EP0236701A1 - Process for the recovery of carbon-containing wastes - Google Patents
Process for the recovery of carbon-containing wastes Download PDFInfo
- Publication number
- EP0236701A1 EP0236701A1 EP87100875A EP87100875A EP0236701A1 EP 0236701 A1 EP0236701 A1 EP 0236701A1 EP 87100875 A EP87100875 A EP 87100875A EP 87100875 A EP87100875 A EP 87100875A EP 0236701 A1 EP0236701 A1 EP 0236701A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- waste
- bar
- hydrogen
- hours
- products
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000011084 recovery Methods 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 239000003921 oil Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 238000011282 treatment Methods 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000003245 coal Substances 0.000 claims description 15
- 239000010779 crude oil Substances 0.000 claims description 14
- 235000013311 vegetables Nutrition 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- -1 aluminum silicates Chemical class 0.000 claims description 12
- 239000010426 asphalt Substances 0.000 claims description 12
- 239000002028 Biomass Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000010815 organic waste Substances 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002956 ash Substances 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000010791 domestic waste Substances 0.000 claims description 6
- 239000003027 oil sand Substances 0.000 claims description 6
- 239000003586 protic polar solvent Substances 0.000 claims description 6
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000002864 coal component Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000004058 oil shale Substances 0.000 claims description 5
- 239000003415 peat Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 239000003077 lignite Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000007669 thermal treatment Methods 0.000 claims 1
- 238000009997 thermal pre-treatment Methods 0.000 abstract description 7
- 238000012958 reprocessing Methods 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000887 hydrating effect Effects 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000003079 shale oil Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 239000010784 textile waste Substances 0.000 description 3
- 239000010920 waste tyre Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000002916 wood waste Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011324 bead Substances 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/18—Treating trash or garbage
Definitions
- the invention relates to an improved process for reprocessing carbon-containing wastes by thermal pretreatment thereof in the presence or absence of hydrogen and subsequent hydrogenation of the pretreated material at elevated temperature and at least 200 bar hydrogen pressure.
- Waste has been used in landfills for decades, e.g. stored in abandoned gravel pits, mine pits and elsewhere. For a long time, the chemical structure of the waste and its long-term effects on soil and groundwater have not been taken into account. More recently, certain waste has been stored in so-called special landfills. Here, efforts are made to seal the landfill from groundwater and soil.
- Pyrolysis is now also being operated on a technical scale (see, for example, "United Economic Services GmbH", October 4, 1985, p. 9).
- pyrolysis has the disadvantages of the predominant formation of gaseous products and a heavily contaminated coke residue in a relatively large amount and the formation of effluent containing hydrochloric acid from waste containing nitrogen (Rubbish and Waste, 6 (1980) p. 189, right column).
- This invention relates to the hydrating treatment with or without catalyst, synthetic waste materials such as.
- synthetic waste materials such as.
- the hydrogenating treatment at pressures from 30 to 500 bar, preferably from 50 to 450 bar and particularly preferably from 50 to 350 bar is carried out and at temperatures from 200 to 600 ° C, preferably from 200 to 540 ° C and particularly preferably from 300 to 540 ° C and residence times from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 minutes up to 4 hours.
- Rubbing oils can be added to the waste feed products as well as coal, coal components, crude oil, crude oil components and crude oil residues, shale oils and shale oil components, oil sand extracts and their components, bitumen, asphalt, asphaltenes and similar materials.
- the feed product or the feed mixture can also be treated with solvents and then the extract can be used in the hydrogenating treatment.
- the pre-sorting of waste materials is preferably carried out in such a way that carbon-containing organic wastes of synthetic origin, such as plastics and mixtures of plastics, rubber, waste tires, textile wastes or mixtures of these materials, as well as further organic synthetic wastes, are at least roughly separated from vegetable waste and / or biomass be and are subsequently subjected to a hydrotreating or the same organic chemicals, waste from industrial plants, organic synthetic shredder waste from the automobile industry, sewage sludge, waste oils or other industrial organic waste olisten mixed with organic industrial waste synthetic origin, such as paints and F, synthetic origin of the Be subjected to hydrogenation.
- organic wastes of synthetic origin such as plastics and mixtures of plastics, rubber, waste tires, textile wastes or mixtures of these materials, as well as further organic synthetic wastes
- waste materials such as paper, food scraps, agricultural and forestry waste, plant residues and others can be roughly separated or remain to some extent in the synthetic portion.
- Household waste can be processed, for example, in such a way that plastics, rubber, textiles and other synthetic materials are roughly separated and separately subjected to a hydrogenation treatment, or mixed with waste tires and / or industrial chemicals and / or plastic waste and / or waste oils and others are subjected to this hydrating treatment.
- coal components such as, for example, residual oils from coal, coal oils, pyrolysis oils, crude oil, residual oils from crude oil, other crude oil components, oil shale and oil shale components, oil sand extracts, asphalt and Bitumen and similar materials as well as mixtures of these materials.
- the separation of the above-mentioned inorganic materials from the carbon-containing waste can be carried out according to the prior art. These inorganic materials can be stored in landfills unless they are recycled and reprocessed. The crushing and shredding and separation of waste materials can also be carried out according to the prior art. If this is not contradicted by equipment, the process can also be carried out in the presence of inorganic materials.
- Waste components that cannot be converted to hydrocarbons such as sulfur, nitrogen, oxygen and halogens in the form of their compounds, are converted into their gaseous hydrogen compounds, namely H 2 S, NH 3 , HC1, H 2 0 and others. These compounds can be separated by gas washing and further work-up according to the prior art.
- Another advantage of the process is that the formation of hazardous compounds which occur during waste incineration, namely NO, SO or dioxins, is avoided. Furthermore, plastics, such as polyvinyl chloride, which are problematic in combustion, can be obtained without risk the environment.
- the hydrogenation of carbon-containing waste materials can, according to this disclosure, be carried out with very good results in the absence of catalysts. However, improved results, particularly with regard to the selective formation of certain hydrocarbon fractions, can be obtained in the presence of catalysts, e.g. in the presence of metals and their compounds which are catalytically active in hydrogenation reactions, e.g.
- catalysts can consist of a single active component or a mixture of at least 2 of the components mentioned, and wherein these metals or their compounds can be used on catalyst supports, such as on aluminum oxide, silicon oxide, aluminum silicate, zeolites and other supports which are known from the prior art, as well as on mixtures of these supports or also without a support. Certain zeolites and other carriers are also active as catalysts in the disclosed process without doping.
- Suitable catalysts are so-called Wegwerfkata- ysatoren l as lignite coke, gasification dusts and -slag, ash such as high-temperature Winkler dust and ash, dusts and ashes which are obtained in the hydrogenating coal gasification, is formed in the methane (HKV dust) , also materials containing iron oxides such as red mud, Bayer mass, Lux mass, dusts from the steel industry and others.
- These materials can be used as such as catalysts or doped with metals and / or metal compounds which are active in hydrogenations, in particular with heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd, furthermore alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.
- heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd, furthermore alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.
- the catalysts can optionally be sulfided before or during the process.
- All catalysts can be used as individual components or in a mixture of at least two of the components.
- the hydrating treatment can be carried out within wide limits of temperature and pressure, depending on the waste material used, namely from 200-600 ° C. and 30-500 bar, with residence times of 1 minute to 8 hours.
- the hydrogenation gas can be of different quality, it can contain, for example, certain amounts of CO, CO 2 , H 2 S, methane, ethane, steam and others in addition to hydrogen.
- Suitable hydrogen qualities are, for example, those which are obtained when gasifying carbon-containing materials.
- Such materials can be residues from mineral oil processing or other oils or hydrocarbons from mineral oil origin, or coal such as lignite, but also hard coal, wood, peat or residues from coal processing such as coal hydrogenation.
- Suitable V are ergasungsmaterialien biomass of vegetable and portion vomHausmüll. Of course, pure hydrogen qualities, such as those obtained electrolytically, are also very suitable.
- Household waste can accordingly be processed in such a way that first a separation into a vegetable and a synthetic part takes place and then the vegetable Portion is gasified to provide hydrogen in the H y, third process, while the synthetic portion is treated with hydrogen.
- treatment with suitable solvents is also possible, in particular with hydrogen-transferring solvents, this treatment being carried out before the actual hydrogenation.
- dissolved and undissolved material can be separated from one another and subjected separately to a hydrogenation, or dissolved and undissolved material can be reacted together in a reactor in a hydrogenating manner.
- the solvent can be separated off and recycled by subsequent distillation.
- the undissolved material can be subjected to gasification or coking.
- waste material used can be mixed with coal and coal components, crude oil and crude oil components and other similar materials, as already stated above.
- Suitable hydrogen-transferring solvents are, for example, tetralin, anthracene oil, isopropanol, oils containing cresols, decalin, naphthalene, tetrahydrofuran, dioxane and other hydrocarbons from crude oil and coal or hydrocarbons which originate from the process itself, and also oxygen-containing hydrocarbons and oils.
- water and steam can also be added, the latter also being able to be added to the alternative hydrogenating treatments already explained above.
- the waste material can first of all be separated into a vegetable, bicmass or cellulose fraction and a synthetic fraction, with both fractions being processed separately, and with the vegetable, bicmass or cellulose fraction being split essentially hydrolytically, for example in the presence of bases or acids, this conversion preferably being carried out in the presence of protic solvents, in particular water and alcohols and / or in the presence of carbon monoxide and / or hydrogen and, on the other hand, the essentially synthetic portion of the hydrogenating treatment described above .
- the pretreatment according to the invention can be carried out in the presence of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents and in an inert atmosphere or in solvents which do not act as hydrogen transfer agents.
- the process can also be carried out with or without catalysts.
- the splitting pretreatment is carried out according to the invention in mixing devices in a general sense, in particular in extruders and mixing / kneading devices, since these generally convey into a downstream apparatus without pulsation.
- extruders can be used, for example, with single or multiple screw conveyors or, for example, those as described in DE-OS 30 01 318 or in DE-OS 29 49 537, in the latter the screw conveyor (s) behind the actual conveyor section into one extended reaction space protrudes, so that this additional diam by the screw (s).
- numerous other mixing devices such as kneading disc screw presses, kneaders, hollow screw heat exchangers,
- Screw kneaders, kneading extruders, stirring apparatuses, continuous mixers, kneaders, grinding devices or mills such as bead, hammer or vibrating mills are suitable for the pretreatment according to the invention.
- a feed extruder can optionally be connected downstream, which brings about an increase in pressure up to the pressure of the hydrogenation reactor.
- Apparatus which are very suitable according to the invention are, in particular, apparatus which mix and knead at the same time.
- the desired plasticization, dispersion, homogenization, degassing and degradation reaction which leads to the desired viscosities, takes place in a particularly suitable manner.
- the reaction rate can also be increased by improving the mixing.
- the devices mentioned can optionally also be adapted to certain feedstocks, such as containing gas feeds, feed devices at different points on the pretreatment section, drying, heating and cooling sections, addition devices for liquid feed products and the like. Furthermore, several of the devices mentioned can be connected in series or in parallel so that overall at the input of (the) downstream of the hydrogenation reactor (s) is a feedstock mixture of the desired characteristics is present, in particular with respect to degree of degradation and viscosity by V is-.
- J e are employed by waste products and biomass in front of the aforementioned devices, for example, coarse mills, cutters, separators for inorganic materials Aufschmelzvortechniken, devices for metal deposition and the like., If necessary. Can also be a G efrierzerkleintation be applied.
- products with the desired physical states can already be used in the mixing device used for the pretreatment according to the invention.
- the pretreatment according to the invention is carried out in conjunction with hydrogen, hydrogen-containing gases or hydrogen-transferring solvents, the devices mentioned are preferably selected from the point of view that a sufficient amount of hydrogen required for the reaction reaches the feedstock to be converted.
- stirring devices for example, stirring devices, mixing / kneading devices, extruders or the devices disclosed in DE-OS 30 01 318 and DE-OS 29 43 537 are suitable or other of the devices mentioned can be used, if appropriate with appropriate feeds for hydrogen.
- hydrogen can also be supplied upstream of the mixing device.
- the hydrogenating treatment is carried out in the pretreatment device at a temperature of 75-600 ° C, preferably 75-540 ° C, particularly preferably 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar , particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours, the desired amount of hydrogen being able to be supplied in one or more stages, depending on the mixing device.
- the thermal pretreatment is carried out in the mixing device at 75-600 ° C., preferably from 75-540 ° C., particularly preferably at 120-475 ° C., a pressure of 1-600 bar, preferably of 1-500 bar, particularly preferably of 1-350 bar and a residence time of 1 minute to 6 hours, preferably 1 minute to 4 hours.
- the pretreatment according to the invention in particular in the case of thermal pretreatment, can also be carried out under a pressure lower than 1 bar.
- inert gas can be introduced in one or more stages, depending on the mixing device used.
- Inert gases can be, for example, nitrogen, carbon dioxide, steam, carbon monoxide, methane and other low-boiling hydrocarbons, as well as mixtures of these gases.
