JP2015145529A - Silver recovery method - Google Patents
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- JP2015145529A JP2015145529A JP2014019447A JP2014019447A JP2015145529A JP 2015145529 A JP2015145529 A JP 2015145529A JP 2014019447 A JP2014019447 A JP 2014019447A JP 2014019447 A JP2014019447 A JP 2014019447A JP 2015145529 A JP2015145529 A JP 2015145529A
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 128
- 239000004332 silver Substances 0.000 title claims abstract description 128
- 238000011084 recovery Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 124
- 239000010457 zeolite Substances 0.000 claims abstract description 86
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 85
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 14
- 229940100890 silver compound Drugs 0.000 claims abstract description 9
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 description 8
- 150000003464 sulfur compounds Chemical class 0.000 description 8
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- JKLNYGDWYRKFKR-UHFFFAOYSA-N ethyl methyl sulfate Chemical compound CCOS(=O)(=O)OC JKLNYGDWYRKFKR-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 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
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、銀を含有するゼオライトから、効率的に銀を回収するための方法に関する。より詳しくは、触媒、吸着剤として使用された硫黄成分と銀とを含むゼオライトから銀を回収する方法に関する。 The present invention relates to a method for efficiently recovering silver from a zeolite containing silver. More specifically, the present invention relates to a method for recovering silver from a zeolite containing a sulfur component and silver used as a catalyst and an adsorbent.
金属を含有するゼオライトは各種の吸着剤や触媒として使用されている。特に、銀を含有するゼオライトは硫黄化合物の吸着剤等（例えば、非特許文献１など）として検討されている。このような銀を含有するゼオライトは、吸着活性又は触媒活性が劣化するまで使用され、その後、硫黄化合物を含んだ状態で産業廃棄物として処分されている。 Metal-containing zeolites are used as various adsorbents and catalysts. In particular, zeolite containing silver has been studied as an adsorbent for sulfur compounds (for example, Non-Patent Document 1). Such silver-containing zeolite is used until the adsorption activity or catalytic activity is deteriorated, and then disposed of as industrial waste in a state containing a sulfur compound.
一方、これまで、銀を含む産業廃棄物からの銀回収が検討されている。例えば、特許文献１には銀、金、及び白金族を含む貴金属、並びに銅と鉛とを含む原料からの銀の回収方法が報告されている。当該回収方法では、最初に該原料から硫酸溶液で銅を除去した後、銀を含む沈殿物を生成させる。その後、塩酸での処理により沈殿から金、白金族成分を除去する。その後、更に沈殿と鉄粉とを混合することで銀を金属状態とする。このようにして得られた金属状態の銀を含む混合物を高温酸化させてスラグとし、最後に電解を行うことで、高純度の銀を回収する方法であった。 Meanwhile, recovery of silver from industrial waste containing silver has been studied. For example, Patent Literature 1 reports a method for recovering silver from a noble metal including silver, gold, and a platinum group, and a raw material including copper and lead. In the recovery method, first, copper is removed from the raw material with a sulfuric acid solution, and then a precipitate containing silver is generated. Thereafter, gold and platinum group components are removed from the precipitate by treatment with hydrochloric acid. Then, silver is made into a metal state by further mixing the precipitate and the iron powder. It was the method of collect | recovering highly purified silver by oxidizing the mixture containing the silver of the metal state obtained in this way at high temperature to make slag, and finally electrolyzing.
また、特許文献２には難溶性銀化合物原料から銀を抽出し、回収する方法が開示されている。この方法では、最初に分子中に硫黄を含む有機燐化合物で原料を溶解し、銀を有機相に抽出する。その後、得られた有機相から亜硫酸アルカリ水溶液により銀を逆抽出し、この逆抽出液から銀を還元析出させる方法であった。 Patent Document 2 discloses a method for extracting and recovering silver from a hardly soluble silver compound raw material. In this method, first, a raw material is dissolved with an organic phosphorus compound containing sulfur in the molecule, and silver is extracted into an organic phase. Thereafter, silver was back-extracted from the obtained organic phase with an aqueous alkali sulfite solution, and silver was reduced and precipitated from this back-extracted solution.
