EP4170003A1 - Verfahren zur herstellung eines kohlenwasserstoffprodukts - Google Patents
Verfahren zur herstellung eines kohlenwasserstoffprodukts Download PDFInfo
- Publication number
- EP4170003A1 EP4170003A1 EP21203750.1A EP21203750A EP4170003A1 EP 4170003 A1 EP4170003 A1 EP 4170003A1 EP 21203750 A EP21203750 A EP 21203750A EP 4170003 A1 EP4170003 A1 EP 4170003A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbon
- ppm
- organically bound
- composition
- hydrocarbon mixture
- 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.)
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 81
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 81
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 46
- 150000002830 nitrogen compounds Chemical group 0.000 claims abstract description 46
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 43
- 150000002367 halogens Chemical class 0.000 claims abstract description 41
- -1 halide ions Chemical class 0.000 claims abstract description 21
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229920003023 plastic Polymers 0.000 claims description 28
- 239000004033 plastic Substances 0.000 claims description 28
- 239000004800 polyvinyl chloride Substances 0.000 claims description 21
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 20
- 239000010779 crude oil Substances 0.000 claims description 19
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 238000000197 pyrolysis Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 150000003335 secondary amines Chemical class 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 150000004074 biphenyls Chemical class 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 22
- 229910052801 chlorine Inorganic materials 0.000 description 22
- 229920000915 polyvinyl chloride Polymers 0.000 description 19
- 239000012071 phase Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 8
- 150000002896 organic halogen compounds Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000004045 organic chlorine compounds Chemical class 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000007068 beta-elimination reaction Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000004794 expanded polystyrene Substances 0.000 description 2
- 239000004795 extruded polystyrene foam Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 108700031620 S-acetylthiorphan Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010792 electronic scrap Substances 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
-
- 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
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/121—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing NH3 only (possibly in combination with NH4 salts)
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
Definitions
- Contamination with organic halogen compounds is a problem in many refinery processes. For example, this affects the production of synthetic crude oils from the pyrolysis of plastic material or other raw materials.
- Plastic mixtures often contain halogenated polymers, such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE) or also halogenated flame retardants, which enter the process during pyrolysis and can be found in the respective products in the form of organic halogen compounds. This significantly reduces the product quality.
- PVC polyvinyl chloride
- PTFE polytetrafluoroethylene
- flame retardants also halogenated flame retardants
- Organically bound halogen can be partially removed by ⁇ -elimination at high temperatures.
- some hydrogen chloride can be eliminated with cleavage of the organic carbon-chlorine bonds.
- these reactions often do not go to completion and organic chlorine compounds remain in large quantities.
- hydrocarbon products for example synthetic crude oils or crude oil products. It is an object of the present invention to provide such methods. In particular, it is an object of the invention to provide methods which use Allow hydrocarbon mixtures containing high amounts of organically bound halogen or which allow a reduction in the content of organically bound halogen in the hydrocarbon product.
- the content of organically bound halogen in the hydrocarbon product can be significantly reduced if, during production, a hydrocarbon stream obtained from the starting material is brought into contact with nitrogen compounds in the gas phase.
- the added nitrogen compounds can enter into nucleophilic substitution reactions with the organic halogen compounds and thus split the carbon-halogen bonds.
- Organically bonded halogen is thus converted into halide ions, which can then be easily removed, for example by washing with an aqueous solution or by distillation.
- Carrying out the substitution reactions in the gas phase has the advantage, on the one hand, that the hydrocarbon stream is mixed particularly well with the nitrogen compounds and, on the other hand, that the substitution reactions proceed particularly efficiently and a short reaction time is made possible.
- the inventive method thus makes it possible to hydrocarbon mixtures with a high content of organically bound halogen than Use starting material and at the same time obtain hydrocarbon products with a low content of organically bound halogen.
- organically bound halogen is preferably understood to mean halogens which are present bound to carbon in chemical compounds.
- the content of organically bound halogen is preferably determined according to DIN EN 14077:2004-03.
- the content of organically bound halogen can also be determined according to DIN EN 14582:2016-12.
- ASTM D7359:2014 07 01 standard is also suitable for determining organically bound halogen, in particular organically bound fluorine and/or chlorine.
- the organically bound halogen is selected from organically bound fluorine, chlorine, bromine, iodine or mixtures thereof; particularly preferably chlorine, bromine, iodine or mixtures thereof; most preferably chlorine.
- the process according to the invention has proven to be particularly suitable for removing organic chlorine compounds.
