては、特に制限はなく、一般的な固形物の脱水、固液分離の装置等を使用することができ、例えばフィルタープレス、ドラムフィルター、スクリュープレスなどが挙げられる。また、遠心分離による分離も可能である。これらの中でも、廃棄物スラリー中の酸化スズ粒子の粒径が細かいことから、フィルタープレスのような加圧式の濾過機が好適である。なお、この精製工程から排出される濾液（排水）は、塩化カルシウムが主体であり、高濃度であるため、中和剤としての再利用が可能である。
<Purification process>
The purification step is a step of purifying tin oxide by solid-liquid separation of a waste slurry in which components other than tin and tin oxide are dissolved.
There is no restriction | limiting in particular as said solid-liquid separation, The apparatus of dehydration of general solid substance, solid-liquid separation, etc. can be used, For example, a filter press, a drum filter, a screw press etc. are mentioned. Separation by centrifugation is also possible. Among these, since the particle size of the tin oxide particles in the waste slurry is fine, a pressure filter such as a filter press is suitable. In addition, since the filtrate (drainage) discharged | emitted from this refinement | purification process is mainly calcium chloride and is high concentration, it can be reused as a neutralizing agent.
−洗浄工程−
前記洗浄工程は、固液分離された固形分を洗浄して酸化スズ精製物を得る工程である。
前記洗浄としては、特に制限はなく、目的に応じて適宜選択することができ、例えば濾過後にリパルプせずに通水のみによる洗浄を行っても、リパルプして洗浄を行い、再度脱水してもよい。通水のみの洗浄を行う場合、通水量の目安は脱水量の１〜３倍量の水量とする。
前記洗浄工程により得られる酸化スズ精製物中の塩素含有量は、２質量％以下である。
-Washing process-
The said washing | cleaning process is a process of wash | cleaning the solid content isolate | separated into solid and liquid, and obtaining a tin oxide refined | purified substance.
The washing is not particularly limited and may be appropriately selected depending on the purpose. For example, washing may be performed only by passing water without repulping after filtration, washing by repulping, and dehydrating again. Good. When cleaning only with water flow, the standard of water flow is 1 to 3 times the amount of dewatering.
The chlorine content in the tin oxide purified product obtained by the washing step is 2% by mass or less.
−乾燥工程−
前記乾燥工程は、前記洗浄工程で得られた酸化スズ精製物を乾燥する工程である。
前記酸化スズ精製物の乾燥方法としては、酸化スズ精製物を乾燥できれば特に制限はなく、目的に応じて適宜選択することができ、例えば一般的な乾燥機、乾燥炉、バンドドライヤ、ロータリードライヤ、ドラムドライヤ、スプレードライヤ等の使用が可能であり、熱風乾燥、真空乾燥、マイクロ波の利用、赤外線の利用等が適用可能である。
前記乾燥工程における温度は、水を蒸発させる程度の温度が好ましく、例えば１０５℃程度で乾燥させてもよく、又はそれ以上の温度をかけて乾燥時間を減らしてもよいが、２００℃〜２５０℃の熱風乾燥が一般的である。
-Drying process-
The drying step is a step of drying the purified tin oxide obtained in the washing step.
The method for drying the tin oxide purified product is not particularly limited as long as the tin oxide purified product can be dried, and can be appropriately selected according to the purpose. For example, a general dryer, a drying furnace, a band dryer, a rotary dryer, A drum dryer, a spray dryer or the like can be used, and hot air drying, vacuum drying, use of microwaves, use of infrared rays, or the like can be applied.
The temperature in the drying step is preferably a temperature at which water is evaporated, for example, it may be dried at about 105 ° C., or the drying time may be reduced by applying a temperature higher than 200 ° C. to 250 ° C. Drying with hot air is common.
本発明のスズ含有廃棄物の精製方法によれば、酸化スズ精製物中の塩素含有量を低減することができ、スズ含有廃棄物からガラスの澄泡剤として再利用できる酸化スズ精製物を効率よく精製することができる。 According to the method for purifying tin-containing waste of the present invention, it is possible to reduce the chlorine content in the tin oxide-purified product, and to efficiently use the tin oxide-purified product that can be reused as a glass foam from the tin-containing waste. It can be purified well.
