JP2001198561A - Method for recovering bromine from waste printed circuit board - Google Patents
Method for recovering bromine from waste printed circuit boardInfo
- Publication number
- JP2001198561A JP2001198561A JP2000008695A JP2000008695A JP2001198561A JP 2001198561 A JP2001198561 A JP 2001198561A JP 2000008695 A JP2000008695 A JP 2000008695A JP 2000008695 A JP2000008695 A JP 2000008695A JP 2001198561 A JP2001198561 A JP 2001198561A
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- printed circuit
- hydrogen bromide
- circuit board
- recovering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 65
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 21
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 32
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 31
- 238000000197 pyrolysis Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000010992 reflux Methods 0.000 abstract description 15
- 239000007789 gas Substances 0.000 abstract description 14
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract 5
- 239000011269 tar Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- -1 bromine compound Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0496—Pyrolysing the materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3425—Printed circuits
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、廃プリント基板からの
有価物回収処理に関わり、特にガラスエポキシ樹脂積層
基板などの臭素含有樹脂を構成材料とするプリント基板
廃棄物から、含有する臭素を分離し、再利用可能な形
（具体的には臭化水素水溶液）として回収するための方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for recovering valuable resources from waste printed circuit boards, and more particularly to the separation of bromine contained from printed circuit board waste containing bromine-containing resin such as a glass epoxy resin laminated board. And a method for recovering it as a reusable form (specifically, an aqueous solution of hydrogen bromide).
【０００２】[0002]
【従来の技術】廃家電・廃ＯＡ機器などの電気製品廃棄
物は、プリント基板を始めとする銅・銀・金等を含有す
るため、これら有価金属回収のためのスクラップとして
処理されている。プリント基板には難燃剤として有機系
の臭素化合物が樹脂に添加されており、樹脂分中の臭素
含有率は３〜１３％、廃プリント基板スクラップ全体で
１〜４％に達する。2. Description of the Related Art Waste electrical appliances such as waste home appliances and waste OA equipment contain printed circuit boards and other copper, silver, gold, and the like, and are therefore treated as scrap for the recovery of valuable metals. An organic bromine compound is added to a resin as a flame retardant in a printed circuit board, and the bromine content in the resin reaches 3 to 13%, and the waste scrap of the entire printed circuit board reaches 1 to 4%.
【０００３】臭素は、工業的には海水やかん水などの少
量の臭素を含む液を原料として製造されている有価物で
ある。しかし、従来は、上記のプリント基板に含まれる
高濃度の臭素を直接回収することは行われていなかっ
た。プリント基板に含まれる臭素の回収技術としては、
臭素を含む廃棄物全体を焼却し、燃焼後の排ガスに含ま
れる臭化水素をアルカリ液スクラバーで水洗捕集し、洗
浄液に濃縮した臭化物を化学処理して分離する方法があ
った。化学処理の方法としては、臭素の工業的製造に用
いられている、水洗液を弱酸性として空気酸化すること
で単体の臭素を分離回収する方法が適用できる。[0003] Bromine is a valuable resource industrially produced from a liquid containing a small amount of bromine such as seawater or brine. However, conventionally, the high concentration of bromine contained in the printed circuit board has not been directly recovered. As a technology for recovering bromine contained in printed circuit boards,
There has been a method in which the entire waste containing bromine is incinerated, hydrogen bromide contained in the exhaust gas after combustion is washed and collected with an alkaline scrubber, and bromide concentrated in the washing liquid is chemically treated and separated. As a chemical treatment method, a method of separating and recovering single bromine by subjecting a washing liquid to weak acidity and air oxidation, which is used in industrial production of bromine, can be applied.
【０００４】[0004]
【発明が解決しようとする課題】しかし、この方法は多
量のスクラバー洗浄液を中和処理する必要があり、燃焼
排ガス中のＨＢｒ濃度や共存するＳＯｘなどの酸性物質
の量によっては、臭素が経済的な回収対象となる濃度ま
で蓄積した洗浄液を回収することが困難であった。However, this method requires a large amount of scrubber cleaning solution to be neutralized, and bromine is economical depending on the HBr concentration in the flue gas and the amount of coexisting acidic substances such as SOx. It has been difficult to collect the washing liquid accumulated up to a concentration that is a target of the recovery.