特許文献１の方法では、複数の金属と同時に銀を回収するため、その工程は複雑、かつ、高温酸化や電解など、大型設備を必要とする工程を多く使用するため、大規模な処理施設を必要とする。また、特許文献２に記載の方法は、金などを含む難溶性銀化合物から、銀を抽出回収するために有機溶媒に抽出させる。しかしながら、有機溶媒での抽出は複数回の繰返しを要することに加え、有機溶媒を使用する当該工程は、水溶液系により処理と比べて特殊な設備を必要とするため、産業廃棄物の処理方法としてはコストが高くなりすぎる。 In the method of Patent Document 1, since silver is recovered simultaneously with a plurality of metals, the process is complicated, and many processes that require large equipment such as high-temperature oxidation and electrolysis are used. I need. In the method described in Patent Document 2, silver is extracted from an insoluble silver compound containing gold or the like into an organic solvent in order to extract and recover the silver. However, extraction with an organic solvent requires a plurality of repetitions, and the process using an organic solvent requires special equipment compared to the treatment with an aqueous solution system. Is too expensive.
さらに、特許文献１及び２に記載の方法で対象とする材料は、金や白金など、より高価な貴金属を含む銀含有物であるのに対し、通常、吸着剤や触媒等として使用されるゼオライトに含まれる貴金属は銀のみであり、更にその量はごく少ない。そのため、回収できる銀の価値以上に回収コストがかかり、特許文献１及び２の方法は、ゼオライトからの銀の回収に適した方法ではなかった。 Furthermore, while the materials targeted by the methods described in Patent Documents 1 and 2 are silver-containing materials containing more expensive noble metals such as gold and platinum, they are usually used as adsorbents and catalysts. The precious metal contained in is only silver, and the amount is very small. For this reason, the recovery cost exceeds the value of recoverable silver, and the methods of Patent Documents 1 and 2 are not suitable methods for recovering silver from zeolite.
さらに、銀を含むゼオライトからの回収方法はもちろん、硫黄成分と銀を含むゼオライトに適した銀の回収方法はこれまで報告されていない。 Furthermore, not only a recovery method from zeolite containing silver, but also a recovery method of silver suitable for zeolite containing a sulfur component and silver has not been reported so far.
これらの課題に鑑み、本発明は、硫黄成分と銀とを含むゼオライトから銀を回収する方法を提供することを目的とする。 In view of these problems, an object of the present invention is to provide a method for recovering silver from a zeolite containing a sulfur component and silver.
本発明者らは、銀を含むゼオライト、特に硫黄成分と銀とを含むゼオライトに適した銀の回収方法について検討した。その結果、硫黄成分と銀を含むゼオライトは、硫黄成分を含まないゼオライトとは銀の挙動が異なること、更には硫黄成分と銀とを含むゼオライトは、前処理の条件を制御することで、簡便な処理で、銀が酸抽出できることを見出した。 The present inventors examined a silver recovery method suitable for a zeolite containing silver, particularly a zeolite containing a sulfur component and silver. As a result, zeolite containing a sulfur component and silver has a silver behavior different from that of a zeolite not containing a sulfur component. Further, zeolite containing a sulfur component and silver can be simplified by controlling pretreatment conditions. It was found that silver can be acid extracted by simple treatment.
すなわち、本発明は、硫黄成分と銀とを含有するゼオライトから銀を回収する方法であって、前記ゼオライトの耐熱温度以下の温度で熱処理する熱処理工程、前記熱処理工程後のゼオライトを無機酸水溶液と混合する酸処理工程、及び、前記酸処理工程後の無機酸水溶液から銀化合物を得る回収工程を含むことを特徴とする銀の回収方法である。 That is, the present invention is a method for recovering silver from a zeolite containing a sulfur component and silver, a heat treatment step in which heat treatment is performed at a temperature not higher than the heat resistant temperature of the zeolite, and the zeolite after the heat treatment step is used as an inorganic acid aqueous solution. A silver recovery method comprising: an acid treatment step of mixing, and a recovery step of obtaining a silver compound from the inorganic acid aqueous solution after the acid treatment step.