（酸化スズ精製物）
本発明の酸化スズ精製物は、本発明の前記スズ含有廃棄物の精製方法により精製される。
前記酸化スズ精製物中の塩素含有量は、２質量％以下であり、１質量％以下が好ましく、０．７質量％以下がより好ましい。
前記酸化スズ精製物中のスズ酸化物の含有量は、乾燥質量で９５質量％以上であることが好ましい。前記スズ酸化物の含有量が、９５質量％未満であると、酸化スズ精製物の再利用を考慮した場合、製品価値が低下することがある。
前記スズ酸化物の含有量は、例えば波長分散型Ｘ線装置などにより測定することができる。
(Purified tin oxide)
The purified tin oxide of the present invention is purified by the method for purifying tin-containing waste of the present invention.
The chlorine content in the tin oxide purified product is 2% by mass or less, preferably 1% by mass or less, and more preferably 0.7% by mass or less.
The tin oxide content in the purified tin oxide is preferably 95% by mass or more in terms of dry mass. When the content of the tin oxide is less than 95% by mass, the product value may be lowered in consideration of the reuse of the tin oxide purified product.
The tin oxide content can be measured by, for example, a wavelength dispersive X-ray apparatus.
−用途−
前記酸化スズ精製物は、例えばガラスの澄泡剤、はんだ、ブリキ、電線、伸銅品、瓦や陶磁器の顔料、導電材料、などに用いられる。これらの中でも、ガラスの澄泡剤が特に好ましい。
前記酸化スズ精製物をガラスの澄泡剤として再利用することがエネルギーの消費量を削減し、環境負荷を下げることができガラス製造における環境負荷を低減する点、資源の有効利用の点で好ましい。また、酸化スズ精製物を用いることはヒ素やアンチモン等のように有害でない点でも好ましい。
本発明の酸化スズ精製物をガラスの澄泡剤として再利用した場合、ガラス澄泡性評価試験における泡数は、５個／ｃｍ３以下であることが好ましい。前記泡数が、５個／ｃｍ３を超えると、脱泡の効果が不十分となり、ガラス製品の品質低下を招くことがある。
-Application-
The tin oxide purified product is used, for example, for glass fining agents, solder, tinplate, electric wires, copper-plated products, roof tiles, ceramic pigments, conductive materials, and the like. Among these, a glass foaming agent is particularly preferable.
Reusing the tin oxide refined product as a glass defoaming agent is preferable in terms of reducing energy consumption, reducing the environmental load, reducing the environmental load in glass production, and effective use of resources. . Moreover, it is preferable to use a purified tin oxide because it is not harmful like arsenic or antimony.
When the refined tin oxide of the present invention is reused as a glass clear foaming agent, the number of bubbles in the glass clear foam evaluation test is preferably 5 / cm 3 or less. When the number of bubbles exceeds 5 / cm 3 , the effect of defoaming becomes insufficient and the quality of the glass product may be deteriorated.
前記澄泡剤は、ガラス中の泡をなくすことができるので、例えば液晶ディスプレイ用ガラス基板、磁気ディスク用ガラス、ＣＤ、ＭＤ、ＤＶＤ、その他各種光ディスクシステムの光ピックアップレンズ、ビデオカメラ、一般のカメラの撮影用レンズ等の光学レンズ；ＣＣＤ、ＣＭＯＳ等の固体撮像素子等のカバーガラスなどに好適に用いられる。 Since the clear foaming agent can eliminate bubbles in the glass, for example, glass substrates for liquid crystal displays, glass for magnetic disks, CDs, MDs, DVDs, optical pickup lenses for various optical disk systems, video cameras, general cameras, etc. It is suitably used for an optical lens such as a photographing lens; a cover glass for a solid-state imaging device such as a CCD or CMOS.
前記ガラスの組成としては、特に制限はなく、目的に応じて適宜選択することができ、例えばＳｉＯ２が４０質量％〜６５質量％、Ａｌ２Ｏ３が１０質量％〜２０質量％、Ｂ２Ｏ３が８質量％〜１２質量％、ＭｇＯが２質量％〜６質量％、ＣａＯが２質量％〜８質量％、ＳｒＯが６質量％〜１０質量％であり、ガラスの澄泡剤として利用するＳｎＯ２の濃度は０．０１質量％〜１質量％が好ましい。
その他必要に応じて、清澄、着色、消色等の目的で清澄剤や着色剤等を前記ガラス組成に適量添加してもよい。
The composition of the glass is not particularly limited and may be appropriately selected depending on the purpose, for example, SiO 2 is 40 wt% to 65 wt%, Al 2 O 3 is 10% by mass to 20%, B 2 O 3 is 8% by mass to 12% by mass, MgO is 2% by mass to 6% by mass, CaO is 2% by mass to 8% by mass, SrO is 6% by mass to 10% by mass, and is used as a glass clear foaming agent. The concentration of SnO 2 is preferably 0.01% by mass to 1% by mass.