【０００５】[0005]
【課題を解決するための手段】本発明は、以上の課題を
解決し、 （１）臭素系難燃剤を添加した樹脂を含むプリント基板
廃棄物を乾留処理して生じる臭素含有有機分解物蒸気を
分離し、この分離した前記有機分解物を単独で再熱分解
し、含有する臭素を臭化水素として分離回収するプリン
ト基板廃棄物からの臭素回収方法。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and (1) removes bromine-containing organic decomposition product vapor produced by dry-distilling printed circuit board waste containing a resin to which a bromine-based flame retardant has been added. A method for recovering bromine from printed circuit board waste, comprising separating and rethermally decomposing the separated organic decomposition product independently and separating and recovering the contained bromine as hydrogen bromide.
【０００６】（２）上記（１）において、前記プリント
基板廃棄物の乾留温度が３００℃〜１０００℃であるプ
リント基板廃棄物からの臭素回収方法。 （３）上記（１）において、乾留で生じる臭素含有有機
分解物の再熱分解温度が１８０℃〜３００℃であるプリ
ント基板廃棄物からの臭素回収方法。(2) The method for recovering bromine from printed circuit board waste as described in (1) above, wherein the dry distillation temperature of the printed circuit board waste is 300 ° C. to 1000 ° C. (3) The method for recovering bromine from printed circuit board waste as described in (1) above, wherein the bromine-containing organic decomposition product generated by dry distillation has a re-thermal decomposition temperature of 180 ° C to 300 ° C.
【０００７】（４）上記（１）において、臭素含有有機
分解物の再熱分解で生じる臭化水素の分離回収方法とし
て、再熱分解後の分解油に溶解する残留臭化水素を分解
油を水洗して水溶液として分離回収するプリント基板廃
棄物からの臭素回収方法。を提供する。(4) In the above (1), as a method for separating and recovering hydrogen bromide generated by rethermal decomposition of a bromine-containing organic decomposition product, residual hydrogen bromide dissolved in decomposed oil after rethermal decomposition is treated with decomposed oil. A method for recovering bromine from printed circuit board waste that is washed with water and separated and recovered as an aqueous solution. I will provide a.
【０００８】以下本発明に関して詳細に述べる。プリン
ト基板に添加されている臭素系難燃剤は、テトラブロモ
ビスフェノールＡ（ＴＢＰ）に代表される臭化フェノー
ル類が主体である。これら難燃剤は、３００℃以上で一
部が分解して臭素の一部は臭素ラジカルとなり最終的に
は臭化水素ガスとして脱離するが、含有する臭素の大半
は有機物の骨格と結合したまま、臭素含有有機分解物
（解裂した臭化フェノール類）の蒸気として樹脂から脱
離する。Hereinafter, the present invention will be described in detail. The brominated flame retardant added to the printed circuit board is mainly a brominated phenol represented by tetrabromobisphenol A (TBP). These flame retardants partially decompose at 300 ° C. or higher, and part of bromine turns into bromine radicals and is eventually released as hydrogen bromide gas. However, most of the contained bromine remains bound to the organic skeleton. As a vapor of bromine-containing organic decomposition products (broken phenols).
【０００９】この時、プリント基板の主成分樹脂（エポ
キシ樹脂、フェノール樹脂）も同時に分解し、フェノー
ル類の蒸気とコークス状の残渣となる。このため、プリ
ント基板を乾留し、分解蒸気を捕集すると、臭化フェノ
ールを含有するフェノール類の混合物からなる分解物タ
ールとして、臭素の大半を分離できる。At this time, the main component resins (epoxy resin, phenol resin) of the printed circuit board are simultaneously decomposed to form phenol vapor and coke-like residue. Therefore, when the printed circuit board is carbonized and the decomposition vapor is collected, most of the bromine can be separated as a decomposition product tar composed of a mixture of phenols containing brominated phenol.
【００１０】発明者等は、この臭素含有分解物タール
は、再度加熱すると臭素化合物が徐々に熱分解し、臭素
は臭化水素ガスとして脱離することを見出した。本発明
は、この反応を利用して、廃プリント基板を乾留熱分解
して臭素含有有機物タールを分離した後、このタールを
再び熱分解して含有する臭素を臭化水素として分離し、
最終的に臭化水素水溶液を回収する技術を提案するもの
である。 このフローの概要を図１に示す。The present inventors have found that when the bromine-containing decomposition product tar is heated again, the bromine compound is gradually thermally decomposed, and the bromine is eliminated as hydrogen bromide gas. The present invention utilizes this reaction to separate the bromine-containing organic tar by dry distillation pyrolysis of the waste printed circuit board and then pyrolyze the tar again to separate the contained bromine as hydrogen bromide.