- Hydrogen can also be present in small quantities. Small amounts of oxygen or air may also be permitted.
- mixing devices for hydrating or thermal pretreatment can be combined in parallel connection or in series connection.
- the gases mentioned can also be added before the actual pretreatment.
- a hydrogen-transferring solvent or a mixture of such solvents can also be used as such or in combination with additional hydrogen or inert gas.
- the hydrogenating pretreatment is carried out at a temperature of 75-600 ° C, preferably at 75-540 ° C and particularly preferably at 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar and particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours.
- the conversion in the mixing device can also be carried out in the presence of protic solvents, in particular in the presence of water or methanol and / or at least one component from the group: Ethanol, C 3 -C 4 alcohols and higher alcohols.
- Protic solvents depending on the type of waste used, at least partially lead to hydrolysis. If the reaction is carried out in the pretreatment mixing device, temperatures of 75-600 ° C. are used, preferably from 75-540 ° C and particularly preferably from 120-500 ° C , pressures from 1-600 bar, preferably from 1-500 bar, particularly preferably from 1-350 bar and residence times from 1 minute to 6 hours, preferably from 1 Minute to 4 hours.
- the hydrolysis can also be carried out in the presence of hydrogen, hydrogen-containing gases or hydrogen-transferring solvents with or without a catalyst or with or without CO. Typical hydrolysis catalysts, such as acids or bases including organic amines, can be used. The catalysts mentioned on pages 6 and 7 can also be included.
- the pretreatment according to the invention can be carried out in the presence of solvents which do not have a hydrogen transfer effect, such as of aromatics such as benzene, toluene or the xylenes.
- solvents which do not have a hydrogen transfer effect such as of aromatics such as benzene, toluene or the xylenes.
- Non-aromatic solvents can also be used, such as saturated or substantially saturated aliphatic hydrocarbons in boiling ranges between, for example, 30 and more than 500 ° C.
- the high-boiling fractions can, for example, be residual oils, as already mentioned above.
- the hydrogenating cleavage in the pretreatment device can be set to the desired extent, up to a breakdown as described in the hydrogenating treatment of waste according to DE-PS 34 42 506 or in the European subsequent application No. 85 11 4535.9.
- a downstream hydrogenation reactor can be dispensed with.
- the hydrogenating pretreatment can be carried out with or without the catalysts which are disclosed on pages 6 and 7.
- Catalysts can be introduced into the pretreatment device or added before it.
- the waste from organic synthetic materials can be converted into liquid hydrocarbons which boil essentially in the naphtha or gasoline range or middle distillate range. Examples of such waste are disclosed on pages 3 and 4.
- a particular advantage of the method according to the invention results from the fact that the conditions in the pretreatment device can be set so that a product is obtained which can be handled without problems in subsequent steps, for example pumped or conveyed via screw conveyors, the conditions being based on Art of the waste used can be adjusted, which as pointed out above plastic materials, paint residues, paint compositions I ndustriechemikalien such as those that need to be deposited in special dumps according to the prior art, shredded waste from the automobile industry, used lubricating oils, elastomers, fabrics but also in to a certain extent paper, cardboard and other cellulose-containing materials such as wood waste, sawdust or vegetable matter from household waste.
- the pretreated product can also be conveyed directly from the pretreatment device into the hydrogenation reactor, for example by means of an extruder.
- the method according to the invention therefore also allows only a little pre-sorted waste to be implemented. However, for reasons of equipment, it is desirable to separate inorganic materials such as stones, metals, glass and others before the pretreatment, at least rough materials.
- Vegetables can be processed separately, for example by fermentation.
- An important advantage of the present invention results from the fact that the hydrogenating or thermal pretreatment according to the invention, in combination with the subsequent hydrogenation of the pretreated waste, means that even very inhomogeneous waste mixtures can be used as the feed product, these being converted into valuable liquid hydrocarbons in high yields.
- the heteroatoms such as oxygen, sulfur, nitrogen or halogens, which are contained in many waste materials, are converted according to the invention into their hydrogen derivatives, which can be worked up further according to the prior art without any problems.
- halogenated wastes are, for example P olychlorbiphenylene, polyvinyl chloride, fluorine-containing polymers or halogen-containing solvent.
- a particularly advantageous effect of the thermal or hydrating pretreatment is the result that depends As a result of the temperature, dwell time and pressure, halogens are largely eliminated in the pretreatment, essentially as hydrogen halides. For example, about 90% of the halogen is already removed from waste containing polyvinyl chloride at 250 ° C., a residence time of 30 minutes and a hydrogen or nitrogen pressure of 10 bar or less as hydrogen chloride.
- Halogen elimination can also be promoted by increasing the temperature and increasing the residence time. Halogen elimination can also be promoted by catalysts such as those mentioned on pages 6 and 7. Such catalysts which are used according to the prior art for the elimination of hydrogen halide, such as Friedel-Crafts catalysts and / or organic amines and / or other basic compounds, can also be used according to the invention. As a result, hydrogen halides can be split off even under mild conditions.
- materials can also the waste used are added or be added in the preconditioner or the hydrogenation reactor, such as crude oil, R ohölkomponenten and products derived from crude oil, asphalt, bitumen, mineral tars, coal, coal components, products from coal, lignite , Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.
- crude oil, R ohölkomponenten and products derived from crude oil, asphalt, bitumen, mineral tars, coal, coal components, products from coal, lignite , Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.
- a hydrolysis stage can precede the thermal or hydrogenating pretreatment.
- the hydrolysis reaction is preferably carried out in a mixed premix performed as described above, in the presence of protic solvents - medium, especially in the presence of water and / or methanol and / or at least one component from the group:
- Ethanol, C 3 -C 4 alcohols and higher alcohols at a pressure of 1-150 bar, preferably of 1-120 bar and a temperature of 50-300 ° C and preferably 75-250 ° C. Lower pressures are preferred if the gases that are formed during the hydrolysis are to be removed from the hydrolysis device.
- the hydrolysis stage can alternatively be switched between the pretreatment and the actual hydrogenation.
- the hydrolysis conditions are preferably adapted to the temperature and the pressure in the pretreatment stage or hydrogenation stage or both.
- vegetables and biomass can be hydrolytically split and separated from waste of synthetic organic origin.
- the hydrolysis reaction can be accelerated by adding acids or bases in accordance with the prior art.
- the hydrolytic reaction can also be carried out in the presence of hydrogen, hydrogen-containing gases, hydrogen-transferring solvents, catalysts as exemplified on pages 6 and 7 or solvents which are not suitable for mass transfer, or in the presence of inert gases.
- So-called Anreiböle may also or adaptationsvortechnisch according to the invention in the V or be added before this or after this.
- the grinding oils can originate from the process itself or can be of foreign origin.
- metals or metal compounds which are present in the waste can advantageously be worked up, since they occur in residues or ashes in a relatively high concentration after the hydrogenation. These residues or ashes can be worked up, for example, to obtain the pure metals.
- Example 1 was repeated, but under a nitrogen pressure of 10 bar. In the case of the temperature of 300 ° C, an additional nitrogen pressure of 2 bar was used. The results are shown in Table 2.
- a mixture of mineral residual oils and a waste mixture consisting of 10% by weight of old tires, 70% by weight of essentially synthetic-organic waste from a technical waste separation system and 20% by weight of polyvinyl chloride was mixed and kneaded at 350 ° C for 20 minutes and 450 ° C treated with a hydrogen or nitrogen pressure of 200 bar.
- the ratio of waste to oil was 1: 3.
- FeSO 4 treated with NaOH was used as the catalyst.
- Waste which consisted predominantly of organic synthetic material and was obtained from a technical waste sorting plant, with 15% by weight polyvinyl chloride, was treated in a mixer / kneader at 200 bar hydrogen and temperatures of 350 ° C and 470 ° C for 30 minutes each. At the temperature of 350 ° C, an experiment was carried out with and without a catalyst. A nickel / molybdenum catalyst was used as the catalyst. No rubbing oil was used. The viscosities obtained are shown in Table 6.
- Waste which consisted essentially of organic synthetic material from a technical waste separation plant and which contained 5% by weight of perfluorinated polyethylene (Teflon) and 20% by weight of textile waste from 50% wool and 50% polyacrylonitrile was treated as described in Example 6.
- the viscosities obtained are shown in Table 8.
- the results according to the invention are of great importance for waste hydrogenation on an industrial scale, since the downstream hydrogenation reactors and other parts of the plant which are exposed to high pressures can be made from less valuable materials.
- the process according to the invention is therefore of particular importance for waste feed materials which contain chlorinated constituents.
- the examples also show that, under suitable conditions and conditions, increased degradation takes place under nitrogen compared to hydrogen.
- the conditions of the pretreatment can be varied over a wide range of temperature, pressure and residence times, the conditions for the subsequent hydrogenation can also be varied over a wide range, the two treatments complementing one another.
- the pretreatment according to the invention is carried out at a relatively high temperature and residence time or corresponding pressure, in particular at a relatively high hydrogen pressure
- the subsequent hydrogenation can, depending on the product used, be carried out under relatively mild conditions. This applies in particular if the pretreatment has already led to extensive dismantling.
- Both stages therefore complement one another in accordance with the invention and can be adapted excellently to the operational waste material as required.
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Abstract
Die Erfindung betrifft ein verbessertes Verfahren zur Wiederaufarbeitung Kohlenstoff enthaltender Abfälle durch thermische Vorbehandlung derselben in Gegenwart oder Abwesenheit von Wasserstoff und anschließende Hydrierung des vorbehandelten Materials bei erhöhter Temperatur.The invention relates to an improved process for the reprocessing of carbon-containing wastes by thermal pretreatment of the same in the presence or absence of hydrogen and subsequent hydrogenation of the pretreated material at elevated temperature.
Description
Die Erfindung betrifft ein verbessertes Verfahren zur Wiederaufarbeitung Kohlenstoff enthaltender Abfälle durch thermische Vorbehandlung derselben in Gegenwart oder Abwesenheit von Wasserstoff und anschließende Hydrierung des vorbehandelten Materials bei erhöhter Temperatur und wenigstens 200 bar Wasserstoffdruck.The invention relates to an improved process for reprocessing carbon-containing wastes by thermal pretreatment thereof in the presence or absence of hydrogen and subsequent hydrogenation of the pretreated material at elevated temperature and at least 200 bar hydrogen pressure.
Es ist in der Öffentlichkeit allgemein bekannt, daß die sich weltweit ansammelnden Abfälle ein zunehmendes Umweltproblem darstellen.It is well known to the public that waste accumulating worldwide is an increasing environmental problem.
Seit Jahrzehnten wird bis heute Abfall in Deponien, z.B. in verlassenen Kiesgruben, Bergwerksgruben und an anderen Stellen gelagert. Lange Zeit hat man hierbei die chemische Struktur des Abfalls und seine langfristige Einwirkung auf Boden und Grundwasser nicht beachtet. In jüngerer Zeit werden bestimmte Abfälle in sog. Sonderdeponien gelagert. Hierbei bemüht man sich, die Deponie gegenüber Grundwasser und Boden abzudichten.Waste has been used in landfills for decades, e.g. stored in abandoned gravel pits, mine pits and elsewhere. For a long time, the chemical structure of the waste and its long-term effects on soil and groundwater have not been taken into account. More recently, certain waste has been stored in so-called special landfills. Here, efforts are made to seal the landfill from groundwater and soil.
Die Fachwelt hat sich daher seit einiger Zeit intensiv um eine Aufarbeitung bzw. Verarbeitung des Abfalls bemüht, einmal zur Schonung der Umwelt und zum anderen um verwertbare Produkte aus dem Abfall zu gewinnen.For some time now, experts have made intensive efforts to process and process the waste, firstly to protect the environment and secondly to obtain usable products from the waste.
So wird in "The Oil and Gas Journal", Dec. 25, 1978, S. 80, eine Pilotanlage beschrieben, in der durch Pyrolyse Kunststoffe in Gase und Öle umgewandelt werden können.So in "The Oil and Gas Journal", Dec. 25, 1978, p. 80, described a pilot plant in which plastics can be converted into gases and oils by pyrolysis.
In "Hydrocarbon Processing", April 1979, S. 183, wird eine Verbrennungsanlage, insbesondere für spezielle Abfälle beschrieben.In "Hydrocarbon Processing", April 1979, p. 183, an incineration plant is described, in particular for special waste.
Auch der biochemische Abbau von Kunststoffen wurde untersucht (s. z.B. "European Chemical News", Sept. 10, 1979, S. 28). In "Chemical Engineering", 13. August 1979, S. 41, wird ein Verfahren beschrieben, nach dem gefährliche Abfälle in erhärtende Materialien, z.B. Zement eingegossen werden.The biochemical degradation of plastics has also been investigated (see e.g. "European Chemical News", Sept. 10, 1979, p. 28). In Chemical Engineering, August 13, 1979, p. 41, a method is described according to which hazardous wastes are deposited in hardening materials, e.g. Cement to be poured.