In addition, an appropriate amount of a clarifier, a colorant, or the like may be added to the glass composition for the purpose of clarification, coloring, decoloring or the like, if necessary.
前記ガラスの製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、各成分の原料として各々相当する酸化物、炭酸塩、硝酸塩、リン酸塩、正リン酸等を用い、所望の割合に秤量し、粉末又は液体で十分に混合して調合原料とする。この調合原料を、例えば所定の溶融温度に加熱された電気炉中の石英るつぼ又は白金坩堝に投入し、溶融清澄後、攪拌し、均質化して予め加熱しておいた鉄製の鋳型に鋳込み、徐冷して製造する。
前記溶融温度は、１，３００℃〜１，７００℃が好ましく、液晶ガラスにおいては、溶融温度は１，５００℃〜１，７００℃がより好ましい。
The method for producing the glass is not particularly limited and can be appropriately selected depending on the purpose. As the raw materials of the respective components, corresponding oxides, carbonates, nitrates, phosphates, orthophosphoric acids and the like are used. , Weigh to a desired ratio, and mix well with powder or liquid to prepare a blended raw material. For example, this mixed raw material is put into a quartz crucible or platinum crucible in an electric furnace heated to a predetermined melting temperature. Cool to manufacture.
The melting temperature is preferably 1,300 ° C to 1,700 ° C, and in the liquid crystal glass, the melting temperature is more preferably 1,500 ° C to 1,700 ° C.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（実施例１）
精製に用いたスズ含有廃棄物の組成を表１に示す。このスズ含有廃棄物は、太陽電池基板の製造方法における酸化スズの蒸着工程で生じたものである。
Example 1
Table 1 shows the composition of the tin-containing waste used for purification. This tin-containing waste is generated in the vapor deposition step of tin oxide in the solar cell substrate manufacturing method.
次に、前記スズ含有廃棄物１トン、及び工業用水２ｍ３を混合し、廃棄物スラリーを調製した（リパルプ工程）。この廃棄物スラリーのｐＨは１１．８であった。
次に、攪拌槽に送液し、工業用水を７ｍ３追加した。次いで、塩酸（和光純薬株式会社製、一級塩酸、純度３５％〜３７％）を、篩を通過したスラリー中に、ｐＨが４になるように調整しながら添加した。その時の塩酸使用量は７４６リットルであった（溶解工程）。なお、ｐＨは、以下に記載の方法により測定した。
次に、攪拌しながら６時間反応させた。その後、攪拌を止め、１２時間静置し、上澄みをポンプで除去し、あたらしく水を６ｍ３追加した。この操作を２回繰り返すことで、液中に存在する塩素成分を除去した（上澄み置換回数２回）。
次に、スラリーをフィルタープレスにて濾過し、その後、洗浄水を１０ｍ３通水し、洗浄した（洗浄工程）。得られた含水固形物を１０５℃で乾燥させて、酸化スズ精製物を得た。
得られた酸化スズ精製物の組成を、以下に示すようにして分析した。得られた精製物の塩素含有量は０．６２質量％であった。結果を表２に示す。
Next, 1 ton of the tin-containing waste and 2 m 3 of industrial water were mixed to prepare a waste slurry (repulping step). The pH of this waste slurry was 11.8.
Next, the solution was sent to a stirring tank, and 7 m 3 of industrial water was added. Subsequently, hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., primary hydrochloric acid, purity 35% to 37%) was added to the slurry that passed through the sieve while adjusting the pH to be 4. The amount of hydrochloric acid used at that time was 746 liters (dissolution step). The pH was measured by the method described below.
Next, it was made to react for 6 hours, stirring. Thereafter, stirring was stopped, the mixture was allowed to stand for 12 hours, the supernatant was removed with a pump, and 6 m 3 of water was newly added. By repeating this operation twice, the chlorine component present in the liquid was removed (the supernatant was replaced twice).
Next, the slurry was filtered with a filter press, and then washed with 10 m 3 of washing water (washing step). The obtained water-containing solid was dried at 105 ° C. to obtain a purified tin oxide.