Finally, a technique for recovering an aqueous hydrogen bromide solution is proposed. FIG. 1 shows an outline of this flow.
【００１１】以下、本発明における処理方法と条件につ
いて、その詳細を説明する。 （１）乾留処理 該プリント基板スクラップは、図２に示す形式の乾留装
置を用いて、不活性雰囲気下で加熱乾留して臭素含有有
機分解物を留出させる。乾留温度３００℃〜１０００℃
で行うことが好ましい。これは、乾留温度が３００℃よ
り低いと臭素脱離反応が不十分で、乾留後のコークス化
した残渣に臭素が残り好ましくなく、乾留温度１０００
℃より高くしたとしても臭素の除去効果は無いためであ
る。ただより望ましい温度範囲は、３５０℃〜８００℃
である。より効率的に反応が行われるからである。Hereinafter, the processing method and conditions in the present invention will be described in detail. (1) Dry distillation treatment The printed circuit board scrap is heated to dry distillation under an inert atmosphere using a dry distillation apparatus of the type shown in FIG. 2 to distill bromine-containing organic decomposition products. Carbonization temperature 300 ℃ ～ 1000 ℃
It is preferable to carry out in. If the carbonization temperature is lower than 300 ° C., the bromine elimination reaction is insufficient, bromine remains in the coked residue after carbonization, which is not preferable.
This is because there is no bromine removal effect even if the temperature is higher than ° C. However, a more desirable temperature range is 350 ° C to 800 ° C.
It is. This is because the reaction is performed more efficiently.
【００１２】乾留処理で生じる臭素含有有機分解物蒸気
および分解ガスは、冷却部に導き凝縮させて臭素含有有
機物をタールとして捕集する。乾留熱分解の段階で臭素
の一部は臭化水素（ＨＢｒ）ガスの形まで分解するが、
凝縮部を５０℃以下まで冷却すれば 大半のＨＢｒガス
は分解ガス中の水蒸気とともに凝縮し、高濃度（２０〜
４５重量％）の臭化水素酸水溶液としてタールとともに
捕集される。必要であるならば排ガスをさらに水洗して
冷却部で捕集しきれないＨＢｒを捕集した後、排ガスを
二次燃焼処理などに送って処理する。[0012] The bromine-containing organic decomposition product vapor and the decomposition gas generated in the dry distillation treatment are led to a cooling section where they are condensed to collect the bromine-containing organic substances as tar. At the stage of pyrolysis pyrolysis, a part of bromine is decomposed into hydrogen bromide (HBr) gas,
If the condensing part is cooled to 50 ° C or less, most of the HBr gas condenses with the water vapor in the decomposition gas, and has a high concentration (20 to
(45% by weight) aqueous solution of hydrobromic acid together with tar. If necessary, the exhaust gas is further washed with water to collect HBr that cannot be collected in the cooling unit, and then the exhaust gas is sent to a secondary combustion process or the like to be processed.
【００１３】前記の方法で分離した臭素含有有機分解物
は、次項の再熱分解（以下加熱還流処理と称す。）を行
う。 （２）加熱還流処理 前記の方法で分離した臭素含有有機分解物のタールは、
図３に示す形式の加熱還流装置に導き加熱分解する。The bromine-containing organic decomposition product separated by the above-mentioned method is subjected to the following re-thermal decomposition (hereinafter referred to as heating reflux treatment). (2) Heat reflux treatment The tar of the bromine-containing organic decomposition product separated by the above method is
It is led to a heating reflux device of the type shown in FIG.