以下、本発明の銀の回収方法（以下、単に「回収方法」ともいう。）について説明する。 Hereinafter, the silver recovery method of the present invention (hereinafter also simply referred to as “recovery method”) will be described.
本発明の回収方法は、ゼオライトから銀を回収する方法である。ゼオライトとしてＹ型ゼオライト又はβ型ゼオライトの少なくともいずれかを挙げることができる。 The recovery method of the present invention is a method for recovering silver from zeolite. As the zeolite, at least one of Y-type zeolite and β-type zeolite can be mentioned.
本発明の回収方法に供するゼオライトは銀を含有するゼオライト（以下、「銀含有ゼオライト」ともいう。）であり、特にイオン交換サイトに銀が担持されたゼオライトであることが好ましい。更に、本発明に供するゼオライトは、硫黄成分を含む銀含有ゼオライトであり、更に硫黄成分として硫黄化合物を含む銀含有ゼオライト、また更にはゼオライトの細孔中に硫黄化合物として硫黄成分を含む銀含有ゼオライトである。 The zeolite used in the recovery method of the present invention is a zeolite containing silver (hereinafter also referred to as “silver-containing zeolite”), and is particularly preferably a zeolite having silver supported on an ion exchange site. Furthermore, the zeolite to be used in the present invention is a silver-containing zeolite containing a sulfur component, and further containing a sulfur compound as a sulfur component, and further containing a sulfur component as a sulfur compound in the pores of the zeolite. It is.
本発明の回収方法に供する、硫黄成分を含む銀含有ゼオライトが有する銀及び硫黄成分の量に制限はないが、通常、銀含有ゼオライトは、ゼオライトの重量に対する銀の重量が１重量％以上、３０重量％以下である。また、硫黄成分は、例えば、ゼオライトの重量に対する硫黄の重量が０．５重量％以上、１０重量％以下を挙げることができる。ここで硫黄成分とは硫黄化合物であり、硫化物や有機硫黄化合物及びこれら混合物を挙げることができる。硫化物としては硫化銀などの金属硫化物を例示することができ、有機硫黄化合物としてはメルカプタン類、サルフェート類及びチオフェン類の群からなる１種以上、更にはメチルメルカプタン、エチルメルカプタン、プロピルメルカプタン、ターシャリブチルメルカプタン、ジメチルサルフェート、エチルメチルサルフェート、ジエチルサルフェート及びテトラヒドロチオフェンの群から選ばれる１種以上を例示することができる。 Although there is no restriction | limiting in the quantity of the silver and sulfur component which the silver containing zeolite containing a sulfur component has in the collection | recovery method of this invention, Usually, as for a silver containing zeolite, the weight of silver with respect to the weight of a zeolite is 1 weight% or more, 30 % By weight or less. Moreover, as for the sulfur component, the weight of sulfur with respect to the weight of a zeolite can mention 0.5 weight% or more and 10 weight% or less, for example. Here, the sulfur component is a sulfur compound, and examples thereof include sulfides, organic sulfur compounds, and mixtures thereof. Examples of the sulfide include metal sulfides such as silver sulfide. Examples of the organic sulfur compound include one or more selected from the group of mercaptans, sulfates and thiophenes, and methyl mercaptan, ethyl mercaptan, propyl mercaptan, One or more types selected from the group of tertiary butyl mercaptan, dimethyl sulfate, ethyl methyl sulfate, diethyl sulfate and tetrahydrothiophene can be exemplified.
硫黄成分を含む銀含有ゼオライトとして、硫黄化合物の吸着反応や硫黄化合物の合成反応の触媒や吸着剤として使用された銀含有ゼオライトを挙げることができる。 Examples of the silver-containing zeolite containing a sulfur component include a silver-containing zeolite used as a catalyst or adsorbent for sulfur compound adsorption reaction or sulfur compound synthesis reaction.