The composition of the obtained tin oxide purified product was analyzed as shown below. The purified product obtained had a chlorine content of 0.62% by mass. The results are shown in Table 2.
＜ｐＨの測定＞
廃棄物スラリーのｐＨは液を１Ｌ採取し、ｐＨ電極（ＧＳＴ−５３１１Ｃ、東亜ＤＫＫ社製）により測定した。
<Measurement of pH>
The pH of the waste slurry was measured with a pH electrode (GST-5311C, manufactured by Toa DKK) after collecting 1 L of the liquid.
＜固形物中のカルシウムの分析＞
カルシウムについては、０．５ｇのスズ含有廃棄物及び酸化スズ精製物を王水中で乾固直前まで加温溶解し、ろ過後、イオン交換水で１００ｍｌまでメスアップし、分析用溶液を得た。その溶液を高周波プラズマ発光分光分析装置（日本ジャーレル・アッシュ株式会社製、ＩＣＡＰ−５７５ＩＩ）により分析し、その濃度から固形物中のカルシウム濃度を計算した。
<Analysis of calcium in solids>
Regarding calcium, 0.5 g of tin-containing waste and purified tin oxide were dissolved by heating in aqua regia until just before drying, and after filtration, the solution was made up to 100 ml with ion-exchanged water to obtain an analytical solution. The solution was analyzed with a high frequency plasma emission spectroscopic analyzer (manufactured by Nippon Jarrell-Ash Co., Ltd., ICAP-575II), and the calcium concentration in the solid matter was calculated from the concentration.
＜塩素及びその他の成分の分析＞
塩素及びその他の成分については、波長分散型Ｘ線装置（リガク社製、 ＺＳＸ ＰｒｉｍｕｓＩＩ）により分析した。
<Analysis of chlorine and other components>
Chlorine and other components were analyzed using a wavelength dispersion X-ray apparatus (manufactured by Rigaku Corporation, ZSX Primus II).
（実施例２）
スズ含有廃棄物１トン、及び工業用水２ｍ３を混合し、廃棄物スラリーを調製した。この廃棄スラリーのｐＨは１１．８であった。塩酸（和光純薬株式会社製、一級塩酸、純度３５％〜３７％）を廃棄スラリー中にｐＨが４になるように調整しながら添加した。その時の塩酸使用量は７５３リットルであった。その後、攪拌しながら６時間反応させた。
その後、攪拌を止め、１２時間静置し、上澄みをポンプで除去し、あたらしく水を６ｍ３追加した。この操作により、液中に存在する塩素成分を除去した（上澄み置換回数１回）。
次に、スラリーをフィルタープレスにより濾過し、その後、洗浄水を１０ｍ３通水し、洗浄した。得られた含水固形物を１０５℃で乾燥させて、酸化スズ精製物を得た。
得られた酸化スズ精製物の組成を、実施例１と同様にして分析した。得られた精製物の塩素含有量は０．９４質量％であった。結果を表２に示す。
(Example 2)
1 ton of tin-containing waste and 2 m 3 of industrial water were mixed to prepare a waste slurry. The pH of this waste slurry was 11.8. Hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., primary hydrochloric acid, purity 35% to 37%) was added to the waste slurry while adjusting the pH to 4. The amount of hydrochloric acid used at that time was 753 liters. Then, it was made to react for 6 hours, stirring.
Thereafter, stirring was stopped, the mixture was allowed to stand for 12 hours, the supernatant was removed with a pump, and 6 m3 of water was newly added. By this operation, the chlorine component present in the liquid was removed (the supernatant was replaced once).
Next, the slurry was filtered with a filter press, and then washed with 10 m 3 of washing water. The obtained water-containing solid was dried at 105 ° C. to obtain a purified tin oxide.
The composition of the obtained tin oxide purified product was analyzed in the same manner as in Example 1. The purified product obtained had a chlorine content of 0.94% by mass. The results are shown in Table 2.
