EP1077747B1 - Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen - Google Patents
Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen Download PDFInfo
- Publication number
- EP1077747B1 EP1077747B1 EP98941357A EP98941357A EP1077747B1 EP 1077747 B1 EP1077747 B1 EP 1077747B1 EP 98941357 A EP98941357 A EP 98941357A EP 98941357 A EP98941357 A EP 98941357A EP 1077747 B1 EP1077747 B1 EP 1077747B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- components
- alkali
- printed circuit
- circuit boards
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 title claims abstract 3
- 239000011347 resin Substances 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229920003002 synthetic resin Polymers 0.000 claims description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 15
- 239000000057 synthetic resin Substances 0.000 claims description 15
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 4
- 238000004870 electrical engineering Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 229920006037 cross link polymer Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007857 degradation product Substances 0.000 description 6
- 230000029087 digestion Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 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 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000006148 magnetic separator Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- -1 aromatic dioxins Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010792 electronic scrap Substances 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/32—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by treatment in molten chemical reagent, e.g. salts or metals
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/36—Detoxification by using acid or alkaline reagents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
Definitions
- PCBs belong due to their complex structure and the ones they contain Pollutants among the most problematic in terms of recycling technology Components of the electronic scrap, and the contained in them Recyclable materials are a scarcely developed resource.
- the common disposal methods such as landfill or Burns are extremely problematic because they are either toxic Heavy metals such as copper, tin or lead occur in the leachate or when burning because of the content of bromine Flame retardants both aggressive acids as well aromatic dioxins and furans can arise.
- a circuit board is usually made up of numerous components equipped, of which particularly problematic such as batteries, Capacitors, rectifiers and mercury switches be removed before processing. This also happens with particularly valuable components such as gold-plated connector strips.
- the partial denaturation is environmentally friendly Utilization or disposal absolutely necessary, since All processes that have been carried out so far have at least a rough crushing is connected upstream. Otherwise it would become one Distribution of pollutants and recyclables, which come recovery is difficult as well as possible Pollutant release leads. The risk of one Pollutant emissions could only be reduced by: all process stages in hermetically sealed devices be carried out, which is of course expensive.
- the proportions of components and detached circuit board are approximately the same size (45%: 55%). It is advisable to separate all components from the circuit board beforehand, since the components contain about 95% of chromium and 85% of nickel and iron, while around 80% of tin, copper and lead can be found in the circuit board. As a rule, such complete dismantling is not yet carried out in practice, although the necessary methods are known (DE-PS 42 05 405, DE-OS 41 31 620). Component-free printed circuit boards are therefore usually production waste.
- a printed circuit board is mainly made of metal (30% by weight), glass fiber (50% by weight) and polymer resin (20% by weight), so far only the metals are considered as valuable materials. To regain them, they first need to be enriched and separated from the residues as much as possible become. There are several procedures for this, which also work together can be combined.
- US Pat. No. 5,580,905 describes a method for hydrolytic Cleavage of polyesters, namely polyalkylene terephthalates using caustic solutions of alkali hydroxides, in which the mixture is heated and the polyester to underlying salt and polyol is broken down. The reaction always takes place at temperatures up to the boiling point of the Polyols, so up to about 200 ° C to evaporate and cut off.
- the use described in column 6 / 30-32 of powdery or melted hydroxides is related to see with the overall disclosure of the aforementioned U.S.
- DE-OS 4 001 897 describes a method for Dissolution of circuit boards (printed circuit boards) known, in which this with the exclusion of oxygen at temperatures above 400 ° C introduced into a melt of alkali hydroxide and alkali oxide become.
- the alkali oxide converted into peroxide which is then converted into the Melt diffuses and oxidizable components such as carbon or hydrogen-containing compounds from the boards breaks down.
- the melt of alkali hydroxide and alkali oxide used as a matrix for the oxidation in this mode of operation (Column 1 / 25-32) and prevents the occurrence of toxic gases, how they would be created by combustion.
- column 1 / 29-34 is a raw material recovery and Can not be used for the synthetic resin or for the glass fibers.
- the object of the invention is now to develop a method that the material bond between metal, glass and Polymer dissolves.
- isolating largely pure Metal, glass and polymer fractions are said to be further processed and thus a substantial reduction or one largely avoidance of residual fractions to be disposed of become.
- the invention now relates to a method for material Digestion of composite materials containing synthetic resin, in which the high molecular structure of the synthetic resin chemical reaction in melts of alkali metal hydroxides is broken down at temperatures of 250 ° to 370 ° C.