Ein Überblick über die wichtigsten Verfahren ist in "Chemical and Engineering News", 01. Okt. 1979, S. 34 dargestellt. Hier wird insbesondere die Vergasung von Biomasse, nämlich Holzabfällen und dergl. zu Kohlenmonoxid und Wasserstoff beschrieben. Auf S. 36, linke Spalte dieser Schrift wird auch ein Versuchsprogramm zur Umsetzung von zerkleinertem Holz in Wasser suspendiert, mit Wasserstoff in Gegenwart von Raney-Nickel, als Katalysator beschrieben.An overview of the most important processes is given in "Chemical and Engineering News", Oct. 01, 1979, p. 34. Here, in particular, the gasification of biomass, namely wood waste and the like to carbon monoxide and hydrogen, is described. On page 36, left column of this document, a test program for converting shredded wood into water is also described, using hydrogen in the presence of Raney nickel as a catalyst.
In Europa Chemie", 25, 1979, S. 417, wird ein Verfahren beschrieben, nach dem unsortierte Kunststoffabfälle plastifiziert und verpresst werden.In Europa Chemie ", 25, 1979, p. 417, a method is described according to which unsorted plastic waste is plasticized and pressed.
Die Wirbelschichtverbrennung von Abfällen wird in "Chemische Industrie", XXXII, April 1980, S. 248, beschrieben. Die Umwandlung von Abfällen und Biomasse durch Erhitzen mit Wasser und Alkalien wird in "Chemistry International", 1980, No. 4, S. 20 beschrieben.The W irbelschichtverbrennung of waste is described in "Chemical Industry", XXXII, May 1980, p 248. The conversion of waste and biomass by heating with water and alkalis is described in "Chemistry International", 1980, no. 4, p. 20.
Zahlreiche andere Publikationen sind darüber hinaus bekannt geworden.Numerous other publications have also become known.
In jüngster Zeit wurde vor allem die Verbrennung in modernsten Anlagen weiter entwickelt und Großanlagen errichtet, die nach diesem Verfahren arbeiten. Obgleich Entstaubung und Rauchgaswäsche in solchen Anlagen integriert sind, entweichen Schadstoffe auch bei sorgfältiger Reinigung, so z.B. Schwermetalle, S02, NOx u.a., in kleinen Anteilen in die Atmosphäre.In recent times, combustion has been further developed in the most modern plants, and large plants have been built that work according to this process. Although dedusting and flue gas scrubbing are integrated in such systems, pollutants escape into the atmosphere in small proportions even with careful cleaning, such as heavy metals, SO 2 , NO x and others.
Auch die Pyrolyse wird inzwischen in technischem Umfang betrieben (s. beispielsweise "Vereinigte Wirtschaftsdienste GmbH", 04. Okt. 1985, S. 9). Die Pyrolyse hat jedoch die Nachteile der überwiegenden Bildung gasförmiger Produkte und eines stark verschmutzten Koksrückstandes in relativ großer Menge und die Bildung Bläusäure enthaltender Abwässer aus Stickstoff enthaltenden Abfällen (Müll und Abfall, 6 (1980) S. 189, rechte Spalte).Pyrolysis is now also being operated on a technical scale (see, for example, "United Economic Services GmbH", October 4, 1985, p. 9). However, pyrolysis has the disadvantages of the predominant formation of gaseous products and a heavily contaminated coke residue in a relatively large amount and the formation of effluent containing hydrochloric acid from waste containing nitrogen (Rubbish and Waste, 6 (1980) p. 189, right column).
Das Problem der Abfall- und Biomasse-Verarbeitung ist gemäß diesem Stand der Technik daher nach wie vor nicht zufriedenstellend gelöst.The problem of waste and biomass processing is therefore still not satisfactorily solved according to this prior art.
Eine überraschende, im Vergleich zum Stand der Technik viel günstigere Lösung dieses Problems, insbesondere im Hinblick auf die hohen Ausbeuten an wertvollen flüssigen Produkten, ist vom gleichen Anmelder in dem Deutschen Patent DE-PS 34 42 506 offenbart sowie in der europäischen Nachanmeldung Nr. 85 11 5435.9.A surprising, much cheaper solution to this problem compared to the prior art, in particular with regard to the high yields of valuable liquid products, is disclosed by the same applicant in German patent DE-PS 34 42 506 and in European subsequent application No. 85 11 5435.9.
Diese Erfindung betrifft die hydrierende Behandlung mit oder ohne Katalysator, von synthetischen Abfallmaterialien wie z. B. Kunststoffen bzw. Kunststoffgemischen, Gummi, Abfallreifen, Textilabfällen, chemischen Industrieabfällen, Abfallölen, Altölen und anderen oder Gemischen dieser Materialien, wobei die hydrierende Behandlung bei Drucken von 30 bis 500 bar, vorzugsweise von 50 bis 450 bar und besonders bevorzugt von 50 bis 350 bar durchgeführt wird sowie bei Temperaturen von 200 bis 600°C, vorzugsweise von 200 bis 540°C und besonders bevorzugt von 300 bis 540°C und Verweilzeiten von 1 Minute bis 8 Stunden, vorzugsweise von 10 Minuten bis 6 Stunden und besonders bevorzugt von 15 Minuten bis 4 Stunden.This invention relates to the hydrating treatment with or without catalyst, synthetic waste materials such as. B. Plastics or plastic mixtures, rubber, waste tires, textile waste, chemical industrial waste, waste oils, waste oils and other or mixtures of these materials, the hydrogenating treatment at pressures from 30 to 500 bar, preferably from 50 to 450 bar and particularly preferably from 50 to 350 bar is carried out and at temperatures from 200 to 600 ° C, preferably from 200 to 540 ° C and particularly preferably from 300 to 540 ° C and residence times from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 minutes up to 4 hours.
Zu den Abfall-Einsatzprodukten können Anreiböle zugefügt werden sowie Kohle, Kohlebestandteile, Rohöl, Rohölbestandteile und Rohölrückstände, Schieferöle und Schieferölbestandteile, Ölsandextrakte und ihre Bestandteile, Bitumen, Asphalt, Asphaltene und ähnliche Materialien.Rubbing oils can be added to the waste feed products as well as coal, coal components, crude oil, crude oil components and crude oil residues, shale oils and shale oil components, oil sand extracts and their components, bitumen, asphalt, asphaltenes and similar materials.
Das Einsatzprodukt bzw. das Einsatzgemisch kann ferner mit Lösungsmitteln behandelt werden und anschließend der Extrakt in die hydrierende Behandlung eingesetzt werden.The feed product or the feed mixture can also be treated with solvents and then the extract can be used in the hydrogenating treatment.
Das Verfahren erlaubt, nach Abtrennung anorganischer Bestandteile wie Glas, Metallen, Steinmaterialen und anderen, die synthetischen Abfallmaterialien ohne weitere Trennung in wertvolle Kohlenwasserstoffe umzuwandeln. Diese sind gasförmige C1-C4-Rohlenwasserstoffe, flüssige Kohlenwasserstoffe im Naphtha-Siedebereich sowie Mitteldestillate und schwere Öle, die als Heizöle bzw. Dieselkraftstoff eingesetzt werden können. Die Vorsortierung von Abfallmaterialien erfolgt bevorzugt in der Weise, daß Kohlenstoff enthaltende organische Abfälle synthetischen Ursprungs wie z.B. Kunststoffe und Gemische von Kunststoffen, Gummi, Abfallreifen, Textilabfälle bzw. Gemische dieser Materialien sowie weitere organische synthetische Abfälle wenigstens grob von vegetabilischem Abfall und/ oder Biomasse abgetrennt werden und anschließend einer hydrierenden Behandlung unterworfen werden oder dieselben im Gemisch mit organischen Industrieabfällen synthetischen Ursprungs wie z.B. Lack- und Farbresten, organischen Chemikalien, Abfällen aus Industrieanlagen, organischen synthetischen Shredderabfällen aus der Autoindustrie, Klärschlamm, Altölen oder anderen industriellen organischen Abfällen synthetischen Ursprungs der Hydrierung unterworfen werden.After separating inorganic components such as glass, metals, stone materials and others, the process allows the synthetic waste materials to be converted into valuable hydrocarbons without further separation. These are gaseous C 1 -C 4 hydrocarbons, liquid hydrocarbons in the naphtha boiling range as well as middle distillates and heavy oils, which can be used as heating oils or diesel fuel. The pre-sorting of waste materials is preferably carried out in such a way that carbon-containing organic wastes of synthetic origin, such as plastics and mixtures of plastics, rubber, waste tires, textile wastes or mixtures of these materials, as well as further organic synthetic wastes, are at least roughly separated from vegetable waste and / or biomass be and are subsequently subjected to a hydrotreating or the same organic chemicals, waste from industrial plants, organic synthetic shredder waste from the automobile industry, sewage sludge, waste oils or other industrial organic waste arbresten mixed with organic industrial waste synthetic origin, such as paints and F, synthetic origin of the Be subjected to hydrogenation.
Andere Abfallmaterialien wie Papier, Lebensmittelreste, landwirtschaftliche und forstwirtschaftliche Abfälle, Pflanzenrückstände und andere können grob abgetrennt werden oder verbleiben in dem synthetischen Anteil in gewissem Umfang.Other waste materials such as paper, food scraps, agricultural and forestry waste, plant residues and others can be roughly separated or remain to some extent in the synthetic portion.
Hausmüll kann beispielsweise in der Weise aufgearbeitet werden, daß Kunststoffe, Gummi, Textilien und andere synthetische Materialien grob abgetrennt werden und getrennt einer hydrierenden Behandlung unterworfen werden, oder gemischt mit Abfallreifen und/oder Industriechemikalien und/oder Plastikabfällen und/oder Altölen und anderen dieser hydrierenden Behandlung unterworfen werden.Household waste can be processed, for example, in such a way that plastics, rubber, textiles and other synthetic materials are roughly separated and separately subjected to a hydrogenation treatment, or mixed with waste tires and / or industrial chemicals and / or plastic waste and / or waste oils and others are subjected to this hydrating treatment.
Das Verfahren ist auch sehr gut geeignet für die hydrierende Behandlung der genannten Abfälle bzw. Abfallgemische in Kombination mit Kohle, Kohlekomponenten wie beispielsweise Rückstandsölen aus Kohle, Kohleölen, Pyrolyseölen, Rohöl, Rückstandsölen aus Rohöl, anderen Rohölkomponenten, Ölschiefer und Ölschieferkomponenten, Ölsandextrakten, Asphalt und Bitumen und ähnlichen Materialien sowie mit Gemischen der genannten Materialien.The process is also very well suited for the hydrogenating treatment of the waste or waste mixtures mentioned in combination with coal, coal components such as, for example, residual oils from coal, coal oils, pyrolysis oils, crude oil, residual oils from crude oil, other crude oil components, oil shale and oil shale components, oil sand extracts, asphalt and Bitumen and similar materials as well as mixtures of these materials.
Die Abtrennung der oben genannten anorganischen Materialien vom Kohlenstoff enthaltenden Abfall kann gemäß dem Stand der Technik durchgeführt werden. Diese anorganischen Materialien können in Deponien gelagert werden, sofern sie nicht recycled und wiederaufarbeitet werden. Die Zerkleinerung und das Shredden und Abtrennen von Abfallmaterialien kann ebenfalls gemäß dem Stand der Technik durchgeführt werden. Sofern apparative Gründe dem nicht entgegen stehen, kann das Verfahren auch in Gegenwart anorganischer Materialien durchgeführt werden.The separation of the above-mentioned inorganic materials from the carbon-containing waste can be carried out according to the prior art. These inorganic materials can be stored in landfills unless they are recycled and reprocessed. The crushing and shredding and separation of waste materials can also be carried out according to the prior art. If this is not contradicted by equipment, the process can also be carried out in the presence of inorganic materials.
Abfallkomponenten, die nicht in Kohlenwasserstoff umgewandelt werden können, wie z.B. Schwefel, Stickstoff, Sauerstoff und Halogene in Form ihrer Verbindungen, werden in ihre gasförmigen Wasserstoffverbindungen umgewandelt, nämlich H2S, NH3, HC1, H20 und andere. Diese Verbindungen können durch Gaswäsche und weitere Aufarbeitung gemäß dem Stand der Technik getrennt werden.Waste components that cannot be converted to hydrocarbons, such as sulfur, nitrogen, oxygen and halogens in the form of their compounds, are converted into their gaseous hydrogen compounds, namely H 2 S, NH 3 , HC1, H 2 0 and others. These compounds can be separated by gas washing and further work-up according to the prior art.
Ein weiterer Vorzug des Verfahrens ist, daß die Bildung gefährlicher Verbindungen, die bei der Abfallverbrennung auftreten, nämlich NO , SO oder Dioxine, vermieden wird. Weiter- hin können Kunststoffe, wie beispielsweise Polyvinylchlorid, die in der Verbrennung problematisch sind, ohne Risiko bezüglich der Umwelt aufgearbeitet werden.Another advantage of the process is that the formation of hazardous compounds which occur during waste incineration, namely NO, SO or dioxins, is avoided. Furthermore, plastics, such as polyvinyl chloride, which are problematic in combustion, can be obtained without risk the environment.