（比較例１）
スズ含有廃棄物３０ｇ、及びイオン交換水２７０ｇを混合し、廃棄物スラリーを調製した。このスラリーのｐＨは１１．８であった。塩酸（和光純薬株式会社製、一級塩酸、純度３５％〜３７％）をスラリー中にｐＨ１．２になるように調整しながら添加した。その時の塩酸使用量は３０．７ｍｌであった。その後、攪拌しながら６時間反応させた。上澄み液の置換操作は行わなかった。
次に、スラリーを加圧型濾過機により濾過し、その後、洗浄水を３００ｍｌ通水し、洗浄した。得られた含水固形物を１０５℃で乾燥させて、酸化スズ精製物を得た。
得られた酸化スズ精製物の組成を、実施例１と同様にして分析した。結果を表２に示す。
(Comparative Example 1)
A waste slurry was prepared by mixing 30 g of a tin-containing waste and 270 g of ion-exchanged water. The pH of this slurry was 11.8. Hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., primary hydrochloric acid, purity 35% to 37%) was added to the slurry while adjusting the pH to 1.2. The amount of hydrochloric acid used at that time was 30.7 ml. Then, it was made to react for 6 hours, stirring. The supernatant liquid was not replaced.
Next, the slurry was filtered with a pressure filter, and then 300 ml of washing water was passed through and washed. The obtained water-containing solid was dried at 105 ° C. to obtain a purified tin oxide.
The composition of the obtained tin oxide purified product was analyzed in the same manner as in Example 1. The results are shown in Table 2.
（実施例３）
−ガラスの作製−
実施例１の酸化スズ精製物を用い、表３に示すガラス組成（酸化スズ０．１質量％含有）を３０分間手で混合し、１，６００℃で４時間溶融して、図１に示す形状のガラスを作製した。
(Example 3)
-Production of glass-
Using the purified tin oxide of Example 1, the glass composition shown in Table 3 (containing 0.1% by mass of tin oxide) was mixed by hand for 30 minutes, melted at 1,600 ° C. for 4 hours, and shown in FIG. Shaped glass was produced.
(実施例４)
−ガラスの作製−
実施例３において、実施例２の酸化スズ精製物を用いた以外は、実施例３と同様にして、図１に示す形状のガラスを作製した。
Example 4
-Production of glass-
In Example 3, glass having the shape shown in FIG. 1 was produced in the same manner as in Example 3, except that the tin oxide purified product of Example 2 was used.
(比較例２)
−ガラスの作製−
実施例３において、比較例１の酸化スズ精製物を用いた以外は、実施例３と同様にして、図１に示す形状のガラスを作製した。
(Comparative Example 2)
-Production of glass-
In Example 3, glass having the shape shown in FIG. 1 was produced in the same manner as in Example 3 except that the purified tin oxide of Comparative Example 1 was used.
(比較例３)
−ガラスの作製−
実施例３において、市販品の酸化スズ（三津和化学株式会社製、酸化スズ純度９９．９質量％）を用いた以外は、実施例３と同様にして、図１に示す形状のガラスを作製した。
(Comparative Example 3)
-Production of glass-
In Example 3, glass having the shape shown in FIG. 1 was produced in the same manner as in Example 3 except that a commercially available tin oxide (manufactured by Mitsuwa Chemical Co., Ltd., tin oxide purity 99.9% by mass) was used. did.
次に、実施例３〜４及び比較例２〜３で作製した各ガラスの泡数を、以下のようにして計測した。結果を表４に示す。また、実施例３〜４及び比較例２における塩素含有量と、泡数との関係を図２に示す。 Next, the bubble number of each glass produced in Examples 3-4 and Comparative Examples 2-3 was measured as follows. The results are shown in Table 4. Moreover, the relationship between the chlorine content in Examples 3 to 4 and Comparative Example 2 and the number of bubbles is shown in FIG.
＜泡数の計測＞
泡数の計測は、図１に示す縦４ｃｍ×横４ｃｍ×厚さ３ｃｍの範囲について、単位体積当たりの泡数を実態顕微鏡（Ｎｉｋｏｎ社製、ＳＭＺ−１０）で計測した。測定は接眼レンズ倍率１０倍、ズーム４倍で行った。
<Measurement of the number of bubbles>
For the measurement of the number of bubbles, the number of bubbles per unit volume was measured with an actual microscope (SMZ-10, manufactured by Nikon) in the range of 4 cm long × 4 cm wide × 3 cm thick shown in FIG. The measurement was performed at an eyepiece magnification of 10 times and a zoom of 4 times.