- the hydroxides of the alkali metals are preferred NaOH or KOH and particularly preferably mixtures of NaOH and KOH.
- the proportion is: Potassium hydroxide for example 3 to 60% by weight, preferably 5 up to 20% by weight - the relatively small amount of potassium hydroxide is also due to the higher price Substance-related.
- the reaction temperatures are generally in the range between 260 ° and 370 ° C, preferably in the range between 280 ° and 370 ° C and particularly preferably in the range between 300 and 350 ° C.
- the choice of the most suitable temperature depends naturally on the type and composition of the starting materials from, it should be borne in mind that at higher temperatures both the speed of reaction and the danger the thermal formation of unwanted degradation products increased becomes. In general, can also within the above Temperature ranges when using potassium hydroxide work at a lower temperature than at of sodium hydroxide, and when using mixtures of Sodium and potassium hydroxide at even lower temperatures.
- reaction can be carried out using reaction aids are supported, which the wettability of the Improve the composite material with alkali metal hydroxides, lower or lower the melting point of the alkali metal hydroxides the reaction conditions a solvent or swelling power for the Have synthetic resin or its degradation products.
- the wettability of the composite improve come for example with the Reaction temperatures resistant surfactants into consideration.
- the alkali metal hydroxides e.g. B. inorganic salts of alkali, alkaline earth or earth metals or of metals of the fourth group of the periodic Systems or of metals of subgroups with strong or weak inorganic acids.
- the use of salts from Metals already contained in the raw materials can also support the reaction. This also has the advantage that no foreign elements in the system be introduced.
- the one Dissolving or swelling capacity for the synthetic resin or its degradation products own come z.
- B. oligomeric fragments or Base body of the synthetic resin into consideration under the reaction conditions are stable. In the event of digestion come from starting materials containing epoxy resin, for example the phenolic bases bisphenol A and F (4,4 ' Diphenylol-2,2-propane or -methane) into consideration.
- the synthetic resins are networked or uncrosslinked Polymers that are chemically cleavable in the main chain contain functional groups, such as polyesters, polyamides, Polyethers, polyurethanes, but preferably polyimides such as Polyphthalimides and poly-bimalinimides, polyaramides and polycyanate esters, but especially epoxy resins. These consist of usually from condensation products of bisphenols, such as Bisphenol A and bisphenol F, and epichlorohydrin. This list is to be understood as exemplary and not restrictive. Restrictions result from the type of chemical Disclosure and are obvious to the expert.
- the amount of alkali metal hydroxide used for digestion can be varied within wide limits.
- the in the amount applied in practice must be at least sufficient to to ensure that the procedure is carried out. For example but 50% by weight, based on the synthetic resin content, is sufficient out. But is useful for easier handling a significantly larger amount of alkali metal hydroxide is used.
- the prior art also produces dust-like ones Shares that are separated and disposed of as filter dust.
- the method according to the invention now has the advantage that such dusts by themselves or in combination with the comminuted reaction material to be subjected to the digestion can. It is a particular advantage of the invention that it is also suitable for processing such dusts, which contain flame retardants and / or metals as they do especially when shredding in electrical engineering usual composite materials.
- the crushed Laminate was made with the same weight percentage Added alkali hydroxide and in a tempered metal bath implemented. According to Example 1 was with NaOH at 340 ° C, according to Example 2 with KOH at 320 ° C and according to Example 3 with a Mixture of equal parts by weight of NaOH and KOH at 300 ° C implemented. The reaction was in less than 5 minutes each finished with gas evolution. The resulting gas could be used as Water to be condensed. After the reaction was over Cooled reaction mixture and washed with cold water, until the wash water was about neutral. After separating the dismantled Polymers and subsequent drying made metal and glass fraction are simply separated from one another.
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
DE-OS 41 31 620). Bei bauelementfreien Leiterplatten handelt es sich daher in der Regel um Produktionsabfälle.
- Beim Standard-Mahlverfahren kann es durch thermische Belastungen zur Bildung von polybromierten aromatischen Dibenzodioxinen (PBDD) und polybromierten Dibenzofuranen (PBDF) aus dem Flammschutzmittel kommen.
- Beim Kryo-Mahlverfahren wird bei so tiefen Temperaturen gemahlen, daß das Material versprödet. Dabei wird die Bildung thermischer Abbauprodukte vermieden. Diesen Vorteilen stehen jedoch höhere Energiekosten gegenüber, wobei unerheblich ist, ob die Kühlung direkt, z.B. mit flüssigem Stickstoff, oder indirekt über eine Kältekaskade erfolgt.