Die Hydrierung Kohlenstoff enthaltender Abfallmaterialien kann, gemäß dieser Offenbarung mit sehr guten Ergebnissen in Abwesenheit von Katalysatoren durchgeführt werden. Verbesserte Ergebnisse, insbesondere bezüglich der selektiven Bildung bestimmter Kohlenwasserstoff-Fraktionen können jedoch in Gegenwart von Katalysatoren erhalten werden, wie z.B. in Gegenwart von Metallen und deren Verbindungen, die in Hydrierreaktionen katalytisch aktiv sind, wie z.B. Fe, Cr, Zn, Mo, W, Mn, Ni, Pd, Co, Pt, weiterhin Alkali und Erdalkalien wie Li, Na, K, Rb, Be, Mg, Ca, Sr oder Ba und anderen Metallen und/oder ihren Verbindungen, wobei diese Katalysatoren aus einer einzelnen aktiven Komponente oder einem Gemisch von wenigstens 2 der genannten Komponenten bestehen können, und wobei diese Metalle bzw. ihre Verbindungen auf Katalysatorträgern angewandt werden können, wie z.B. auf Aluminiumoxid, Siliziumoxid, Aluminiumsilikat, Zeolithen und anderen Trägern, die gemäß dem Stand der Technik bekannt sind, ebenso wie auf Gemischen dieser Träger oder auch ohne Träger. Bestimmte Zeolithe und andere Träger sind auch ohne Dotierung im offenbarten Verfahren als Katalysator aktiv.The hydrogenation of carbon-containing waste materials can, according to this disclosure, be carried out with very good results in the absence of catalysts. However, improved results, particularly with regard to the selective formation of certain hydrocarbon fractions, can be obtained in the presence of catalysts, e.g. in the presence of metals and their compounds which are catalytically active in hydrogenation reactions, e.g. Fe, Cr, Zn, Mo, W, Mn, Ni, Pd, Co, Pt, furthermore alkali and alkaline earths such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and other metals and / or their compounds , wherein these catalysts can consist of a single active component or a mixture of at least 2 of the components mentioned, and wherein these metals or their compounds can be used on catalyst supports, such as on aluminum oxide, silicon oxide, aluminum silicate, zeolites and other supports which are known from the prior art, as well as on mixtures of these supports or also without a support. Certain zeolites and other carriers are also active as catalysts in the disclosed process without doping.
Andere geeignete Katalysatoren sind sogenannte Wegwerfkata- lysatoren wie Herdofenkoks, Vergasungsstäube und -aschen wie beispielsweise Hochtemperatur-Winkler-Staub und -Asche, Stäube und Aschen die bei der hydrierenden Vergasung von Kohle erhalten werden, bei der Methan gebildet wird (HKV-Staub), weiterhin Materialien, die Eisenoxide enthalten wie beispielsweise Rotschlamm, Bayer-Masse, Lux-Masse, Stäube aus der Stahlindustrie und andere. Diese Materialien können als solche als Katalysatoren eingesetzt werden oder dotiert mit Metallen und/oder Metallverbindungen, die bei Hydrierungen aktiv sind, insbesondere mit Schwermetallen und/oder ihren Verbindungen wie Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt, Pd, weiterhin Alkali und Erdalkalimetallen bzw. deren Verbindungen wie Li, Na, K, Rb, Be, Mg, Ca, Sr oder Ba sowie Gemischen dieser Metalle und/oder deren Verbindungen.Other suitable catalysts are so-called Wegwerfkata- ysatoren l as lignite coke, gasification dusts and -slag, ash such as high-temperature Winkler dust and ash, dusts and ashes which are obtained in the hydrogenating coal gasification, is formed in the methane (HKV dust) , also materials containing iron oxides such as red mud, Bayer mass, Lux mass, dusts from the steel industry and others. These materials can be used as such as catalysts or doped with metals and / or metal compounds which are active in hydrogenations, in particular with heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd, furthermore alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.
Die Katalysatoren können ggfs. vor oder während des Verfahrens sulfidiert werden.The catalysts can optionally be sulfided before or during the process.
Alle Katalysatoren können als Einzelkomponenten oder im Gemisch von wenigstens zwei der Komponenten eingesetzt werden.All catalysts can be used as individual components or in a mixture of at least two of the components.
Die hydrierende Behandlung kann in weiten Grenzen von Temperatur und Druck durchgeführt werden in Abhängigkeit von dem eingesetzten Abfallmaterial, nämlich von 200-600°C und 30-500 bar, bei Verweilzeiten von 1 Minute bis 8 Stunden.The hydrating treatment can be carried out within wide limits of temperature and pressure, depending on the waste material used, namely from 200-600 ° C. and 30-500 bar, with residence times of 1 minute to 8 hours.
Das Hydriergas kann von verschiedener Qualität sein, es kann beispielsweise außer Wasserstoff gewisse Mengen an CO, C02, H2S, Methan, Ethan, Dampf und anderen enthalten.The hydrogenation gas can be of different quality, it can contain, for example, certain amounts of CO, CO 2 , H 2 S, methane, ethane, steam and others in addition to hydrogen.
Geeignete Wasserstoffqualitäten sind beispielsweise solche, die bei Vergasungen von Kohlenstoff enthaltenden Materialien erhalten werden.Suitable hydrogen qualities are, for example, those which are obtained when gasifying carbon-containing materials.
Solche Materialien können Rückstände aus der Mineralölverarbeitung sein oder andere Öle oder Kohlenwasserstoffe von Mineralölursprung, oder Kohle wie beispielsweise Braunkohle, aber auch Steinkohle, Holz, Torf oder Rückstände aus der Kohleverarbeitung wie beispielsweise der Kohlehydrierung. Geeignete Vergasungsmaterialien sind auch Biomasse und der vegetabilische Anteil vomHausmüll. Selbstverständlich sind reine Wasserstoffqualitäten, wie sie beispielsweise elektolytisch gewonnen werden, ebenfalls sehr gut geeignet.Such materials can be residues from mineral oil processing or other oils or hydrocarbons from mineral oil origin, or coal such as lignite, but also hard coal, wood, peat or residues from coal processing such as coal hydrogenation. Suitable V are ergasungsmaterialien biomass of vegetable and portion vomHausmüll. Of course, pure hydrogen qualities, such as those obtained electrolytically, are also very suitable.
Hausmüll kann demgemäß in der Weise aufgearbeitet werden, daß zunächst eine Trennung in einen vegetabilischen und einen synthetischen Anteil erfolgt und anschließend der vegetabilische Anteil vergast wird zur Bereitstellung von Wasserstoff im Hy-, drierverfahren, während der synthetische Anteil mit Wasserstoff behandelt wird.Household waste can accordingly be processed in such a way that first a separation into a vegetable and a synthetic part takes place and then the vegetable Portion is gasified to provide hydrogen in the H y, third process, while the synthetic portion is treated with hydrogen.
Gemäß diesem Verfahren ist auch eine Behandlung mit geeigneten Lösungsmitteln möglich, insbesondere mit Wasserstoff übertragenden Lösungsmitteln, wobei diese Behandlung vor der eigentlichen Hydrierung vorgenommen wird. Anschließend kann gelöstes und ungelöstes Material von einander getrennt werden und getrennt einer Hydrierung unterworfen werden oder gelöstes und ungelöstes können gemeinsam in einem Reaktor hydrierend umgesetzt werden. Durch nachfolgende Destillation kann das Lösungsmittel abgetrennt und rückgeführt werden. Alternativ kann das nichtgelöste Material einer Vergasung oder Verkokung unterworfen werden.According to this method, treatment with suitable solvents is also possible, in particular with hydrogen-transferring solvents, this treatment being carried out before the actual hydrogenation. Subsequently, dissolved and undissolved material can be separated from one another and subjected separately to a hydrogenation, or dissolved and undissolved material can be reacted together in a reactor in a hydrogenating manner. The solvent can be separated off and recycled by subsequent distillation. Alternatively, the undissolved material can be subjected to gasification or coking.
Auch bei dieser Variante kann das eingesetzte Abfallmaterial mit Kohle und Kohlekomponenten, Rohöl und Rohölkomponenten und anderen, ähnlichen Materialien gemischt werden, wie oben bereits ausgeführt.In this variant too, the waste material used can be mixed with coal and coal components, crude oil and crude oil components and other similar materials, as already stated above.
Geeignete Wasserstoff übertragende Lösungsmittel sind beispielsweise Tetralin, Anthrazenöl, Isopropanol, Kresole enthaltende Öle, Dekalin, Naphthalin, Tetrahydrofuran, Dioxan und andere Kohlenwasserstoffe aus Rohöl und Kohle oder auch Kohlenwasserstoffe die aus dem Prozeß selbst stammen, ferner Sauerstoff enthaltende Kohlenwasserstoffe und Öle. Schließlich kann auch Wasser und Dampf zugesetzt werden, wobei letzterer auch den bereits oben erläuterten alternativen hydrierenden Behandlungen zugesetzt werden kann.Suitable hydrogen-transferring solvents are, for example, tetralin, anthracene oil, isopropanol, oils containing cresols, decalin, naphthalene, tetrahydrofuran, dioxane and other hydrocarbons from crude oil and coal or hydrocarbons which originate from the process itself, and also oxygen-containing hydrocarbons and oils. Finally, water and steam can also be added, the latter also being able to be added to the alternative hydrogenating treatments already explained above.
Andererseits kann das Abfallmaterial zunächst in einen Vegetabilien-, Bicmass- oder Cellulose-Anteil und einen synthetischen Anteil getrennt werden, wobei beide Anteile getrennt weiter verarbeitet werden, und wobei der Vegetabilien-, Bicmass- oder Cellulose-Anteil im wesentlichen hydrolytisch gespalten wird, beispielsweise in Gegenwart von Basen oder Säuren, wobei diese Umwandlung vorzugsweise in Gegenwart protischer Lösungsmittel, insbesondere von Wasser und Alkoholen durchgeführt werden kann und/oder in Gegenwart von Kohlenmonoxid und/oder Wasserstoff und andererseits der im wesentlichen synthetische Anteil der oben beschriebenen hydrierenden Behandlung unterworfen wird.On the other hand, the waste material can first of all be separated into a vegetable, bicmass or cellulose fraction and a synthetic fraction, with both fractions being processed separately, and with the vegetable, bicmass or cellulose fraction being split essentially hydrolytically, for example in the presence of bases or acids, this conversion preferably being carried out in the presence of protic solvents, in particular water and alcohols and / or in the presence of carbon monoxide and / or hydrogen and, on the other hand, the essentially synthetic portion of the hydrogenating treatment described above .
Eine Verbesserung dieses in DE-PS 34 42 503 bzw. der europäischen Nachanmeldung Nr. 85 11 4535.9 offenbarten Verfahrens liegt in der vorliegenden Erfindung vor, welche die Behandlung Kohlenstoff enthaltender organischer Abfälle synthetischen oder überwiegend synthetischen Ursprungs mit Wasserstoff und/oder Wasserstoff enthaltendenden Gasen und/oder Wasserstoff übertragenden Lösungsmitteln betrifft,gegebenenfalls in Gegenwart eines (von) Katalysators(en), dadurch gekennzeichnet, daß
- a, die Behandlung bei einer Temperatur von 200-600°C·durchgeführt wird, vorzugsweise von 200-540"C, besonders bevorzugt von 300-540°C, bei einem Druck von 30-500 bar, vorzugsweise von 50-450 bar, besonders bevorzugt von 50-350 bar und einer Verweilzeit von 1 Minute bis 8 Stunden, vorzugsweise von 10 Minuten bis 6 Stunden und besonders bevorzugt von 15 Minuten bis 4 Stunden,
- b, das Kohlenstoff enthaltende organische Abfallmaterial synthetischen bzw. überwiegend synthetischen Ursprungs zumindest teilweise einer Vorbehandlung unter Wasserstoff und/oder Wasserstoff enthaltenden Gasen und/oder Wasserstoff übertragende Lösungsmittel unterworfen wird, bei einer Temperatur von 75-600°C, vorzugsweise von 75-540°C und besonders bevorzugt von 120-500°C, einem Druck von 1 bis 600 bar, vorzugsweise von 1 bis 500 bar und besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1. Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden und/ oder zumindestens teilweise einer Vorbehandlung unter (einem) Inertgas unterworfen wird, bei einer Temperatur von 75-600°C, vorzugsweise von 75-500°C, besonders bevorzugt von 120-475°C, einem Druck von 1-600 bar, vorzugsweise von 1-500 bar und besonders bevorzugt von 1-350 bar und einer Ver- weilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden.