表４及び図２の結果から、実施例３及び４は、比較例２に比べて、酸化スズ精製物中の塩素含有量を低減することで、泡の数が少なくなり、清澄性が向上し、ガラスの澄泡剤としての特性が高くなることが分かった。
また、市販品を用いた比較例３のガラスの泡数が５個／ｃｍ３であることから、泡数が５個／ｃｍ３程度まではリサイクル品としても使用できる範囲と考えることができ、図２から、酸化スズ含有廃棄物の精製物を再利用する際には、塩素含有量を２．０質量％以下とすることが好ましいと言える。
From the results of Table 4 and FIG. 2, Examples 3 and 4 have a reduced content of chlorine in the purified tin oxide compared to Comparative Example 2, thereby reducing the number of bubbles and improving clarity. It has been found that the properties of glass as a clear foaming agent are improved.
Moreover, since the number of bubbles of the glass of Comparative Example 3 using a commercially available product is 5 / cm 3 , it can be considered that the number of bubbles is about 5 / cm 3 and can be used as a recycled product. From FIG. 2, it can be said that the chlorine content is preferably 2.0% by mass or less when the purified product of the tin oxide-containing waste is reused.
本発明のスズ含有廃棄物の精製方法は、スズ及び酸化スズの少なくともいずれかを含有するスズ含有廃棄物から、塩素含有量が少なく、ガラスの澄泡剤として再利用が可能な酸化スズ精製物を効率よく精製することができ、得られた酸化スズ精製物は、ガラスの澄泡剤として好適に用いられる。 The method for refining a tin-containing waste according to the present invention is a tin oxide-purified product that has a low chlorine content and can be reused as a glass foaming agent from a tin-containing waste containing at least one of tin and tin oxide. Can be efficiently purified, and the obtained tin oxide purified product is suitably used as a glass foaming agent.
Claims (11)
前記廃棄物スラリーと酸溶液を混合してスズ及びスズ酸化物以外の成分を溶解する溶解工程と、
スズ及びスズ酸化物以外の成分を溶解した後の廃棄物スラリーを固液分離してスズ酸化物を精製する精製工程と、
前記固液分離した固形分を洗浄して酸化スズ精製物を得る洗浄工程と、を含み、
前記酸化スズ精製物中の塩素含有量が、２質量％以下であることを特徴とするスズ含有廃棄物の精製方法。 A repulping step of preparing a waste slurry by adding at least one of water and an acid solution to a tin-containing waste containing at least one of tin and tin oxide;
A dissolution step of mixing the waste slurry and the acid solution to dissolve components other than tin and tin oxide;
A purification step of refining tin oxide by solid-liquid separation of the waste slurry after dissolving components other than tin and tin oxide;
Washing the solid-liquid separated solid content to obtain a tin oxide purified product,
The method for purifying tin-containing waste, wherein a chlorine content in the purified tin oxide is 2% by mass or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009234537A JP5473523B2 (en) | 2009-10-08 | 2009-10-08 | Method for purifying tin-containing waste and glass foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009234537A JP5473523B2 (en) | 2009-10-08 | 2009-10-08 | Method for purifying tin-containing waste and glass foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011079714A true JP2011079714A (en) | 2011-04-21 |
| JP5473523B2 JP5473523B2 (en) | 2014-04-16 |
Family
ID=44074174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009234537A Expired - Fee Related JP5473523B2 (en) | 2009-10-08 | 2009-10-08 | Method for purifying tin-containing waste and glass foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5473523B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101336121B1 (en) * | 2011-11-30 | 2013-12-03 | 한국지질자원연구원 | Method for recycling Pb-free solder waste using hydrochloric acid |
| WO2014030878A1 (en) * | 2012-08-20 | 2014-02-27 | 한국해양대학교 산학협력단 | Method for separating and collecting useful metals from waste lead-free solder |
| KR20180007561A (en) * | 2016-07-13 | 2018-01-23 | 주식회사 엘지화학 | Method of refining tin metal |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073619A (en) * | 2006-09-21 | 2008-04-03 | Sharp Corp | Method of treating liquid crystal panel |
| JP2008297607A (en) * | 2007-05-31 | 2008-12-11 | Mitsubishi Materials Corp | In-Sn SEPARATING/RECOVERING METHOD |
| JP2009035808A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Materials Corp | Method for separating tin from coexistence metal |
| JP2010042954A (en) * | 2008-08-12 | 2010-02-25 | Dowa Eco-System Co Ltd | Method for purifying tin-containing waste and method for reusing tin-containing waste |
| JP2010163340A (en) * | 2009-01-19 | 2010-07-29 | Mitsubishi Materials Corp | METHOD AND APPARATUS FOR RECOVERING Sn, AND METHOD FOR PRODUCING Sn OXIDE POWDER |
| JP2011073941A (en) * | 2009-09-30 | 2011-04-14 | Dowa Eco-System Co Ltd | Method for purifying tin oxide from tin-containing waste and purified tin oxide |