- Durch teilweise Kühlung wird der Bereich zwischen Normal- und Kryoverfahren abgedeckt.
- Beim Ultraschall-Verfahren wird das Verbundmaterial mittels Ultraschall zertrümmert, wobei materialspezifische Korngrößenverteilungen auftreten. Dieses Verfahren ist sehr teuer, erlaubt jedoch die Isolierung von bis zu vier verschiedenen Metallfraktionen.
- Nach einer anderen Arbeitsweise, dem Naßzerkleinerungs-Verfahren werden feuchte Leiterplatten gemahlen, wodurch sowohl das Mahlgut vor thermischer Belastung geschützt als auch eine Staubentwicklung vermieden wird. Die anschlies-sende Wertstofftrennung erfolgt gewöhnlich über ein flotationsähnliches Verfahren mit anschließender Trocknung.
- Liegt der Edelmetallgehalt über 0,02 %, so lohnt sich die Aufarbeitung für Edelmetallscheideanstalten. Hierbei werden die Edelmetalle entweder mit einer schwach alkalischen Cyanidlösung ausgelaugt und anschließend reduktiv zurückgewonnen oder thermometallurgisch bei 1000-1200 °C im Schachtofen mit Blei extrahiert. Im Anschluß hieran wird das Blei im Treibofen als Bleiglätte wieder entfernt. Die Aufarbeitung erfolgt in beiden Fällen elektrolytisch, und die edelmetallfreien Rückstände werden an Kupferhütten weitergegeben.
- Liegt der Edelmetallgehalt unter 0,02 Gew.%, so wird das Material in die zweite Stufe des Kupferherstellungsprozesses eingeschleust. Hierbei wird das Rohkupfer in einem Drehrohrofen (Peirce Smith Konverter) unter Silikatzusatz vom Eisen befreit, wobei sich eine Eisensilikatschlacke bildet, welche andere Schwermetalle dauerhaft einschließt und als Baumaterial Verwendung findet (Kopfsteinpflaster) . Das Kupfer wird anschließend elektrolyrisch gereinigt, wobei sich die Edelmetalle im Anodenschlamm wiederfinden.
Claims (10)
- Verfahren zum stofflichen Aufschluß von Kunstharz enthaltenden Verbundwerkstoffen,
dadurch gekennzechnet, daß
die hochmolekulare Struktur des Kunstharzanteils durch chemische Reaktion mit Hydroxiden der Alkalimetalle bei Temperaturen von 250° bis 370° C, zweckmäßig bei Temperaturen zwischen 260° und 370° C, bevorzugt im Bereich zwischen 280° und 370° C, besonders bevorzugt im Bereich zwischen 300° und 350° C abgebaut wird. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, daß
als Hydroxid der Alkalimetalle NaOH oder KOH, bevorzugt aber Gemische aus NaOH und KOH verwendet werden. - Verfahren nach Anspruch 1 oder 2,
dadurch gekennzeichnet, daß
Reaktionshilfsmittel verwendet werden, welche die Benetzbarkeit des Verbundwerkstoffes durch Alkalimetallhydroxide verbessern, den Schmelzpunkt der Alkalimetallhydroxide senken oder unter den Reaktionsbedingungen ein Lösevermögen für das Kunstharz oder dessen Abbauprodukte besitzen. - Verfahren nach einem oder mehreren der Ansprüche 1 - 3,
dadurch gekennzeichnet, daß
es sich bei den Kunstharzen um vernetzte oder unvernetzte Polymere handelt, welche in der Hauptkette chemisch spaltbare funktionelle Gruppen enthalten wie Polyester, Polyamide, Polyether, Polyurethane, vorzugsweise Polyimide, Polyaramide und Polycyanatester und insbesondere Epoxidharze. - Verfahren nach einem oder mehreren der Ansprüche 1 - 4,
dadurch gekennzeichnet, daß
der Verbundwerkstoff metallische Komponenten enthält. - Verfahren nach einem oder mehreren der Ansprüche 1 - 5,
dadurch gekennzeichnet, daß
das Ausgangsmaterial ein in der Elektrotechnik üblicher Verbundwerkstoff ist und insbesondere aus Leiterplatten, Bauelementen oder Produktionsabfall bei der Herstellung von Leiterplatten oder Bauelementen besteht, wobei vorzugsweise die Leiterplatten und die darauf befindlichen Bauelemente vor der Reaktion getrennt werden. - Verfahren nach Anspruch 6,
dadurch gekennzeichnet, daß
das Ausgangsmaterial aus bei der Zerkleinerung anfallenden Stäuben besteht oder solche enthält, insbesondere solche, die Flammschutzmittel und/oder Metalle enthalten. - Verfahren nach einem oder mehreren der Ansprüche 1 - 7,
dadurch gekennzeichnet, daß
die Reaktion diskontinuierlich in einem Rührkessel, bevorzugt in einer Rührkesselkaskade, oder kontinuierlich in einem Extruder oder einer Extruderkaskade, bevorzugt in einem Zweischneckenextruder durchgeführt wird. - Verfahren nach einem oder mehreren der Ansprüche 1 - 8,
dadurch gekennzeichnet, daß
die Menge des Alkalimetallhydroxids mindestens 50 Gew.%, bezogen auf den Kunstharzanteil beträgt. - Weitere Ausgestaltung des Verfahrens nach einem oder mehreren der Ansprüche 1 - 9,
dadurch gekennzeichnet, daß
die Bestandteile der Verbundwerkstoffe nach der Reaktion voneinander getrennt und gegebenenfalls teilweise oder ganz aufgearbeitet werden.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP1998/004467 WO2000003764A1 (de) | 1998-07-17 | 1998-07-17 | Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1077747A1 EP1077747A1 (de) | 2001-02-28 |
EP1077747B1 true EP1077747B1 (de) | 2001-12-12 |
Family
ID=8167006
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98941357A Expired - Lifetime EP1077747B1 (de) | 1998-07-17 | 1998-07-17 | Verfahren zum stofflichen aufschluss von kunstharz enthaltenden verbundwerkstoffen |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1077747B1 (de) |
JP (1) | JP2002520196A (de) |
AT (1) | ATE210482T1 (de) |
AU (1) | AU8976798A (de) |
DE (1) | DE59802480D1 (de) |
WO (1) | WO2000003764A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2849854B1 (fr) * | 2003-01-09 | 2006-12-15 | Electricite De France | Procede de valorisation de dechets de materiaux a base de resine epoxyde. |
DE102010050153B4 (de) * | 2010-11-02 | 2012-10-25 | Adam Handerek | Reaktor und Verfahren zum zumindest teilweisen Zersetzen und/oder Reinigen von Kunststoffmaterial |
DE102010050152B4 (de) * | 2010-11-02 | 2016-02-11 | Adam Handerek | Reaktor und Verfahren zum zumindest teilweisen Zersetzen, insbesondere Depolymerisieren, und/oder Reinigen von Kunststoffmaterial |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2509634B1 (fr) * | 1981-07-20 | 1986-10-10 | Cirta Ct Int Rech Tech Appliqu | Procede de destruction de produits a base de matieres organiques contenant du soufre et/ou des halogenes et applications de celui-ci |
DE4001897C2 (de) * | 1990-01-21 | 1999-11-25 | Atp Arbeit Tech Photosynthese | Verfahren zur umweltfreundlichen Auflösung von Platinen |
EP0554761A1 (de) * | 1992-02-04 | 1993-08-11 | MENGES, Georg, Prof. Dr.-Ing. | Verfahren zum Recycling von Polymerwerkstoffen |
CA2140822A1 (en) * | 1994-07-21 | 1996-01-22 | Gary D. Schnittgrund | Molten salt destruction of composite materials |
-
1998
- 1998-07-17 AT AT98941357T patent/ATE210482T1/de not_active IP Right Cessation
- 1998-07-17 EP EP98941357A patent/EP1077747B1/de not_active Expired - Lifetime
- 1998-07-17 WO PCT/EP1998/004467 patent/WO2000003764A1/de active IP Right Grant
- 1998-07-17 DE DE59802480T patent/DE59802480D1/de not_active Expired - Fee Related
- 1998-07-17 AU AU89767/98A patent/AU8976798A/en not_active Abandoned
- 1998-07-17 JP JP2000559898A patent/JP2002520196A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
ATE210482T1 (de) | 2001-12-15 |
DE59802480D1 (de) | 2002-01-24 |
WO2000003764A1 (de) | 2000-01-27 |
AU8976798A (en) | 2000-02-07 |
JP2002520196A (ja) | 2002-07-09 |
EP1077747A1 (de) | 2001-02-28 |
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