- a, the treatment is carried out at a temperature of 200-600 ° C., preferably 200-540 ° C., particularly preferably 300-540 ° C., at a pressure of 30-500 bar, preferably 50-450 bar, particularly preferably from 50-350 bar and a residence time from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 minutes to 4 hours,
- b, the carbon-containing organic waste material of synthetic or predominantly synthetic origin is at least partially subjected to pretreatment under hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, at a temperature of 75-600 ° C., preferably of 75-540 ° C and particularly preferably from 120-500 ° C, a pressure from 1 to 600 bar, preferably from 1 to 500 bar and particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 Hours and / or at least partially subjected to a pretreatment under (an) inert gas, at a temperature of 75-600 ° C, preferably of 75-500 ° C, particularly preferred of 120-475 ° C, a pressure of 1-600 bar, preferably 1-500 bar, and more preferably from 1-350 bar and a V ER- residence time of 1 minute to 6 hours, preferably from 1 minute to 4 hours.
Die Untersuchungen der Anmelderin haben gezeigt, daß durch die erfindungsgemäße Vorbehandlung von Abfällen, die anschließend einer Hydrierung unterworfen werden, diese Abfälle in Produkte umgewandelt werden können, die als Folge der erhaltenen Viskositäten in den Folgeschritten viel einfacher gehandhabt werden können,verglichen mit solchen Materialien, die nur aufgeschmolzen oder aufgelöst werden, während einer kurzen Behandlungszeit. So können die erfindungsgemäßen Produkte beispielsweise problemlos gepumpt oder mit Schneckenfördererngefördert werden und je nach angewandten Bedingungen wesentlich leichter in flüssige Kohlenwasserstoffe in der anschließenden Hydrierung umgewandelt werden.The investigations of the applicant have shown that the pretreatment of wastes according to the invention, which are subsequently subjected to hydrogenation, can convert these wastes into products which, as a result of the viscosities obtained, can be handled much more easily in the subsequent steps compared to such materials. that only melt or dissolve during a short treatment period. For example, the products according to the invention can be pumped without problems or conveyed with screw conveyors and, depending on the conditions used, can be converted into liquid hydrocarbons in the subsequent hydrogenation much more easily.
Die erfindungsgemäße Vorbehandlung kann in Gegenwart von Wasserstoff und/oder Wasserstoff enthaltenden Gasen und/oder Wasserstoff übertragenden Lösungsmitteln durchgeführt werden sowie in Inertatmosphere oder in Lösungsmitteln, welche nicht als Wasserstoffüberträger wirken. Das Verfahren kann ferner mit oder ohne Katalysatoren durchgeführt werden.The pretreatment according to the invention can be carried out in the presence of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents and in an inert atmosphere or in solvents which do not act as hydrogen transfer agents. The process can also be carried out with or without catalysts.
Die spaltende Vorbehandlung erfolgt erfindungsgemäß in Mischvorrichtungen im allgemeinen Sinn, insbesondere in Extrudern und Misch/Knet-Vorrichtungen, da diese im allgemeinen pulsationsfrei in eine nachgeschaltete Apparatur fördern. Hierzu können Extruder beispielsweise mit Einfach- oder Mehrfachschneckenförderung verwendet werden oder beispielsweise solche wie sie in der DE-OS 30 01 318 oder in der DE-OS 29 49 537 beschrieben sind, wobei in letzteren die Förderschnecke(n) hinter der eigentlichen Förderstrecke in einen erweiterten Reaktionsraum hineinragt(en), so daß auch in diesem zusätzliche Durchmischung durch die Schnecke(n) erfolgt. Jedoch auch zahlreiche andere Mischvorrichtungen wie beispielsweise Knetscheiben-Schneckenpressen, Ko-Kneter, Hohlschnecken-Wärmetauscher,The splitting pretreatment is carried out according to the invention in mixing devices in a general sense, in particular in extruders and mixing / kneading devices, since these generally convey into a downstream apparatus without pulsation. For this purpose, extruders can be used, for example, with single or multiple screw conveyors or, for example, those as described in DE-OS 30 01 318 or in DE-OS 29 49 537, in the latter the screw conveyor (s) behind the actual conveyor section into one extended reaction space protrudes, so that this additional diam by the screw (s). However, numerous other mixing devices such as kneading disc screw presses, kneaders, hollow screw heat exchangers,
Schneckenkneter, Knet-Extruder, Rührapparaturen, Durchlaufmischer, Kneter, Mahlvorrichtungen bzw. Mühlen wie Perl-, Hammer- oder Schwingmühlen sind für die erfindungsgemäße Vorbehandlung geeignet. Im Falle von Knetern, Rührbehältern, Mühlen und dergl. kann ggfs. ein Förderextruder nachgeschaltet werden, der eine Druckerhöhung bis zum Druck des Hydrierreaktors bewirkt.Screw kneaders, kneading extruders, stirring apparatuses, continuous mixers, kneaders, grinding devices or mills such as bead, hammer or vibrating mills are suitable for the pretreatment according to the invention. In the case of kneaders, stirred tanks, mills and the like, a feed extruder can optionally be connected downstream, which brings about an increase in pressure up to the pressure of the hydrogenation reactor.
Erfindungsgemäß sehr gut geeignete Apparate sind insbesondere solche, die gleichzeitig mischen und kneten. Hierbei erfolgt in besonders geeigneter Weise die gewünschte Plastifizierung, Dispergierung, Homogenisierung, Entgasung und Abbau-Reaktion, die zu den gewünschten Viskositäten führt. Bekanntlich läßt sich durch Verbesserung der Durchmischung auch eine Erhöhung der Reaktionsgeschwindigkeit erreichen.Apparatus which are very suitable according to the invention are, in particular, apparatus which mix and knead at the same time. The desired plasticization, dispersion, homogenization, degassing and degradation reaction, which leads to the desired viscosities, takes place in a particularly suitable manner. As is known, the reaction rate can also be increased by improving the mixing.
Die genannten Vorrichtungen können ggfs. bestimmten Einsatzstoffen zusätzlich angepaßt werden, wie beispielsweise Gaszuführungen enthalten, Aufgabevorrichtungen an unterschiedlichen Stellen der Vorbehandlungsstrecke, Trocknungs-, Erhitzungs-und Kühlstrecken, Zugabevorrichtungen für flüssige Einsatzprodukte und dergl. Ferner können mehrere der genannten Vorrichtungen hintereinander oder parallel geschaltet sein, so daß insgesamt am Eingang des (der) nachgeschalteten Hydrierreaktors(en) ein Einsatzproduktgemisch der gewünschten Eigenschaften vorliegt, insbesondere bezüglich Abbaugrad und Vis- kosität.The devices mentioned can optionally also be adapted to certain feedstocks, such as containing gas feeds, feed devices at different points on the pretreatment section, drying, heating and cooling sections, addition devices for liquid feed products and the like. Furthermore, several of the devices mentioned can be connected in series or in parallel so that overall at the input of (the) downstream of the hydrogenation reactor (s) is a feedstock mixture of the desired characteristics is present, in particular with respect to degree of degradation and viscosity by V is-.
Je nach einzusetzenden Abfallprodukten und Biomasse befinden sich vor den genannten Vorrichtungen beispielsweise Grobmühlen, Schneidvorrichtungen, Abtrennvorrichtungen für anorganische Materialien, Aufschmelzvorrichtungen, Vorrichtungen zur Metallabscheidung und dergl., ggfs. kann auch eine Gefrierzerkleinerung angewendet werden. Hierdurch können be-, reits in der zur erfindungsgemäßen Vorbehandlung eingesetzten Mischvorrichtung Produkte mit den gewünschten Aggregatzuständen eingesetzt werden. Wird die erfindungsgemäße Vorbehandlung in Verbindung mit Wasserstoff, Wasserstoff enthaltenden Gasen oder Wasserstoff übertragenden Lösungsmitteln durchgeführt, so werden die genannten Vorrichtungen vorzugsweise unter dem Gesichtspunkt ausgewählt, daß eine genügende für die Umsetzung erforderliche Wasserstoffmenge zum umzusetzenden Einsatzprodukt gelangt. Hierzu eignen sich beispielsweise Rührvorrichtungen, Misch /Knetvorrichtungen, Extruder oder die in DE-OS 30 01 318 und DE-OS 29 43 537 offenbarten Vorrichtungen oder es können andere der genannten Vorrichtungen eingesetzt werden, ggfs. mit zweckentsprechenden Zuführungen für Wasserstoff. Alternativ kann Wasserstoff auch bereits vor der Mischvorrichtung zugeführt werden. J e are employed by waste products and biomass in front of the aforementioned devices, for example, coarse mills, cutters, separators for inorganic materials Aufschmelzvorrichtungen, devices for metal deposition and the like., If necessary. Can also be a G efrierzerkleinerung be applied. As a result, products with the desired physical states can already be used in the mixing device used for the pretreatment according to the invention. If the pretreatment according to the invention is carried out in conjunction with hydrogen, hydrogen-containing gases or hydrogen-transferring solvents, the devices mentioned are preferably selected from the point of view that a sufficient amount of hydrogen required for the reaction reaches the feedstock to be converted. For this purpose, for example, stirring devices, mixing / kneading devices, extruders or the devices disclosed in DE-OS 30 01 318 and DE-OS 29 43 537 are suitable or other of the devices mentioned can be used, if appropriate with appropriate feeds for hydrogen. Alternatively, hydrogen can also be supplied upstream of the mixing device.
Erfindungsgemäß wird die hydrierende Behandlung in der Vorbehandlungsvorrichtung durchgeführt bei einer Temperatur von 75-600°C, vorzugsweise von 75-540°C, besonders bevorzugt von 120-500°C, einem Druck von 1-600 bar, vorzugsweise von 1-500 bar, besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden, wobei die gewünschte Wasserstoffmenge in einer oder mehreren Stufen, in Abhängigkeit von der Mischvorrichtung, zugeführt werden kann. Die thermische Vorbehandlung wird in der Mischvorrichtung bei 75-600°C durchgeführt, vorzugsweise von 75-540°C, besonders bevorzugt bei 120-475°C, einem Druck von 1-600 bar, vorzugsweise von 1-500 bar, besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden.According to the invention, the hydrogenating treatment is carried out in the pretreatment device at a temperature of 75-600 ° C, preferably 75-540 ° C, particularly preferably 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar , particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours, the desired amount of hydrogen being able to be supplied in one or more stages, depending on the mixing device. The thermal pretreatment is carried out in the mixing device at 75-600 ° C., preferably from 75-540 ° C., particularly preferably at 120-475 ° C., a pressure of 1-600 bar, preferably of 1-500 bar, particularly preferably of 1-350 bar and a residence time of 1 minute to 6 hours, preferably 1 minute to 4 hours.
-Grundsätzlich kann die erfindungsgemäße Vorbehandlung, insbesondere im Falle der thermischen Vorbehandlung, auch unter einem geringeren Druck als 1 bar durchgeführt werden.In principle, the pretreatment according to the invention, in particular in the case of thermal pretreatment, can also be carried out under a pressure lower than 1 bar.
Im Falle der thermischen Vorbehandlung kann Inertgas in einer oder mehreren Stufen eingeführt werden, in Abhängigkeit von der verwendeten Mischvorrichtung. Inertgase können beispielsweise Stickstoff, Kohlendioxid, Dampf, Kohlenmonoxid, Methan und andere niedrig siedende Kohlenwasserstoffe sein sowie Gemische dieser Gasen. Auch Wasserstoff kann in kleinen Mengen zugegen sein. Auch kleine Mengen Sauerstoff bzw. Luft sind ggfs. zulässig.In the case of thermal pretreatment, inert gas can be introduced in one or more stages, depending on the mixing device used. Inert gases can be, for example, nitrogen, carbon dioxide, steam, carbon monoxide, methane and other low-boiling hydrocarbons, as well as mixtures of these gases. Hydrogen can also be present in small quantities. Small amounts of oxygen or air may also be permitted.
Erfindungsgemäß können Mischvorrichtungen zur hydrierenden bzw. thermischen Vorbehandlung kombiniert werden in paralleler Schaltung oder in Hintereinanderschaltung. Die genannten Gase können auch vor der eigentlichen Vorbehandlung zugesetzt werden.According to the invention, mixing devices for hydrating or thermal pretreatment can be combined in parallel connection or in series connection. The gases mentioned can also be added before the actual pretreatment.
Ein Wasserstoff übertragendes Lösungsmittel oder ein Gemisch solcher Lösungsmittel kann ebenfalls als solches oder in Kombination mit zusätzlichem Wasserstoff oder Inertgas eingesetzt werden. Auch in diesem Fall wird die hydrierende Vorbehandlung bei einer Temperatur von 75-600°c durchgeführt, vorzugsweise bei 75-540°C und besondersbevorzugt bei 120-500°C, einem Druck von 1-600 bar, vorzugsweise von 1-500 bar und besonders bevorzugt von 1-350 bar und einer Verweilzeit von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden.A hydrogen-transferring solvent or a mixture of such solvents can also be used as such or in combination with additional hydrogen or inert gas. In this case too, the hydrogenating pretreatment is carried out at a temperature of 75-600 ° C, preferably at 75-540 ° C and particularly preferably at 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar and particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours.
Erfindungsgemäß kann die Umwandlung in der Mischvorrichtung auch in Gegenwart protischer Lösungsmittel durchgeführt werden, insbesondere in Gegenwart von Wasser oder Methanol und/ oder wenigstens einer Komponente aus der Gruppe:
Ethanol, C3-C4-Alkohole und höhere Alkohole.According to the invention, the conversion in the mixing device can also be carried out in the presence of protic solvents, in particular in the presence of water or methanol and / or at least one component from the group:
Ethanol, C 3 -C 4 alcohols and higher alcohols.
Protische Lösungsmittel führen, in Abhängigkeit von der Art des eingesetzten Abfalls, wenigstens teilweise zur Hydrolyse. Wird die Reaktion in der Vorbehandlungs-Mischvorrichtung durchgeführt, so werden Temperaturen von 75-600°C angewandt, vorzugsweise von 75-540°C und besonders bevorzugt von 120-500°C, Drucke von 1-600 bar, vorzugsweise von 1-500 bar, besonders bevorzugt von 1-350 bar und Verweilzeiten von 1 Minute bis 6 Stunden, vorzugsweise von 1 Minute bis 4 Stunden. Die Hydrolyse kann ebenfalls durchgeführt werden in Gegenwart von Wasserstoff, Wasserstoff enthaltenden Gasen oder Wasserstoff übertragenden Lösungsmitteln mit oder ohne Katalysator oder mit oder ohne CO. Es können typische Hydrolysekatalysatoren eingesetzt werden, wie beispielsweise Säuren oder Basen einschließlich organischer Amine. Die auf Seite 6 und 7 genannten Katalysatoren können ebenfalls beigefügt sein.Protic solvents, depending on the type of waste used, at least partially lead to hydrolysis. If the reaction is carried out in the pretreatment mixing device, temperatures of 75-600 ° C. are used, preferably from 75-540 ° C and particularly preferably from 120-500 ° C , pressures from 1-600 bar, preferably from 1-500 bar, particularly preferably from 1-350 bar and residence times from 1 minute to 6 hours, preferably from 1 Minute to 4 hours. The hydrolysis can also be carried out in the presence of hydrogen, hydrogen-containing gases or hydrogen-transferring solvents with or without a catalyst or with or without CO. Typical hydrolysis catalysts, such as acids or bases including organic amines, can be used. The catalysts mentioned on pages 6 and 7 can also be included.
Weiterhin kann die erfindungsgemäße Vorbehandlung in Gegenwart von Lösungsmitteln durchgeführt werden, die nicht Wasserstoff übertragend wirken, wie z.B. von Aromaten wie Benzol, Toluol oder den Xylolen. Auch nichtaromatische Lösungsmittel können verwendet werden, wie beispielsweise gesättigte oder im wesentlichen gesättigte aliphatische Kohlenwasserstoffe in Siedebereichen zwischen beispielsweise 30 und mehr als 500°C. Die hochsiedenden Fraktionen können beispielsweise Rückstandsöle, wie oben bereits erwähnt, sein.Furthermore, the pretreatment according to the invention can be carried out in the presence of solvents which do not have a hydrogen transfer effect, such as of aromatics such as benzene, toluene or the xylenes. Non-aromatic solvents can also be used, such as saturated or substantially saturated aliphatic hydrocarbons in boiling ranges between, for example, 30 and more than 500 ° C. The high-boiling fractions can, for example, be residual oils, as already mentioned above.
Erfindungsgemäß kann die hydrierende Spaltung in der Vorbehandlungsvorrichtung auf den gewünschten Umfang eingestellt werden,bis zu einem Abbau, wie er beschrieben ist in der hydrierenden Behandlung von Abfällen gemäß DE-PS 34 42 506 bzw. in der europäischen Nachanmeldung Nr. 85 11 4535.9. In einem solchen Falle kann sich ein nachgeschalteter Hydrierreaktor erübrigen.According to the invention, the hydrogenating cleavage in the pretreatment device can be set to the desired extent, up to a breakdown as described in the hydrogenating treatment of waste according to DE-PS 34 42 506 or in the European subsequent application No. 85 11 4535.9. In such a case, a downstream hydrogenation reactor can be dispensed with.
Die hydrierende Vorbehandlung kann erfindungsgemäß mit oder ohne Katalysatoren durchgeführt werden, die auf den Seiten 6 und 7 offenbart sind. Katalysatoren können in die Vorbehandlungsvorrichtung eingeführt werden oder vor derselben zugesetzt werden.According to the invention, the hydrogenating pretreatment can be carried out with or without the catalysts which are disclosed on pages 6 and 7. Catalysts can be introduced into the pretreatment device or added before it.
Die Abfälle aus organischen-synthetischen Materialien können erfindungsgemäß in flüssige Kohlenwasserstoffe umgewandelt werden, die im wesentlichen im Naphtha- bzw. Benzinbereich oder Mitteldestillatbereich sieden. Beispiele für solche Abfälle sind auf den Seiten 3 und 4 offenbart.According to the invention, the waste from organic synthetic materials can be converted into liquid hydrocarbons which boil essentially in the naphtha or gasoline range or middle distillate range. Examples of such waste are disclosed on pages 3 and 4.
Die erfindungsgemäßen umwandelbaren Abfälle sind jedoch nicht auf die dort angegebenen beschränkt.However, the convertible wastes of the present invention are not limited to those specified there.
Ein besonderer Vorteil des erfindungsgemäßen Verfahrens ergibt sich daraus, daß die Bedingungen in der Vorbehandlungsvorrichtung so eingestellt werden können, daß ein Produkt erhalten wird, das problemlos in Folgeschritten gehandhabt werden kann, z.B. gepumpt oder über Förderschnecken gefördert werden kann, wobei die Bedingungen an die Art des eingesetzten Abfalls angepasst werden können, der wie bereits oben ausgeführt Kunststoffmaterialien, Farbreste, Lackzusammensetzungen, Industriechemikalien wie beispielsweise solche, die nach dem Stand der Technik auf Sonderdeponien deponiert werden müssen, Shredderabfälle aus der Automobilindustrie, gebrauchte Schmieröle, Elastomere, Textilmaterialien aber auch in gewissem Umfang Papier, Pappe und andere Cellulose enthaltende Materialien wie Holzabfälle, Sägespäne oder Vegetabilien aus Hausmüll, enthalten kann.A particular advantage of the method according to the invention results from the fact that the conditions in the pretreatment device can be set so that a product is obtained which can be handled without problems in subsequent steps, for example pumped or conveyed via screw conveyors, the conditions being based on Art of the waste used can be adjusted, which as pointed out above plastic materials, paint residues, paint compositions I ndustriechemikalien such as those that need to be deposited in special dumps according to the prior art, shredded waste from the automobile industry, used lubricating oils, elastomers, fabrics but also in to a certain extent paper, cardboard and other cellulose-containing materials such as wood waste, sawdust or vegetable matter from household waste.
Alternativ zur Förderung durch Pumpen oder Schneckenförderer kann das vorbehandelte Produkt auch direkt aus der Vorbehandlungsvorrichtung in den Hydrierreaktor gefördert werden wie beispielsweise durch Extruder.As an alternative to conveying by pumps or screw conveyors, the pretreated product can also be conveyed directly from the pretreatment device into the hydrogenation reactor, for example by means of an extruder.
Das erfindungsgemäße Verfahren erlaubt daher auch nur wenig vorsortierte Abfälle umzusetzen. Es ist jedoch aus apparativen Gründen wünschenswert, anorganische Materialien wie Steine, Metalle, Glas und andere vor der Vorbehandlung abzutrennen, zumindest grobe Materialien.The method according to the invention therefore also allows only a little pre-sorted waste to be implemented. However, for reasons of equipment, it is desirable to separate inorganic materials such as stones, metals, glass and others before the pretreatment, at least rough materials.
Erfindungsgemäß bevorzugt ist, zumindest überwiegend, Vegeta- - bilien und Cellulose enthaltende Materialien von den organischen Abfällen synthetischen Ursprungs abzutrennen, obgleich eine vollständige Abtrennung der Vegetabilien und Cellulose enthaltenden Materialien erfindungsgemäß nicht erforderlich ist.According to the invention, it is preferred, at least predominantly, to separate materials containing vegetables and cellulose from the organic waste of synthetic origin, although a complete separation of the materials containing cellulose and vegetables is not necessary according to the invention.
Diese Materialien, z.B. Vegetabilien können getrennt, beispielsweise durch Fermentation aufgearbeitet werden.These materials, e.g. Vegetables can be processed separately, for example by fermentation.
Ein wichtiger Vorteil der vorliegenden Erfindung ergibt sich daraus, daß durch die erfindungsgemäß hydrierende oder thermische Vorbehandlung in Kombination mit der anschließenden Hydrierung des vorbehandelten Abfalls auch sehr inhomogene Abfallgemsiche als Einsatzprodukt eingesetzt werden können, wobei diese in hohen Ausbeuten in wertvolle flüssige Kohlenwasserstoffe umgewandelt werden. Die Heteroatome wie beispielsweise Sauerstoff, Schwefel, Stickstoff oder Halogene, die in vielen Abfallmaterialien enthalten sind, werden erfindungsgemäß umgewandelt in ihre Wasserstoffderivate, die problemlos gemäß dem Stand der Technik weiter aufgearbeitet werden können.An important advantage of the present invention results from the fact that the hydrogenating or thermal pretreatment according to the invention, in combination with the subsequent hydrogenation of the pretreated waste, means that even very inhomogeneous waste mixtures can be used as the feed product, these being converted into valuable liquid hydrocarbons in high yields. The heteroatoms such as oxygen, sulfur, nitrogen or halogens, which are contained in many waste materials, are converted according to the invention into their hydrogen derivatives, which can be worked up further according to the prior art without any problems.
Dies ist von besonderer Bedeutung im Falle von Abfällen die Chlor, Brom oder Fluor enthalten.This is particularly important in the case of waste containing chlorine, bromine or fluorine.
Das bisherige Problem der Abfallbeseitigung, insbesondere im Falle von giftigen und halogenierten Abfällen wird daher durch die vorliegende Erfindung ohne Risiko bezüglich der Umwelt gelöst. Solche halogenierten Abfälle sind beispielsweise Polychlorbiphenylene, Polyvinylchlorid, Fluor enthaltende Polymere oder Halogene enthaltende Lösungsmittel.The present problem of waste disposal, particularly in the case of toxic and halogenated waste, is therefore solved by the present invention without any risk to the environment. Such halogenated wastes are, for example P olychlorbiphenylene, polyvinyl chloride, fluorine-containing polymers or halogen-containing solvent.
Eine besonders vorteilhafte Wirkung der thermischen oder hydrierenden Vorbehandlung ist das Ergebnis, daß in Abhängigkeit von Temperatur, Verweilzeit und Druck bereits in der Vorbehandlung eine weitgehende Abspaltung von Halogenen, im we- .sentlichen als Halogenwasserstoffe, erfolgt. Beispielsweise werden aus Polyvinylchlorid enthaltenden Abfällen etwa 90 % des Halogens bereits bei 250°C, einer Verweilzeit von 30 Minuten und einem Wasserstoff- oder Stickstoffdruck von 10 bar oder weniger als Chlorwasserstoff entfernt.A particularly advantageous effect of the thermal or hydrating pretreatment is the result that depends As a result of the temperature, dwell time and pressure, halogens are largely eliminated in the pretreatment, essentially as hydrogen halides. For example, about 90% of the halogen is already removed from waste containing polyvinyl chloride at 250 ° C., a residence time of 30 minutes and a hydrogen or nitrogen pressure of 10 bar or less as hydrogen chloride.
Die Halogenabspaltung kann zusätzlich begünstigt werden, durch Temperaturerhöhung und Erhöhung der Verweilzeit. Weiterhin kann die Halogenabspaltung durch Katalysatoren wie sie beispielsweise auf den Seiten 6 und 7 genannt sind, begünstigt werden. Solche Katalysatoren, die gemäß dem Stand der Technik zur Abspaltung von Halogenwasserstoff verwendet werden, wie beispielsweise Friedel-Crafts-Katalysatoren und/oder organische Amine und/oder andere basische Verbindungen, können erfindungsgemäß ebenfalls eingesetzt werden. Als Ergebnis können Halogenwasserstoffe bereits bei milden Bedingungen abgespalten werden.Halogen elimination can also be promoted by increasing the temperature and increasing the residence time. Halogen elimination can also be promoted by catalysts such as those mentioned on pages 6 and 7. Such catalysts which are used according to the prior art for the elimination of hydrogen halide, such as Friedel-Crafts catalysts and / or organic amines and / or other basic compounds, can also be used according to the invention. As a result, hydrogen halides can be split off even under mild conditions.