-
2009
- 2009-10-08 JP JP2009234537A patent/JP5473523B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073619A (en) * | 2006-09-21 | 2008-04-03 | Sharp Corp | Method of treating liquid crystal panel |
| JP2008297607A (en) * | 2007-05-31 | 2008-12-11 | Mitsubishi Materials Corp | In-Sn SEPARATING/RECOVERING METHOD |
| JP2009035808A (en) * | 2007-07-12 | 2009-02-19 | Mitsubishi Materials Corp | Method for separating tin from coexistence metal |
| JP2010042954A (en) * | 2008-08-12 | 2010-02-25 | Dowa Eco-System Co Ltd | Method for purifying tin-containing waste and method for reusing tin-containing waste |
| JP2010163340A (en) * | 2009-01-19 | 2010-07-29 | Mitsubishi Materials Corp | METHOD AND APPARATUS FOR RECOVERING Sn, AND METHOD FOR PRODUCING Sn OXIDE POWDER |
| JP2011073941A (en) * | 2009-09-30 | 2011-04-14 | Dowa Eco-System Co Ltd | Method for purifying tin oxide from tin-containing waste and purified tin oxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101336121B1 (en) * | 2011-11-30 | 2013-12-03 | 한국지질자원연구원 | Method for recycling Pb-free solder waste using hydrochloric acid |
| WO2014030878A1 (en) * | 2012-08-20 | 2014-02-27 | 한국해양대학교 산학협력단 | Method for separating and collecting useful metals from waste lead-free solder |
| KR20180007561A (en) * | 2016-07-13 | 2018-01-23 | 주식회사 엘지화학 | Method of refining tin metal |
| KR102157890B1 (en) | 2016-07-13 | 2020-09-18 | 주식회사 엘지화학 | Method of refining tin metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5473523B2 (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101328231B1 (en) | Method for preparing metallurgical-grade alumina by using fluidized-bed fly ash | |
| CN105948174B (en) | Chloride process titanium dioxide flour flow design wastewater utilization method | |
| CN101309761A (en) | Method of and apparatus for treating chlorine-containing waste | |
| KR102094398B1 (en) | Method of recycling chlorine bypass dust generated in cement manufacturing process | |
| JP2006347794A (en) | Method of removing and recovering heavy metals from cement production process | |
| JP5473523B2 (en) | Method for purifying tin-containing waste and glass foam | |
| JP5096260B2 (en) | Method for purifying tin-containing waste and method for reusing tin-containing waste | |
| JP5032400B2 (en) | Nickel oxide | |
| JP5511291B2 (en) | Method for purifying tin-containing waste and glass foam | |
| EA035062B1 (en) | Extraction of products from titanium-bearing minerals | |
| EA010106B1 (en) | Process for complete utilization of olivine constituents | |
| JP5431780B2 (en) | A processing method for obtaining a niobium raw material or a tantalum raw material, a method for separating and purifying niobium or tantalum, and a method for producing niobium oxide or tantalum oxide. | |
| CN1271224C (en) | Process for electrolytic production of highly pure zinc or zinc compounds from primary and secondary zinc raw materials | |
| JP5323638B2 (en) | Method for purifying tin-containing waste | |
| JP5904089B2 (en) | Method for producing zinc oxide ore | |
| JPH1150168A (en) | Recovery of rare earth metal component from optical glass sludge | |
| JP2014169199A (en) | Processing method of steelmaking slag | |
| JP2006231245A (en) | Method for treating silicon sludge | |
| JP2004315315A (en) | Method for recovering valuables from waste salt containing potassium fluoride and method for recycling valuables recovered thereby | |
| CN102534257A (en) | Novel bismuth smelting separation method | |
| JP4863887B2 (en) | Method for purifying metal silicon | |
| CN101885495A (en) | Method for preparing high-purity anhydrous sodium carbonate | |
| JP2000135480A (en) | Treatment of residue | |
| CN101205085A (en) | Method for producing secondary ammonium molybdate by molybdenum recovery material | |
| KR0128123B1 (en) | Refining method of wasting acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120823 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131120 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131126 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140110 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140128 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140204 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5473523 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |