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United States Patent (19) 11 Patent Number: 5,731,483 Stabel Et Al

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United States Patent (19) 11 Patent Number: 5,731,483 Stabel Et Al US005731483A United States Patent (19) 11 Patent Number: 5,731,483 Stabel et al. 45 Date of Patent: Mar. 24, 1998 54 RECYCLING OF PLASTICS IN A STEAM 52 U.S. Cl. .......................... 585/241; 585/648; 208/130 CRACKER 58 Field of Search ..................................... 585/241, 648; 208/130 75) Inventors: Uwe Stabel, Edingen-Neckarhausen; Helmut Woerz, Mannheim; Ruediger 56) References Cited Kotkamp, Limburgerhof; Andreas U.S. PATENT DOCUMENTS Fried, Bobenheim-Roxheim, all of Germany 5,364.995 11/1994 Kirkwood et al. ...................... 585,241 73) Assignee: BASFAktiengesellschaft, FOREIGN PATENT DOCUMENTS Ludwigshafen, Germany 2108.968 9/1983 Canada. 2094.456 10/1993 Canada. 21) Appl. No.: 553,658 502 618 9/1992 European Pat. Off. 567 292 10/1993 European Pat. Off. 22 PCT Filed: May 20, 1994 WO93/1812 9/1993 WIPO. (86 PCT No.: PCT/EP94/01647 Primary Examiner-Glenn Caldarola S371 Date: Nov. 17, 1995 Assistant Examiner-Bekir L. Yildirim Attorney, Agent, or Firm-Keil & Weinkauf S 102(e) Date: Nov. 17, 1995 57 ABSTRACT 87 PCT Pub. No.: WO95/03375 A process for recycling plastic waste in a steam cracker, PCT Pub. Date: Feb. 2, 1995 wherein a melt obtained from plastic waste is converted into 30 Foreign Application Priority Data products at from 400° 550° C., and a distillate fraction is separated off from the products at from 180° to 280° C. and Jul. 20, 1993 DEl Germany .......................... 43 24, 112.3 is fed as feed material to a steam cracker, Jan. 10, 1994 DEl Germany .......................... 4400 366.8 (51 int. Cl. .................. C07C 1/00; CO7C 4/22 9 Claims, 2 Drawing Sheets - N 5 AAA' U.S. Patent Mar. 24, 1998 Sheet 1 of 2 5,731,483 FIG. U.S. Patent Mar. 24, 1998 Sheet 2 of 2 5,731,483 FIG.2 5,731,483 1. 2 RECYCLING OF PLASTICS IN A STEAM steam cracking process into olefins. Plastic waste can be CRACKER converted by the combination of fluidized bed apparatus and known steam cracking process into these olefins. An evident disadvantage of this process is that for the This application is a 371 of PCT/EP94/01647 filed on steam cracking process it is necessary to add naphtha to the Sep. 20, 1994, feed materials obtained, ie. it is not possible to convert the The present invention relates to a process for recycling plastic waste into cracked products such as ethylene, pro plastics in a steam cracker. pylene etc. without adding traditional feed materials. It is possible by means of the process according to the Furthermore, the handling of the solids in the fluidized bed invention to convert plastics, for example pure polymeric always proves to be a disadvantage. It is also problematic to plastic waste, mixed plastic waste or sheet waste, including 10 scale up a process of this type to large-scale industrial possible soiling, sticky label materials, fillers, residual con operation. tents etc., into high-value feed materials for the known Patent Application WO 93/18112 published on Sep. 16, steam cracking process. These feed materials are in turn 1993, describes a process for the preparation of olefins from converted in the known steam cracking process, into cracked plastic waste by establishing a desired viscosity by thermal products such as ethylene, propylene, C mixtures, pyrolysis 15 pretreatment of the plastic waste at from 380° to 680° C. and gasoline etc., and these are produced in yields which are subsequent thermal treatment of the product at from 700° to almost the same as or even higher than when the steam 1100° C. The process does not involve any distillative cracker is operated with the traditional feed materials such separation of the product. The process cannot produce a as naphtha, liquid petroleum gas (LPG) and gas oil. It is product which can be evaporated without leaving a residue. therefore possible by means of the process according to the It is an object of the present invention to provide a invention to replace in the steam cracking process the process which can be used industrially on a large scale and abovementioned traditional feed materials by feed materials with which plastic waste is converted into high-value feed obtained from plastic waste, it being unnecessary to admix materials for a steam cracker which may be available, so that naphtha, LPG or gas oil with the feed materials obtained these feed materials can be converted, without the addition from plastic waste. of, for example, naphtha. LPG and gas oil, in the steam The process according to the invention therefore makes cracking process into cracked products such as ethylene. a considerable contribution to the economic recycling of propylene, C mixtures and pyrolysis gasoline in high yield. plastics. We have found that this object is achieved if a melt The known steam cracking process is usually understood obtained from plastic waste is converted into products at as evaporation and heating of the feed materials at up to 650 30 from 400° to 550° C., a distillate fraction being separated off C. with subsequent treatment at in general from 700° to from the products at from 180° to 280° C., preferably from 1100° C., for example from 780° to 860° C., in the course 220° to 260° C., in particular from 230 to 250° C. and said of, usually, from 0.02 to 10, for example from 0.1 to 2. fraction is fed as a feed material to a steam cracker. seconds in the presence of steam. In an advantageous embodiment of the process, It is known that the plastic wastes obtained as garbage 35 consist of about 70% by weight of polyolefins, such as the plastic waste is melted, in general at from 280° to 380 polyethylene and polypropylene, about 15% by weight of C. styrene polymers, about 10% by weight of PVC and minor the melt is fed to a reactor where the polymers are amounts of about 5% by weight of other plastics, such as converted at from 400° to 550° C. into products which polyurethane. polyester and polyamide. These plastic wastes can be evaporated and cracked in a conventional way in are generally soiled, ie. they also contain sticky label the steam cracker, materials, fillers, residual contents, etc. The plastic wastes a distillate fraction is separated by distillation, at from are usually sorted and are therefore obtained in various 200° to 280° C., preferably from 220° to 260° C., in fractions known per se. The bottle or blow molded fraction particular from 230° to 250° C., from the products. composed of bottles, containers, etc., which essentially the other products are returned to the reactor, with the consist of polyolefins, such as polyethylene or exception of residues and solids and any inorganic polypropylene, a mixed plastic fraction, consisting essen acids and possibly aromatics, and tially of polyethelene (PE), polypropylene (PP), styrene the distillate fraction separated off is introduced, if nec polymer, such as polystyrene (PS), and polyvinyl chloride essary after further separation, as a feed material into (PVC); a sheet fraction consisting essentially of PE and PP, 50 the steam cracker. etc. and a light fraction consisting essentially of PE, PP and In some cases, it has proven advantageous to separate of PS. in each case possibly with adherent soiling, sticky label aromatics, such as ethyl benzene and styrene, from the materials, fillers, residual contents, etc., may be mentioned. distillate fraction before it is used in the steam cracker. This Essentially, the fractions contain plastics other than the can be done by known methods, such as extraction or stated ones only in minor amounts, for example less than 55 distillation. The aromatics can then be used separately, for 10% by weight, in many cases less than 5% by weight, in example added directly to the aromatics fraction (pyrolysis particular less than 2% by weight. gasoline) of the products of the steam cracker. A number of processes have been described in the patent The process is advantageously used for blow molded literature for converting plastic waste into products for fractions and sheet fractions. Melting of the plastic waste is further processing, for example catalytic or thermal preferably carried out at from 280° to 350° C., in some cases processes, hydrocracking processes, extrusion processes etc. at from 300° to 350° C., in particular from 290° to 320°, and For example, Europ. Patent Application 0502618 describes the conversion in the reactor at from 400 to 450° C. a process in which plastic waste, specifically polyolefins, is The distillate fraction or fractions is or are preferably converted into lower hydrocarbons. This entails the plastic separated off by a process in which waste being reacted in a fluidized bed apparatus at about 65 the products are separated by means of a 1st column 300-630° C. The resulting lower hydrocarbons, such as which is directly downstream of the tubular furnace paraffins or waxes, can be converted by means of the known into 5,731,483 3 4 a bottom product resulting at from 300 to 420°C., in a liquid fraction which is used as feed material for the particular from 330° to 380°C., which, after removal steam cracker, and into of the residues and solids, is returned to the reactor, an aromatic fraction. and into The heat of condensation of the top product from the first a top product resulting at from 200 to 280°, preferably 5 column can be used for generating steam at various pres from 220° to 260°C., in particular from 230° to 250° SeS C., which, after partial condensation, is fed into a The plastic waste can be melted in suitable apparatuses 2nd column at 70° to 150° C.
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