Erfindungsgemäß können auch Materialien dem eingesetzten Abfall zugesetzt werden, bzw. in die Vorbehandlungseinrichtung oder den Hydrierreaktor zugesetzt werden wie beispielsweise Rohöl, Rohölkomponenten und Produkte die aus Rohöl gewonnen werden, Asphalte, Bitumen, mineralische Teere, Kohle, Kohlekomponenten, Produkte aus Kohle, Braunkohle, Torf, Pyrolyseöle wie beispielsweise solche die aus Verkokungsprozessen oder Pyrolyseprozessen erhalten werden, Ölsande, Ölsandprodukte, Rückstandsöle aus der Rohölverarbeitung, aus Krackanlagen, Vakuumrückstände, Schieferöle und Schieferölprodukte und ähnliche Materialien.According to the invention, materials can also the waste used are added or be added in the preconditioner or the hydrogenation reactor, such as crude oil, R ohölkomponenten and products derived from crude oil, asphalt, bitumen, mineral tars, coal, coal components, products from coal, lignite , Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.
In Abhängigkeit von der Art des eingesetzten Abfalls kann eine Hydrolysestufe der thermischen oder hydrierenden Vorbehandlung vorgeschaltet werden. In diesem Fall wird die Hydrolysereaktion vorzugsweise in einer Mischvorrischtung durchgeführt wie oben beschrieben, in Gegenwart protischer Lösungs- mittel, insbesondere in Gegenwart von Wasser und/oder Methanol und/oder wenigstens einer Komponente aus der Gruppe:Depending on the type of waste used, a hydrolysis stage can precede the thermal or hydrogenating pretreatment. In this case, the hydrolysis reaction is preferably carried out in a mixed premix performed as described above, in the presence of protic solvents - medium, especially in the presence of water and / or methanol and / or at least one component from the group:
Ethanol, C3-C4-Alkohole und höhere Alkohole, bei einem Druck von 1-150 bar, vorzugsweise von 1-120 bar und einer Temperatur von 50-300°C und vorzugsweise von 75-250°C. Niedere Drucke sind bevorzugt falls die Gase die während der Hydrolyse gebildet werden aus der Hydrolysevorrichtung entfernt werden sollen.Ethanol, C 3 -C 4 alcohols and higher alcohols, at a pressure of 1-150 bar, preferably of 1-120 bar and a temperature of 50-300 ° C and preferably 75-250 ° C. Lower pressures are preferred if the gases that are formed during the hydrolysis are to be removed from the hydrolysis device.
Unter gewissen Bedingungen kann die Hydrolysestufe alternativ zwischen die Vorbehandlung und die eigentliche Hydrierung geschaltet werden. In diesem Fall werden die Hydrolysebedingungen bevorzugt an die Temperatur und den Druck in der Vorbehandlungsstufe oder Hydrierstufe oder beide angepasst.Under certain conditions, the hydrolysis stage can alternatively be switched between the pretreatment and the actual hydrogenation. In this case, the hydrolysis conditions are preferably adapted to the temperature and the pressure in the pretreatment stage or hydrogenation stage or both.
Auf diese Weise können beispielsweise Vegetabilien und Biomasse hydrolytisch gespalten werden und von Abfall organisch synthetischen Ursprungs abgetrennt werden. Die Hydrolysereaktion kann dadurch beschleunigt werden, daß man entsprechend dem Stand der Technik Säuren oder Basen zusetzt. Die hydrolytische Reaktion kann ebenfalls durchgeführt werden in Gegenwart von Wasserstoff, Wasserstoff enthaltenden Gasen, Wasserstoff übertragenden Lösungsmitteln, Katalysatoren wie sie auf den Seiten 6 und 7 beispielshaft genannt sind oder Lösungsmitteln, die nicht zur Stoffübertragung geeignet sind, oder in Gegenwart inerter Gase.In this way, for example, vegetables and biomass can be hydrolytically split and separated from waste of synthetic organic origin. The hydrolysis reaction can be accelerated by adding acids or bases in accordance with the prior art. The hydrolytic reaction can also be carried out in the presence of hydrogen, hydrogen-containing gases, hydrogen-transferring solvents, catalysts as exemplified on pages 6 and 7 or solvents which are not suitable for mass transfer, or in the presence of inert gases.
Sogenannte Anreiböle können ebenfalls erfindungsgemäß in der Vorbehandlungsvorrichtung bzw. vor dieser oder nach dieser zugesetzt werden. Die Anreiböle können aus dem Prozeß selbst stammen oder fremden Ursprungs sein.So-called Anreiböle may also orbehandlungsvorrichtung according to the invention in the V or be added before this or after this. The grinding oils can originate from the process itself or can be of foreign origin.
Erfindungsgemäß können Metalle bzw. Metallverbindungen, die in den Abfällen vorhanden sind, vorteilhaft aufgearbeitet werden, da sie nach der Hydrierung in Rückständen bzw. Aschen in relativ hoher Konzentration anfallen. Diese Rückstände bzw. Aschen können beispielsweise zur Gewinnung der reinen Metalle aufgearbeitet werden.According to the invention, metals or metal compounds which are present in the waste can advantageously be worked up, since they occur in residues or ashes in a relatively high concentration after the hydrogenation. These residues or ashes can be worked up, for example, to obtain the pure metals.
In den folgenden Beispielen wird das erfindungsgemäß Verfahren näher erläutert:The process according to the invention is explained in more detail in the following examples:
Ein Gemisch von im wesentlichen organischen-synthetischen Abfällen aus einer technischen Abfallsortieranlage, ohne Polyvinylchlorid und andere Chlor enthaltende Abfälle, wird mit einem gebrauchten Schmieröl in einem Verhältnis von Abfall zu Öl von 1 : 3 gemischt und 2 Stunden unter einem Wasserstoffdruck von 10 bar und Temperaturen von 250°C, 300°C und 350°C in einem Rührreaktor umgesetzt.A mixture of essentially organic-synthetic waste from a technical waste sorting plant, without waste containing polyvinyl chloride and other chlorine, is mixed with a used lubricating oil in a ratio of waste to oil of 1: 3 and for 2 hours under a hydrogen pressure of 10 bar and temperatures of 250 ° C, 300 ° C and 350 ° C in a stirred reactor.
Es werden pumpbare Produkte erhalten mit den in Tabelle l angegebenen Viskositäten.
Beispiel 1 wurde wiederholt, jedoch unter einem Stickstoffdruck von 10 bar. Im Falle der Temperatur von 300°C wurde zusätzlich bei einem Stickstoffdruck von 2 bar gearbeitet. Die Ergebnisse sind dargestellt in Tabelle 2.Example 1 was repeated, but under a nitrogen pressure of 10 bar. In the case of the temperature of 300 ° C, an additional nitrogen pressure of 2 bar was used. The results are shown in Table 2.
Ein Gemisch von im wesentlichen synthetischem Abfall aus einer technischen Abfallsortieranlage, daß 10 Gew.% Polyvinylchlorid enthielt, wurde mit einem gebrauchten Schmieröl im Verhältnis Abfall zu Öl von 1 : 3 gemischt, wie in Beispiel 1 beschrieben und bei Temperaturen von 250°C, 300°C und 350°C zwei Stunden bei einem Druck von 10 bar Stickstoff bzw. Wasserstoff behandelt.A mixture of essentially synthetic waste from an industrial waste sorting plant, which contained 10% by weight of polyvinyl chloride, was mixed with a used lubricating oil in a waste to oil ratio of 1: 3, as described in Example 1 and at temperatures of 250 ° C., 300 ° C and 350 ° C treated for two hours at a pressure of 10 bar nitrogen or hydrogen.
Es wurden pumpbare Produkte erhalten mit den in Tabelle 3 angegebenen Viskositäten.Pumpable products with the viscosities shown in Table 3 were obtained.
Ein Gemisch aus 90 Gew.% im wesentlichen organischen Abfällen synthetischen Ursprungs, die aus einer technischen Abfallsortieranlage gewonnen wurden und aus 10 Gew.% Abfallpapier, gemischt mit einem mineralischem Rückstandsöl im Verhältnis von Abfall zu Ö1 von 1 : 3 wurde 20 Minuten bei 20 bar Wasserstoff in einer Doppelschnecken-Misch/Knetvorrichtung bei 150°C, 250°C und 350°C behandelt, in Gegenwart eines Katalysators, der aus mit 5 Gew.% Eisensulfat behandeltem Herdofenkoks bestand.A mixture of 90% by weight of essentially organic waste of synthetic origin, which was obtained from a technical waste sorting plant, and 10% by weight of waste paper, mixed with a mineral residual oil in the ratio of waste to oil of 1: 3, was 20 minutes at 20 bar Hydrogen treated in a twin-screw mixer / kneader at 150 ° C, 250 ° C and 350 ° C, in the presence of a catalyst consisting of oven coke treated with 5% by weight iron sulfate.
Es wurden pumpbare Produkte enthalten mit den in Tabelle 4 angegebenen Viskositäten.
Ein Gemisch aus mineralischen Rückstandsölen und einem Abfallgemisch bestehend aus 10 Gew.% Altreifen, 70 Gew.% von im wesentlichen synthetischem-organischem Abfall aus einer technischen Mülltrennanlage und 20 Gew.% Polyvinylchlorid wurde in einer Misch/Knetvorrichtung 20 Minuten bei 350°C und 450°C bei einem Wasserstoff- bzw. Stickstoffdruck von 200 bar behandelt. Das Verhältnis von Abfall zu Öl betrug 1 : 3. Als Katalysator wurde mit NaOH behandeltes FeS04 eingesetzt.A mixture of mineral residual oils and a waste mixture consisting of 10% by weight of old tires, 70% by weight of essentially synthetic-organic waste from a technical waste separation system and 20% by weight of polyvinyl chloride was mixed and kneaded at 350 ° C for 20 minutes and 450 ° C treated with a hydrogen or nitrogen pressure of 200 bar. The ratio of waste to oil was 1: 3. FeSO 4 treated with NaOH was used as the catalyst.
Es wurden pumpbare Produkte erhalten mit den in Tabelle 5 angegebenen Viskositäten.Pumpable products with the viscosities shown in Table 5 were obtained.
Abfall, der überwiegend aus organisch-synthetischem Material bestand und aus einer technischen Abfallsortieranlage gewonnen wurde, mit 15 Gew.% Polyvinylchlorid, wurde in einem Mischer/Kneter bei 200 bar Wasserstoff und Temperaturen von 350°C und 470°C jeweils 30 Minuten behandelt. Bei der Temperatur von 350°C wurde jeweils ein Versuch mit und ohne Katalysator durchgeführt. Als Katalysator wurde ein Nickel/Molybdän-Katalysator eingesetzt. Es wurde kein Anreiböl verwendet. Die erhaltenen Viskositäten sind in Tabelle 6 wiedergegeben.
Abfall, aus einer technischen Mülltrennanlage, der im wesentlichen aus folgenden Hartkunststoffen bestand:
- 60 Gew.% Polyethylen und Polypropylen
- 10 Gew.% Polyvinylchlorid
- 15 Gew.% Polycarbonate und
- 15 Gew.% Polyamide
wurde gemischt mit Krackvakuumdestillat im Verhältnis Abfall zu Öl von 1 : 3 und unter 10 bar Stickstoff jeweils 1 Stunde bzw. 2 Stunden in einer Knetvorrichtung bei Temperaturen von 200°C und 250°C behandelt.Waste from a technical waste separation system, which essentially consisted of the following hard plastics:
- 60% by weight of polyethylene and polypropylene
- 10% by weight of polyvinyl chloride
- 15% by weight of polycarbonates and
- 15% by weight of polyamides
was mixed with cracking vacuum distillate in the ratio waste to oil of 1: 3 and under 10 bar nitrogen for 1 hour or 2 hours in a kneader at temperatures of 200 ° C and 250 ° C.
Die Viskositäten der Produkte sind in Tabelle 7 wiedergegeben.
Abfall, der im wesentlichen aus organisch-synthetischem Material bestand aus einer technischen Mülltrennanlage und der 5 Gew.% perfluoriertes Polyethylen (Teflon) und 20 Gew.% Textilabfälle aus 50 % Wolle und 50 % Polyacrylnitril enthielt, wurde wie in Beispiel 6 angegeben behandelt. Die erhaltenen Viskositäten sind in Tabelle 8 wiedergegeben.
Die Beispiele zeigen, daß sowohl unter Stickstoff als auch unter Wasserstoff in den Mischvorrichtungen ein Abbau des Einsatzproduktes erfolgt, wobei Produkte erhalten werden, die in den Folgeschritten gut handbar sind und beispielsweise durch Pumpen oder Schneckenfördern leicht transportierbar sind. Dies gilt auch für solche Abfälle, die aus sehr verschiedenartigen Materialien bestehen.The examples show that the feedstock is broken down both under nitrogen and under hydrogen in the mixing devices, products being obtained which are easy to handle in the subsequent steps and can be easily transported, for example by pumps or screw conveyors. This also applies to waste that consists of very different materials.
Die Beispiele zeigen ferner, daß bei höheren Temperaturen, wie z.B. bei 475°C nahezu quantitative Ölausbeuten mit einem Siedebereich < 500°C erhalten werden können. Weiterhin zeigen die Ergebnisse in den Tabellen 3, 5, 6, 7 und 8, daß die erfindungsgemäße Vorbehandlung zu einer weitgehenden Abspaltung von Chlor, Fluor und Stickstoff führt. Dies gilt auch für Behandlungen unter relativ milden Bedingungen, wie 250°C und 10 bar oder weniger Stickstoff bzw. Wasserstoffdruck in Abhängigkeit von den Ausgangsgemischen.The examples further show that at higher temperatures, e.g. almost quantitative oil yields with a boiling range <500 ° C can be obtained at 475 ° C. Furthermore, the results in Tables 3, 5, 6, 7 and 8 show that the pretreatment according to the invention leads to an extensive elimination of chlorine, fluorine and nitrogen. This also applies to treatments under relatively mild conditions, such as 250 ° C and 10 bar or less nitrogen or hydrogen pressure, depending on the starting mixtures.
Die erfindungsgemäßen Ergebnisse sind von großer Bedeutung für die Abfallhydrierung im technischen Maßstab, da die nachgeschalteten Hydrierreaktoren und andere Anlagenteile, welche hohen Drucken ausgesetzt sind, aus weniger wertvollen Materialien angefertigt werden können.The results according to the invention are of great importance for waste hydrogenation on an industrial scale, since the downstream hydrogenation reactors and other parts of the plant which are exposed to high pressures can be made from less valuable materials.
Ferner wurde das überraschende, nicht vorhersehbare Ergebnis erhalten, daß bei der Behandlung von Abfallmaterialien, welche chlorierte Bestandteile enthalten,sowohl unter Inertgasen als auch unter Wasserstoff ein erhöhter Abbau des Einsatzabfallmaterials eintritt im Vergleich zu Einsatzmaterialien, welche diese chlorierten Komponenten nicht enthalten.Furthermore, the surprising, unpredictable result was obtained that in the treatment of waste materials containing chlorinated constituents, both under inert gases and under hydrogen, there is an increased degradation of the feed waste material compared to feed materials which do not contain these chlorinated components.
Das erfindungsgemäße Verfahren ist daher von besonderer Bedeutung für Abfalleinsatzmaterialien, welche chlorierte Bestandteile enthalten.The process according to the invention is therefore of particular importance for waste feed materials which contain chlorinated constituents.
Die Beispiele zeigen auch, daß unter geeigneten Bedingungen und Verhältnissen ein erhöhter Abbau stattfindet unter Stickstoff im Vergleich zu Wasserstoff.The examples also show that, under suitable conditions and conditions, increased degradation takes place under nitrogen compared to hydrogen.
In Abhängigkeit vom Einsatzgemisch kann zunächst eine Abnahme der Viskosität auftreten, gefolgt von einer Zunahme derselben mit zunehmender Temperatur und schließlich wieder eine Abnahme der Viskosität bei noch höherer Temperatur.Depending on the feed mixture, a decrease in viscosity can initially occur, followed by an increase in the same with increasing temperature and finally a decrease in viscosity at an even higher temperature.
Da die Bedingungen der Vorbehandlung in breiten Temperatur-, Druck- und Verweilzeit-Bereichen variiert werden können, lassen sich die Bedingungen der anschließenden Hydrierung ebenfalls in weiten Bereichen variieren, wobei beide Behandlungen einander ergänzen.Since the conditions of the pretreatment can be varied over a wide range of temperature, pressure and residence times, the conditions for the subsequent hydrogenation can also be varied over a wide range, the two treatments complementing one another.
Wenn z.B. die erfindungsgemäße Vorbehandlung bei relativ hoher Temperatur und Verweilzeit bzw. entsprechendem Druck durchgeführt wird, insbesondere bei einem relativ hohem Wasserstoffdruck, kann die anschließende Hydrierung, in Abhängigkeit vom Einsatzprodukt, bei relativ milden Bedingungen durchgeführt werden. Dies gilt insbesondere dann, wenn die Vorbehandlung bereits zu einem weitgehenden Abbau geführt hat.If e.g. the pretreatment according to the invention is carried out at a relatively high temperature and residence time or corresponding pressure, in particular at a relatively high hydrogen pressure, the subsequent hydrogenation can, depending on the product used, be carried out under relatively mild conditions. This applies in particular if the pretreatment has already led to extensive dismantling.
Umgekehrt können relativ milde Bedingungen in der Vorbehandlung durch schärfere Bedingungen in der Hydrierstufe ausgeglichen werden.Conversely, relatively mild conditions in the pretreatment can be compensated for by more severe conditions in the hydrogenation stage.
Beide Stufen ergänzen sich daher erfindungsgemäß und können je nach Bedarf hervorragend an das Einsatzabfallmaterial angepasst werden.Both stages therefore complement one another in accordance with the invention and can be adapted excellently to the operational waste material as required.
Claims (12)
und/oder daß das Abfalleinsatzgemisch in einer Vorrichtung in Gegenwart (eines) von protischen Lösungsmittel(n) behandelt wird, die der Vorbehandlungsvorrichtung vorgeschaltet ist, vorzugsweise in Gegenwart von Wasser und/oder Methanol und/oder wenigstens einer Komponente aus der Gruppe der C2-C4-Alkohole, bei einer Temperatur von 50-300°C, vorzugsweise von 75-250°C, einem Druck von 1-150 bar, vorzugsweise von 1-120 bar und einer Verweilzeit von 1 Minute bis 6 Stunden vorzugsweise von 1 Minute his A Stunden4. Improved process according to claims 1-3, characterized in that the waste feed product is treated in the pretreatment mixing device in the presence of (a) protic solvent (s), preferably in the presence of water and / or methanol and / or at least one component from the group of the C 2 -C 4 alcohols, at a temperature of 75-600 ° C, preferably 75-540 ° C and particularly preferably 120-500 ° C, a pressure of 1-600 bar, preferably of 1 -500 bar and particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours
and / or that the waste feed mixture is treated in a device in the presence of protic solvent (s) which is connected upstream of the pretreatment device, preferably in the presence of water and / or methanol and / or at least one component from the group of the C 2 -C 4 alcohols, at a temperature of 50-300 ° C, preferably 75-250 ° C, a pressure of 1-150 bar, preferably of 1-120 bar and a residence time of 1 minute to 6 hours, preferably of 1 Minute his A hours
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AT87100875T ATE53859T1 (en) | 1986-01-24 | 1987-01-22 | IMPROVED PROCESS FOR REPROCESSING CARBON CONTAINING WASTE. |
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DE3602041 | 1986-01-24 | ||
DE3602041A DE3602041C2 (en) | 1986-01-24 | 1986-01-24 | Improved process for processing carbon-containing waste |
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EP0236701B1 EP0236701B1 (en) | 1990-05-02 |
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US (1) | US4982027A (en) |
EP (1) | EP0236701B1 (en) |
JP (1) | JPS62253689A (en) |
CN (1) | CN87101612A (en) |
AT (1) | ATE53859T1 (en) |
AU (1) | AU583704B2 (en) |
BR (1) | BR8700298A (en) |
CA (1) | CA1300540C (en) |
DD (1) | DD261170A1 (en) |
DE (2) | DE3602041C2 (en) |
ES (1) | ES2000077B3 (en) |
GR (2) | GR880300006T1 (en) |
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US4584421A (en) * | 1983-03-25 | 1986-04-22 | Agency Of Industrial Science And Technology | Method for thermal decomposition of plastic scraps and apparatus for disposal of plastic scraps |
US4526675A (en) * | 1983-05-26 | 1985-07-02 | Standard Oil Company (Indiana) | Hydrocarbon conversion method |
DE3442506C2 (en) * | 1984-11-22 | 1987-04-16 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | Process for the processing of carbon-containing waste |
GB8511587D0 (en) * | 1985-05-08 | 1985-06-12 | Shell Int Research | Producing hydrocarbon-containing liquids |
DE3543240A1 (en) * | 1985-12-06 | 1987-06-11 | Rheinische Braunkohlenw Ag | IMPROVED METHOD FOR HYDROGENATING TREATMENT OF COAL / MINERAL OIL MIXTURES |
-
1986
- 1986-01-24 DE DE3602041A patent/DE3602041C2/en not_active Expired - Fee Related
-
1987
- 1987-01-20 ZA ZA87408A patent/ZA87408B/en unknown
- 1987-01-21 IN IN44/DEL/87A patent/IN169120B/en unknown
- 1987-01-22 EP EP87100875A patent/EP0236701B1/en not_active Expired - Lifetime
- 1987-01-22 DE DE8787100875T patent/DE3762522D1/en not_active Expired - Lifetime
- 1987-01-22 AT AT87100875T patent/ATE53859T1/en not_active IP Right Cessation
- 1987-01-22 ES ES87100875T patent/ES2000077B3/en not_active Expired - Lifetime
- 1987-01-23 CA CA000527981A patent/CA1300540C/en not_active Expired - Lifetime
- 1987-01-23 DD DD87299432A patent/DD261170A1/en not_active IP Right Cessation
- 1987-01-23 JP JP62012646A patent/JPS62253689A/en active Pending
- 1987-01-23 CN CN198787101612A patent/CN87101612A/en active Pending
- 1987-01-23 PL PL1987263795A patent/PL263795A1/en unknown
- 1987-01-23 BR BR8700298A patent/BR8700298A/en unknown
- 1987-01-27 AU AU68090/87A patent/AU583704B2/en not_active Ceased
-
1989
- 1989-01-26 US US07/303,028 patent/US4982027A/en not_active Expired - Fee Related
- 1989-06-22 GR GR88300006T patent/GR880300006T1/en unknown
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1990
- 1990-06-13 GR GR90400370T patent/GR3000553T3/en unknown
Patent Citations (4)
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GB2106128A (en) * | 1981-07-18 | 1983-04-07 | Inst Gas Technology | Production of synthetic liquid and gaseous hydrocarbon fuels from peat |
DD214749A3 (en) * | 1982-03-09 | 1984-10-17 | Schwarze Pumpe Gas Veb | METHOD FOR THE HYDRAULIC CLEARING OF OLD RUBBER AND RUBBER DEVICES |
EP0157339A2 (en) * | 1984-04-04 | 1985-10-09 | Fried. Krupp Gesellschaft mit beschränkter Haftung | Process for the preparation of hydrocarbons from active sludge |
EP0178001A1 (en) * | 1984-09-14 | 1986-04-16 | Kinetics Technology International B.V. | Process for cleaning of waste materials by refining and/or elimination of biologically Difficult to degrade halogen-, nitrogen- and/or sulfur compounds |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3713730A1 (en) * | 1987-04-24 | 1988-11-10 | Union Rheinische Braunkohlen | IMPROVED METHOD FOR RECOVERING CARBON-CONTAINING WASTE AND BIOMASS |
EP0291698A1 (en) * | 1987-04-24 | 1988-11-23 | RWE Entsorgung Aktiengesellschaft | Improved process for the hydrocracking of carbon containing synthetic wastes |
EP0512482A2 (en) * | 1991-05-03 | 1992-11-11 | RWE Entsorgung Aktiengesellschaft | Process for reducing the formation of coke in the thermal treating of synthetic organic refuse |
EP0512482A3 (en) * | 1991-05-03 | 1993-01-13 | Rwe Entsorgung Aktiengesellschaft | Process for reducing the formation of coke in the thermal treating of synthetic organic refuse |
EP0593911A1 (en) * | 1992-09-26 | 1994-04-27 | RWE Entsorgung Aktiengesellschaft | Accelerated thermal cracking process for synthetic wastes |
EP0594165A1 (en) * | 1992-10-22 | 1994-04-27 | KUHNE ANLAGENBAU GmbH | Method for the recycling of thermoplastic waste and plant for carrying out this method |
EP0606919A1 (en) * | 1993-01-15 | 1994-07-20 | RWE Entsorgung Aktiengesellschaft | Process for controlling the chloron concentration in cracking products from synthetic organic materials |
Also Published As
Publication number | Publication date |
---|---|
DD261170A1 (en) | 1988-10-19 |
GR880300006T1 (en) | 1989-06-22 |
ES2000077A4 (en) | 1987-11-16 |
DE3762522D1 (en) | 1990-06-07 |
CN87101612A (en) | 1987-10-28 |
AU583704B2 (en) | 1989-05-04 |
ZA87408B (en) | 1987-08-26 |
PL263795A1 (en) | 1988-02-04 |
GR3000553T3 (en) | 1991-07-31 |
AU6809087A (en) | 1987-08-06 |
EP0236701B1 (en) | 1990-05-02 |
ATE53859T1 (en) | 1990-06-15 |
IN169120B (en) | 1991-09-07 |
CA1300540C (en) | 1992-05-12 |
US4982027A (en) | 1991-01-01 |
DE3602041A1 (en) | 1987-07-30 |
ES2000077B3 (en) | 1990-08-16 |
BR8700298A (en) | 1987-12-01 |
JPS62253689A (en) | 1987-11-05 |
DE3602041C2 (en) | 1996-02-29 |
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