熱処理工程において、硫黄成分を含む銀含有ゼオライトを耐熱温度以下で熱処理する。銀含有ゼオライトの耐熱温度を超えた温度下における熱処理は、ゼオライトの結晶性を低下させ、これによりゼオライト自体と銀とが反応する。これにより、銀の回収が困難になる。したがって、熱処理は、銀含有ゼオライトの耐熱温度以下の温度で行う。銀含有ゼオライトの耐熱温度は、ゼオライトの結晶性の低下が開始する温度であり、これはゼオライトのフレームタイプにより異なる。銀含有ゼオライトがβ型ゼオライトである場合は８５０℃以下、更には８００℃以下であり、銀含有ゼオライトがＹ型ゼオライトである場合は７５０℃以下、更には７００℃以下である。さらに、銀含有ゼオライトがβ型ゼオライトとＹ型ゼオライトの混合物である場合は、熱処理は７５０℃以下、更には７００℃以下である。 In the heat treatment step, the silver-containing zeolite containing a sulfur component is heat-treated at a heat resistant temperature or lower. The heat treatment at a temperature exceeding the heat-resistant temperature of the silver-containing zeolite reduces the crystallinity of the zeolite, and thereby the zeolite itself and silver react. This makes silver recovery difficult. Accordingly, the heat treatment is performed at a temperature not higher than the heat resistance temperature of the silver-containing zeolite. The heat-resistant temperature of the silver-containing zeolite is a temperature at which the crystallinity of the zeolite starts to decrease, and this varies depending on the flame type of the zeolite. When the silver-containing zeolite is β-type zeolite, it is 850 ° C. or lower, and further 800 ° C. or lower. When the silver-containing zeolite is Y-type zeolite, it is 750 ° C. or lower, and further 700 ° C. or lower. Further, when the silver-containing zeolite is a mixture of β-type zeolite and Y-type zeolite, the heat treatment is 750 ° C. or lower, and further 700 ° C. or lower.
一方、熱処理を施こすことなく、硫黄成分を含む銀含有ゼオライトを酸処理工程に供すると、当該ゼオライト中に銀の不溶性化合物が形成する。これにより、銀の回収が困難になるだけではなく、酸処理工程において硫化水素の生成を伴う場合がある。不溶性化合物の生成を抑えるため、熱処理温度は３００℃以上であることが好ましく、４００℃以上、更には５００℃以上であればよい。 On the other hand, when silver-containing zeolite containing a sulfur component is subjected to an acid treatment step without being subjected to heat treatment, an insoluble silver compound is formed in the zeolite. This not only makes silver recovery difficult, but may also involve the production of hydrogen sulfide in the acid treatment step. In order to suppress the formation of insoluble compounds, the heat treatment temperature is preferably 300 ° C. or higher, 400 ° C. or higher, and more preferably 500 ° C. or higher.
熱処理工程は上記の温度で銀含有ゼオライトが加熱できれば熱処理時間は任意である。熱処理時間としては、０．５時間以上、更には１時間以上、また更には２時間以上行えばよい。 As long as the silver-containing zeolite can be heated at the above temperature, the heat treatment time is arbitrary. The heat treatment time may be 0.5 hour or longer, further 1 hour or longer, and further 2 hours or longer.
熱処理工程は、酸化性雰囲気であればよく、大気中雰囲気であってもよい。 The heat treatment step may be an oxidizing atmosphere and may be an air atmosphere.
熱処理後の銀含有ゼオライトは、これを無機酸水溶液と混合する酸処理工程に供する。酸処理工程により、銀含有ゼオライトに含まれる銀を無機酸水溶液に抽出し、銀を含む無機酸水溶液（以下、「抽出液」とする。）を得ることができる。 The silver-containing zeolite after the heat treatment is subjected to an acid treatment step in which it is mixed with an inorganic acid aqueous solution. Through the acid treatment step, silver contained in the silver-containing zeolite can be extracted into an inorganic acid aqueous solution to obtain an inorganic acid aqueous solution containing silver (hereinafter referred to as “extracted liquid”).
無機酸水溶液は、銀が抽出できるものであれば使用できるが、ゼオライトが溶解しないものであることが好ましい。このような無機酸水溶液として、硫酸、りん酸、硝酸及びフッ酸の群から選ばれる少なくとも１種の水溶液を挙げることができる。銀含有ゼオライトから銀を効率よく抽出するため、無機酸水溶液は硝酸又はフッ酸の少なくともいずれかの水溶液であることが好ましく、硝酸水溶液であることがより好ましい。 The inorganic acid aqueous solution can be used as long as it can extract silver, but it is preferable that the zeolite does not dissolve. Examples of such an inorganic acid aqueous solution include at least one aqueous solution selected from the group consisting of sulfuric acid, phosphoric acid, nitric acid, and hydrofluoric acid. In order to efficiently extract silver from the silver-containing zeolite, the aqueous inorganic acid solution is preferably an aqueous solution of at least one of nitric acid and hydrofluoric acid, and more preferably an aqueous nitric acid solution.
酸処理工程における無機酸水溶液の無機酸濃度が高いほど、銀含有ゼオライトからの銀の抽出が促進される傾向にある。無機酸濃度は、例えば、５０ｇ／Ｌ以上、５００ｇ／Ｌ以下、更には３００ｇ／Ｌ以下であれば、汎用の溶解設備を使用して銀の抽出ができる。 As the inorganic acid concentration of the aqueous inorganic acid solution in the acid treatment step is higher, the extraction of silver from the silver-containing zeolite tends to be promoted. If the inorganic acid concentration is, for example, 50 g / L or more, 500 g / L or less, and further 300 g / L or less, silver can be extracted using a general-purpose dissolution facility.
酸処理工程では、熱処理後の銀含有ゼオライトと無機酸水溶液とを十分に接触させればよく、具体的には銀含有ゼオライトと無機酸水溶液とを混合し、これを攪拌すればよい。銀含有ゼオライトと無機酸水溶液との割合は、攪拌できる程度の銀含有ゼオライトを無機酸水溶液と混合すればよく、例えば、無機酸水溶液に対する銀含有ゼオライトの重量が５重量％以上、５０重量％以下であることを挙げることができる。 In the acid treatment step, the silver-containing zeolite after the heat treatment and the inorganic acid aqueous solution may be sufficiently brought into contact. Specifically, the silver-containing zeolite and the inorganic acid aqueous solution may be mixed and stirred. The proportion of the silver-containing zeolite and the inorganic acid aqueous solution may be such that the silver-containing zeolite that can be stirred is mixed with the inorganic acid aqueous solution. For example, the weight of the silver-containing zeolite with respect to the inorganic acid aqueous solution is 5 wt% or more and 50 wt% or less. Can be mentioned.
酸処理工程により得られた抽出液は、これから銀化合物を得る回収工程に供する。これにより、抽出液に含まれる銀を銀化合物として回収することができる。 The extract obtained by the acid treatment step is subjected to a recovery step for obtaining a silver compound therefrom. Thereby, silver contained in the extract can be recovered as a silver compound.
回収工程では、抽出液と塩化物とを混合することで、塩化銀として抽出液中の銀を回収させることが好ましい。具体的には酸処理工程で得られた抽出液を撹拌しながら、塩化物を添加、反応させることで塩化銀の沈殿を生成させることができる。 In the recovery step, it is preferable that silver in the extract is recovered as silver chloride by mixing the extract and chloride. Specifically, silver chloride precipitates can be generated by adding and reacting chloride while stirring the extract obtained in the acid treatment step.
塩化物としては塩化カリウム、塩化ナトリウムを挙げることができ、溶解性、コストの面から塩化ナトリウムであることが好ましい。 Examples of the chloride include potassium chloride and sodium chloride, and sodium chloride is preferable from the viewpoint of solubility and cost.
回収工程で得られた沈殿物は、無機酸と沈殿物とを適宜分離し、銀を回収すればよい。 The precipitate obtained in the recovery step may be appropriately separated from the inorganic acid and the precipitate to recover silver.
本発明により、硫黄成分と銀とを含むゼオライトから銀を回収する方法を提供することができる。さらに、本発明の回収方法は、貴金属として銀のみを含むゼオライトから、効率よく銀を回収することができる。 According to the present invention, a method for recovering silver from a zeolite containing a sulfur component and silver can be provided. Furthermore, the recovery method of the present invention can recover silver efficiently from zeolite containing only silver as a noble metal.
さらに、本発明の銀の回収方法により、銀を回収した後のゼオライトを再生し、これを触媒担体や吸着剤として再利用することができる。 Furthermore, by the silver recovery method of the present invention, the zeolite after recovering silver can be regenerated and reused as a catalyst carrier or adsorbent.
実施例１
平均直径１．２ｍｍ、及び平均長さ３ｍｍの円柱状であり、ジメチルスルフィド及びターシャリーブチルメルカプタンを硫黄として計３．２重量％、及び銀を１５重量％含有するＹ型ゼオライト成形体からの銀を回収した。
Example 1
Silver from a Y-type zeolite compact having a cylindrical shape with an average diameter of 1.2 mm and an average length of 3 mm and containing 3.2% by weight of dimethyl sulfide and tertiary butyl mercaptan as sulfur and 15% by weight of silver Was recovered.
当該Ｙ型ゼオライト成形体を大気中、５００℃で１時間熱処理した。熱処理後のＹ型ゼオライト成形体は室温まで自然冷却した。 The Y-type zeolite compact was heat-treated at 500 ° C. for 1 hour in the atmosphere. The Y-type zeolite compact after the heat treatment was naturally cooled to room temperature.
自然冷却後のＹ型ゼオライト成形体５ｇを１０重量％硝酸水溶液２００ｇに添加し、室温で３時間、攪拌速度８０ｒｐｍでこれを撹拌した。なお、攪拌中のＹ型ゼオライト成形体の破損は観察されなかった。 5 g of the Y-type zeolite compact after natural cooling was added to 200 g of a 10 wt% aqueous nitric acid solution, and the mixture was stirred at room temperature for 3 hours at a stirring speed of 80 rpm. In addition, the breakage of the Y-type zeolite compact during stirring was not observed.
攪拌後、固液分離により、硝酸水溶液を回収した。回収した硝酸水溶液中の銀濃度は３，４４２ｍｇ／Ｌであった。 After stirring, an aqueous nitric acid solution was recovered by solid-liquid separation. The silver concentration in the collected aqueous nitric acid solution was 3,442 mg / L.
次いで、回収した硝酸水溶液に１．２倍当量の塩化ナトリウムを添加し、室温で１時間、攪拌速度８０ｒｐｍでこれを撹拌することで、沈殿物を得た。 Next, 1.2 times equivalent of sodium chloride was added to the collected aqueous nitric acid solution, and this was stirred at room temperature for 1 hour at a stirring speed of 80 rpm, thereby obtaining a precipitate.
固液分離により硝酸水溶液及び沈殿物を分離し、これらを回収した。回収後の硝酸水溶液中の銀濃度をＩＣＰ法により測定し、以下の式により銀の回収率を求めた。 The aqueous nitric acid solution and the precipitate were separated by solid-liquid separation, and these were collected. The silver concentration in the aqueous nitric acid solution after the recovery was measured by the ICP method, and the silver recovery rate was determined by the following formula.
銀の回収率（％）＝｛１−（Ｗ１−Ｗ２）／Ｗ１｝×１００ Silver recovery rate (%) = {1- (W 1 −W 2 ) / W 1 } × 100
ここで、Ｗ１は処理前のゼオライト中の銀含有量（ｇ）、及び、Ｗ２は回収後の硝酸水溶液中の銀含有量（ｇ）である。本実施例による銀の回収率は８９％であった。 Here, W 1 is the silver content (g) in the zeolite before treatment, and W 2 is the silver content (g) in the aqueous nitric acid solution after recovery. The silver recovery rate according to this example was 89%.
実施例２
熱処理の温度を６００℃としたこと以外は実施例１と同様な方法で銀の回収を行った。本実施例による銀の回収率は９２％であった。
Example 2
Silver was recovered in the same manner as in Example 1 except that the heat treatment temperature was 600 ° C. The silver recovery rate according to this example was 92%.
実施例３
ジメチルスルフィド及びターシャリーブチルメルカプタンを硫黄として計１．２重量％及び銀を５重量％含有するβ型ゼオライト成形体を使用したこと、及び、熱処理を８００℃で２時間としたこと以外は実施例１と同様な方法で銀回収を行った。本実施例による銀の回収率は９８％であった。
Example 3
Example except that dimethyl sulfide and tertiary butyl mercaptan were used as sulfur, and a β-type zeolite compact containing 1.2% by weight and 5% by weight of silver was used, and the heat treatment was performed at 800 ° C. for 2 hours. Silver recovery was performed in the same manner as in 1. The silver recovery rate according to this example was 98%.
比較例１
熱処理を行わなかったこと以外は実施例１と同様な方法で銀の回収を行った。
Comparative Example 1
Silver was recovered in the same manner as in Example 1 except that no heat treatment was performed.
本比較例による銀の回収率は２８％であった。なお、硝酸水溶液の添加時に臭気が発生し、硫化水素が発生していることが確認された。 The silver recovery rate according to this comparative example was 28%. It was confirmed that an odor was generated during the addition of the nitric acid aqueous solution and hydrogen sulfide was generated.
比較例２
熱処理を８００℃で２時間としたこと以外は実施例１と同様な方法で銀の回収を行った。本比較例による銀の回収率は６％であった。
Comparative Example 2
Silver was recovered in the same manner as in Example 1 except that the heat treatment was performed at 800 ° C. for 2 hours. The silver recovery rate according to this comparative example was 6%.
参考例１
硫黄含有量が０．０重量％のＹ型ゼオライトを使用したこと、及び、熱処理を行わなかったこと以外は実施例１と同様な方法で銀回収を行った。
Reference example 1
Silver recovery was performed in the same manner as in Example 1 except that a Y-type zeolite having a sulfur content of 0.0% by weight was used and no heat treatment was performed.
本参考例による銀の回収率は９６％であった。 The silver recovery rate according to this reference example was 96%.
以下、実施例、比較例、及び参考例においての結果を表１に示す。 The results in Examples, Comparative Examples, and Reference Examples are shown in Table 1 below.
参考例１の結果より、硫黄成分を含有しない銀含有ゼオライトは、熱処理を施さなくとも、銀の回収率が９６％と、高い回収率で銀が回収できた。一方、硫黄化合物と銀とが共存する比較例１では、熱処理を施さないと銀の回収率２８％と、著しく回収率が低下した。更には熱処理を施さない場合は、硫化水素の発生が示唆された。 From the results of Reference Example 1, the silver-containing zeolite containing no sulfur component was able to recover silver at a high recovery rate of 96% without performing heat treatment. On the other hand, in Comparative Example 1 in which the sulfur compound and silver coexist, the silver recovery rate was 28% and the recovery rate was significantly reduced unless heat treatment was performed. Furthermore, the generation of hydrogen sulfide was suggested when no heat treatment was performed.
これに対し、実施例１及び実施例２の結果より、硫黄成分を含有する銀含有ゼオライトでは、熱処理を施すことで８０％を超える銀が回収できると、更には熱処理温度が高くなることで、銀の回収率が９０％以上と高くなることが確認できた。 On the other hand, from the results of Example 1 and Example 2, in the silver-containing zeolite containing the sulfur component, when silver exceeding 80% can be recovered by heat treatment, the heat treatment temperature is further increased, It was confirmed that the silver recovery rate was as high as 90% or more.
さらに、実施例３の結果から、含有する銀の量が少ない場合であっても、高い回収率で銀が回収できることが確認できた。 Furthermore, from the results of Example 3, it was confirmed that even when the amount of silver contained was small, silver could be recovered with a high recovery rate.
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