【００１４】この時、有機物とともに水冷部に凝縮した
臭化水素酸水溶液は、タールと共に加熱還流装置に投入
してもよいし、あらかじめ分離してタール分のみを還流
分解してもよい。加熱中のタールの温度は、通常は主成
分のフェノール類の沸点である１８０〜２３０℃で安定
する。温度が１８０℃以上あればタール中の臭化フェノ
ール類は分解する。温度が高いほど分解が早くなるが、
タール中成分の重合や高沸点成分の濃縮のためタールが
粘重化したり、内部での沸騰が激しすぎて冷却器で凝縮
しきれず未分解の有機物蒸気が外部に放出されるため、
内容物の温度は３００℃以下、より好ましくは前記の沸
点の範囲である２００〜２３０℃の範囲で加熱するのが
望ましい。At this time, the aqueous solution of hydrobromic acid condensed in the water cooling section together with the organic matter may be introduced into the heating and reflux apparatus together with the tar, or may be separated in advance and only the tar component is subjected to reflux decomposition. The temperature of the tar during heating is usually stabilized at 180 to 230 ° C., which is the boiling point of the phenol as the main component. If the temperature is 180 ° C. or higher, brominated phenols in the tar are decomposed. The higher the temperature, the faster the decomposition,
Because the tar becomes viscous due to the polymerization of the components in the tar and the concentration of the high-boiling components, and the boiling inside is too intense to condense in the cooler and undecomposed organic vapor is released to the outside,
It is desirable to heat the contents at a temperature of 300 ° C. or lower, more preferably in the range of 200 to 230 ° C. which is the above boiling point range.
【００１５】この時、水冷冷却部の温度と冷却効率を適
切に保てば、分解で生じたＨＢｒガスは同時に生じた水
蒸気とともに共沸混合物（ｂｐ．１２４℃、ＨＢｒ ４
７％）として凝縮し、還流装置内に戻る。分解後の内容
物は冷却して取出す。還流熱分解後は、内容物は臭化水
素酸水溶液と分解油の二層に分離するので、これを分別
する。水相はそのまま高濃度の粗製臭化水素酸水溶液と
して回収する。この時、分解油には臭化水素の一部が溶
解しているが、油を水洗すれば臭化水素は水に逆抽出さ
れる。同体積の水で２回水洗すれば、油中に溶解した臭
化水素の９９％を分離回収できる。At this time, if the temperature and the cooling efficiency of the water-cooled cooling section are appropriately maintained, the HBr gas generated by the decomposition will be mixed with the steam generated at the same time as an azeotropic mixture (bp. 124 ° C., HBr 4
7%) and returns to the reflux system. The content after decomposition is cooled and taken out. After the reflux pyrolysis, the contents are separated into two layers of a hydrobromic acid aqueous solution and a cracked oil, which are separated. The aqueous phase is recovered as it is as a highly concentrated aqueous solution of hydrobromic acid. At this time, part of the hydrogen bromide is dissolved in the cracked oil, but if the oil is washed with water, the hydrogen bromide is back-extracted into water. By washing twice with the same volume of water, 99% of hydrogen bromide dissolved in the oil can be separated and recovered.
【００１６】以上の処理により、臭化水素の大半は 乾
留および／または還流熱分解で得られる高濃度（２５〜
５０重量％）の水溶液として回収できる。この臭化水素
酸には若干の有機物が溶解するが、混入有機物の大半は
フェノール（ｂｐ．１８０℃）およびより高沸点の有機
物のため、分留により共沸点組成（ｂｐ．１２４℃、４
７％）の精製臭化水素水溶液を分離回収する。By the above treatment, most of the hydrogen bromide has a high concentration (25 to 25) obtained by dry distillation and / or reflux pyrolysis.
(50% by weight). Although some organic substances are dissolved in this hydrobromic acid, most of the contaminating organic substances are phenol (bp. 180 ° C.) and higher boiling organic substances.
7%) of a purified aqueous solution of hydrogen bromide.
【００１７】また、他の臭素化合物合成原料として使う
場合には、そのまま利用することもできる。 乾留分解
ガスの水洗液および還流熱分解後分解油の水洗液として
分離回収した低濃度（１重量％以下）のＨＢｒ水溶液か
らは、同様に分留によりＨＢｒを濃縮・回収する。When used as another bromine compound synthesis raw material, it can be used as it is. HBr aqueous solution having a low concentration (1% by weight or less) separated and recovered as a washing liquid of the dry distillation cracked gas and a washing liquid of the cracked oil after reflux pyrolysis is similarly concentrated and recovered by fractional distillation.
【００１８】本発明では、バッチ処理による分解装置を
提示したが、処理装置はこれに限定されるものではな
い。処理スケールによっては、半連続的な処理装置を用
いて、（１）乾留による臭素含有タール分離、と（２）
臭素含有タールの還流熱分解とを行い、発生した臭化水
素を水蒸気とともに分留塔に導いて 蒸留臭化水素酸溶
液を直接回収するプロセスを適用することも可能であ
る。In the present invention, the disassembling apparatus by batch processing is presented, but the processing apparatus is not limited to this. Depending on the treatment scale, semi-continuous treatment equipment is used to (1) separate bromine-containing tars by dry distillation, and (2)
It is also possible to apply a process in which bromine-containing tar is subjected to reflux pyrolysis, and the generated hydrogen bromide is led to a fractionation tower together with steam to directly recover a distilled hydrobromic acid solution.
【００１９】[0019]
【実施例】以下、本発明の効果を検証するため、廃プリ
ント基板を処理した結果を示す。ガラスエポキシ樹脂積
層板（樹脂含有率３０％、Ｂｒ品位３．９％）２００ｇ
を 図２に示す横形乾留炉にチャージして、窒素ガス置
換後、温度３５０℃、５００℃、８００℃の３条件で１
ｈｒ乾留した。The results of processing a waste printed circuit board to verify the effects of the present invention will be described below. Glass epoxy resin laminate (resin content 30%, Br grade 3.9%) 200g
Was charged into a horizontal dry distillation furnace shown in FIG. 2 and replaced with nitrogen gas, and then charged under three conditions of 350 ° C., 500 ° C., and 800 ° C.
hr for carbonization.
【００２０】それぞれの試験で水冷部に凝縮したタール
と臭化水素酸水溶液を分離した後、タールを図３に示す
還流熱分解装置にチャージして、沸点（１８０〜２００
℃）で５ｈｒ加熱した。In each test, the tar condensed in the water cooling section and the aqueous solution of hydrobromic acid were separated, and the tar was charged into a reflux pyrolysis apparatus shown in FIG.
℃) for 5 hours.
【００２１】乾留後の反応物から、水相（臭化水素酸水
溶液）と分解油とを分離し、分解油は同重量の水と３ｍ
ｉｎ攪拌した。乾留および還流熱分解時の排ガスは 洗
気ビンに導きＨＢｒガスを水で捕集した。乾留処理で得
た分解生成物の量と臭素含有率を表１に示す。An aqueous phase (aqueous hydrobromic acid) and a cracked oil are separated from the reaction product after the dry distillation, and the cracked oil is mixed with the same weight of water and 3 m
and stirred. Exhaust gas at the time of carbonization and reflux pyrolysis was led to a washing bottle to collect HBr gas with water. Table 1 shows the amounts of the decomposition products and the bromine content obtained by the carbonization treatment.
【表１】 同じく、表1（Ｂ）項のタールを加熱還流・水洗して得
た分解生成物の量と臭素含有率を表２に示す。[Table 1] Similarly, Table 2 shows the amount of decomposition products and the bromine content obtained by heating the tar in Table 1 (B) under reflux and washing with water.
【表２】 原料基板中の臭素の７６〜７８％を精製臭化水素酸水溶
液として回収できた。[Table 2] 76 to 78% of bromine in the raw material substrate could be recovered as a purified aqueous solution of hydrobromic acid.
【００２２】[0022]
【発明の効果】以上に説明したように、本発明は廃プリ
ント基板を段階的に熱分解することで、含有する臭素を
直接高濃度の臭化水素酸水溶液として回収することがで
きる。As described above, according to the present invention, bromine contained can be directly recovered as a high-concentration aqueous solution of hydrobromic acid by thermally decomposing a waste printed circuit board in stages.
【図１】 本発明における処理フローの概略を示す。FIG. 1 shows an outline of a processing flow in the present invention.
【図２】 本発明における乾留装置の該略図を示す。FIG. 2 shows the schematic diagram of the carbonization apparatus in the present invention.
【図３】 本発明における加熱還流装置の該略図を示
す。FIG. 3 shows the schematic diagram of a heating and reflux apparatus according to the present invention.
１ 加熱炉 ２ 乾留装置 ３ 冷却部（蒸気凝縮部） ４ 廃プリント基板 ５ 臭素含有有機分解物 ６ 不活性ガス ７ 加熱還流装置 ８ 加熱炉 ９ 冷却部 １０ 臭素含有有機分解物 １１ 冷却水 DESCRIPTION OF SYMBOLS 1 Heating furnace 2 Drying apparatus 3 Cooling part (steam condensing part) 4 Waste printed circuit board 5 Bromine-containing organic decomposition product 6 Inert gas 7 Heating recirculation device 8 Heating furnace 9 Cooling part 10 Bromine-containing organic decomposition product 11 Cooling water
Claims (4)
ント基板廃棄物を乾留処理して生じる臭素含有有機分解
物蒸気を分離し、この分離した前記有機分解物を単独で
再熱分解し、含有する臭素を臭化水素として分離回収す
ることを特徴とするプリント基板廃棄物からの臭素回収
方法。1. A bromine-containing organic decomposition product vapor generated by subjecting a printed circuit board waste containing a resin to which a bromine-based flame retardant has been added to dry distillation to be separated, and the separated organic decomposition product is re-thermally decomposed alone. A method for recovering bromine from printed circuit board waste, comprising separating and recovering bromine contained as hydrogen bromide.
物の乾留温度が３００℃〜１０００℃であることを特徴
とするプリント基板廃棄物からの臭素回収方法。2. The method for recovering bromine from printed circuit board waste according to claim 1, wherein the dry distillation temperature of the printed circuit board waste is 300 ° C. to 1000 ° C.
有機分解物の再熱分解温度が１８０℃〜３００℃である
ことを特徴とするプリント基板廃棄物からの臭素回収方
法。3. The method for recovering bromine from printed circuit board waste according to claim 1, wherein the re-decomposition temperature of the bromine-containing organic decomposition product generated by dry distillation is 180 ° C. to 300 ° C.
再熱分解で生じる臭化水素の分離回収方法として、再熱
分解後の分解油に溶解する残留臭化水素を分解油を水洗
して水溶液として分離回収することを特徴とする、プリ
ント基板廃棄物からの臭素回収方法。4. A method for separating and recovering hydrogen bromide generated by rethermal decomposition of a bromine-containing organic decomposition product according to claim 1, wherein the residual hydrogen bromide dissolved in the cracked oil after rethermal decomposition is washed with water. A method for recovering bromine from printed circuit board waste, comprising separating and recovering as an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000008695A JP2001198561A (en) | 2000-01-18 | 2000-01-18 | Method for recovering bromine from waste printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000008695A JP2001198561A (en) | 2000-01-18 | 2000-01-18 | Method for recovering bromine from waste printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001198561A true JP2001198561A (en) | 2001-07-24 |
Family
ID=18536925
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000008695A Pending JP2001198561A (en) | 2000-01-18 | 2000-01-18 | Method for recovering bromine from waste printed circuit board |
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| Country | Link |
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| JP (1) | JP2001198561A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061008A (en) * | 2010-11-09 | 2011-05-18 | 佛山市高明区(中国科学院)新材料专业中心 | Method for reducing bromide content in pyrolysis gas of waste printed circuit board by high-temperature shock heating |
| CN104707557A (en) * | 2015-02-09 | 2015-06-17 | 福建工程学院 | Method for preparing heavy metal adsorption material from waste circuit board non-metal powder |
| CN104889140A (en) * | 2015-05-27 | 2015-09-09 | 福建工程学院 | Processing method for waste printed circuit board |
| WO2020175350A1 (en) | 2019-02-28 | 2020-09-03 | 三菱マテリアル株式会社 | Method for treating waste electronic substrate |
-
2000
- 2000-01-18 JP JP2000008695A patent/JP2001198561A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061008A (en) * | 2010-11-09 | 2011-05-18 | 佛山市高明区(中国科学院)新材料专业中心 | Method for reducing bromide content in pyrolysis gas of waste printed circuit board by high-temperature shock heating |
| CN104707557A (en) * | 2015-02-09 | 2015-06-17 | 福建工程学院 | Method for preparing heavy metal adsorption material from waste circuit board non-metal powder |
| CN104889140A (en) * | 2015-05-27 | 2015-09-09 | 福建工程学院 | Processing method for waste printed circuit board |
| WO2020175350A1 (en) | 2019-02-28 | 2020-09-03 | 三菱マテリアル株式会社 | Method for treating waste electronic substrate |
| JP2020138141A (en) * | 2019-02-28 | 2020-09-03 | 三菱マテリアル株式会社 | Processing method of waste electronic substrate |
| KR20210132049A (en) | 2019-02-28 | 2021-11-03 | 미쓰비시 마테리알 가부시키가이샤 | How to dispose of waste electronic boards |
| JP7146176B2 (en) | 2019-02-28 | 2022-10-04 | 三菱マテリアル株式会社 | Disposal method for waste electronic substrates |
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