- the hydrocarbon mixture contains at least 1 ppm, preferably at least 10 ppm, even more preferably at least 100 ppm, even more preferably at least 1000 ppm, even more preferably at least 2000 ppm, even more preferably at least 5000 ppm, even more preferably at least 10000 ppm, most preferably at least 15,000 ppm of organically bound halogen, in particular organically bound chlorine.
- the hydrocarbon mixture preferably contains from 1 ppm to 70,000 ppm, preferably from 10 ppm to 65,000 ppm, preferably from 100 ppm to 60,000 ppm, even more preferably from 1000 ppm to 50,000 ppm, even more preferably from 2000 ppm to 40,000 ppm from 5,000 ppm to 30,000 ppm, most preferably from 10,000 to 20,000 ppm of organically bound halogen, in particular organically bound chlorine.
- the hydrocarbon mixture preferably contains halohydrocarbons, preferably selected from haloalkanes, haloalkenes, aromatic halohydrocarbons and/or mixtures thereof. It is particularly preferred if Hydrocarbon mixture containing halogenated polymers, in particular PVC and/or PTFE.
- PVC can be found in different feedstocks for refinery processes.
- PVC plays an important role, for example, in the production of synthetic crude oil through the pyrolysis of plastic material, in particular waste plastic. Although some of the carbon-chlorine bonds can be broken by ⁇ -elimination during the pyrolysis process, these reactions usually do not go to completion and chlorine-containing alkenes are found in the products. In order to keep the content of organically bound chlorine in the pyrolysis oil low, the proportion of PVC in the starting material often has to be limited to lower values. In the course of the invention, it has been found that the chlorine-containing alkenes, which are formed as PVC degradation products in the pyrolysis process, can be implemented particularly efficiently in substitution reactions with the nitrogen compounds used.
- the process according to the invention makes it possible to use hydrocarbon mixtures with a high PVC content.
- plastic mixtures from electronic scrap recycling can be used, which typically contain high levels of organochlorine and organobromine, in particular PVC from cables, but also flame retardants such as hexabromocyclododecane (HBCD) or chlorinated paraffins.
- the hydrocarbon mixture therefore contains PVC, preferably at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight, even more preferably at least 0.2% by weight.
- the hydrocarbon mixture preferably contains from 0.001 to 10% by weight, preferably from 0.01 to 8% by weight, more preferably from 0.1 to 7.0% by weight, even more preferably from 0.2 to 6 5% by weight, even more preferably from 0.3 to 6.0% by weight, even more preferably from 0.4 to 5.5% by weight, even more preferably from 0.5 to 5.0% by weight % PVC.
- halogen-containing flame retardants Another source of organic halogen compounds, the can lead to problems in refinery processes are halogen-containing flame retardants.
- used plastics and other plastic mixtures often contain significant amounts of such flame retardants, which are subsequently found as organic halogen compounds in the pyrolysis oils obtained from the plastic mixtures.
- Flame retardants containing bromine are particularly widespread in this context, for example decabromodiphenyl ether (DecaBDE), which is added in considerable amounts to polyamides and polyolefins, or tetrabromobisphenol A (TBBPA), which is added to polyesters, among other things, or hexabromocyclododecane (HBCD) , which, for example, in insulation foams, such as EPS (expanded polystyrene foam) and XPS (extruded polystyrene foam), are used.
- the process according to the invention has also proven to be particularly well suited for removing organically bound halogen from halogen-containing flame retardants, in particular organically bound bromine.
- the hydrocarbon mixture therefore contains halogen-containing, preferably bromine-containing, flame retardants, preferably polybrominated diphenyl ethers and/or polybrominated biphenyls, particularly preferably decabromodiphenyl ether (DecaBDE), tetrabromobisphenol A (TBBPA) and/or hexabromocyclododecane (HBCD).
- halogen-containing, preferably bromine-containing, flame retardants preferably polybrominated diphenyl ethers and/or polybrominated biphenyls, particularly preferably decabromodiphenyl ether (DecaBDE), tetrabromobisphenol A (TBBPA) and/or hexabromocyclododecane (HBCD).
- DecaBDE decabromodiphenyl ether
- TBPA tetrabromobisphenol A
- HBCD hexabromocyclododecane
- Synthetic crude oil sometimes also referred to as syncrude
- the hydrocarbon product is a synthetic crude oil or a fraction thereof.
- the hydrocarbon mixture is a hydrocarbon mixture obtained from plastic material, in particular waste plastic.
- the hydrocarbon mixture is particularly preferably a plastic melt.
- the hydrocarbon mixture is a crude oil, preferably a fossil crude oil or a synthetic crude oil, in particular a pyrolysis oil.
- a crude oil preferably a fossil crude oil or a synthetic crude oil, in particular a pyrolysis oil.
- it may be a crude oil stream contaminated by halogenated solvents.
- the heating of the hydrocarbon mixture takes place in the course of a pyrolysis process, a hydrogenation process or a distillation process.
- This has the advantage that existing processes can be used to obtain the gaseous hydrocarbon stream. Existing processes can be economically supplemented with dosing of nitrogen compounds into the gas stream in order to reduce the content of organically bound halogens in the product.
- the gaseous hydrocarbon stream is the product stream of a Thermal Gasoil Unit (TGU) or a Fluid Catalytic Cracking (FCC) plant.
- TGU Thermal Gasoil Unit
- FCC Fluid Catalytic Cracking
- the hydrocarbon mixture is heated in the course of a pyrolysis process, preferably the pyrolysis of plastic material, for example as in FIG WO 2012/149590 A1 or the US 6,060,631A known.
- the hydrocarbon mixture is preferably heated to obtain a gaseous hydrocarbon stream at a temperature of at least 150° C., preferably at least 200° C., more preferably at least 250° C., even more preferably at least 300° C., even more preferably at least 350° C. most preferably at least 400°C.
- a temperature of at least 150° C. preferably at least 200° C., more preferably at least 250° C., even more preferably at least 300° C., even more preferably at least 350° C. most preferably at least 400°C.
- the temperature of the gaseous hydrocarbon stream when brought into contact with the composition containing the at least one nitrogen compound is at least 150° C., preferably at least 200° C., more preferably at least 250° C., even more preferably at least 300° C., most preferably at least 350oC.
- the temperature is preferably between 150° C. and 550° C., preferably between 200° C. and 500° C., more preferably between 200° C. and 480° C., even more preferably between 250° C. and 460° C., even more preferably between 300°C and 450°C.
- the temperature of the resulting gaseous mixture is at least 150°C, preferably at least 200°C, more preferably at least 250°C, even more preferably at least 300°C, most preferably at least 350°C.
- the temperature is preferably between 150° C. and 550° C., preferably between 200° C. and 500° C., more preferably between 200° C. and 480° C., even more preferably between 250° C. and 460° C., even more preferably between 300°C and 450°C.
- a high temperature of the gaseous mixture favors the course of nucleophilic substitution reactions. This has proven to be particularly advantageous in the removal of organic chlorine compounds since these are less reactive than organic bromine or iodine compounds.
- the nitrogen compounds can be metered in essentially in pure form, ie the composition can essentially consist of one or more nitrogen compounds.
- the composition containing the at least one nitrogen compound is an aqueous composition.
- an even more efficient removal of organically bound halogen can be achieved in this way.
- the water can evaporate quickly when brought into contact with the gaseous hydrocarbon stream and can lead to better mixing of the hydrocarbon stream and nitrogen compounds.
- the concentration of nitrogen compounds in the composition is between 5 and 80% by weight, preferably between 7 and 70% by weight, even more preferably between 10 and 50% by weight.
- a concentration in this range enables the substitution reactions to proceed efficiently.
- the composition is an aqueous composition, there is also a favorable ratio between nitrogen compounds and the water in this range for the nucleophilic substitution reactions to take place.
- the mass ratio between the gaseous hydrocarbon stream and the composition containing the at least one nitrogen compound is preferably at least 5:1, preferably at least 10:1, even more preferably at least 20:1, even more preferably at least 50:1, even more preferably at least 100:1 , more preferably at least 150:1.
- the mass ratio is preferably between 5:1 and 250:1, preferably between 10:1 and 200:1, even more preferably between 20:1 and 150:1, most preferably between 40:1 and 100:1. It has been shown that with such a mass ratio there is a sufficient amount of nitrogen compounds to ensure that the substitution reactions proceed efficiently, but at the same time the hydrocarbon stream is not diluted too much, so that the process can nevertheless be carried out particularly economically.
- the at least one nitrogen compound contained in the composition is preferably a nucleophilic nitrogen compound.
- the nitrogen compound is selected from the group consisting of primary amines, secondary amines, tertiary amines, ammonia and hydrazine.
- the nitrogen compound is preferably selected from the group consisting of diethanolamine, morpholine, dimethylamine, dithylamine, dipropylamine, diisopropylamine, ethyl-isopropylamine, piperidine, pyrrolidine, piperazine, ethanolamine, 2-methoxethylamine, 3-methoxypropylamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine, cyclohexylamine, decylamine, diaminoethane, diaminopropane, diaminobutane, diaminohexane, diaminocyclohexane, ammonia, hydrazine, trimethylamine, triethylamine, triethanolamine and tripropylamine.
- the composition can also contain mixtures of several different nitrogen compounds.
- the nitrogen compound is a primary or a secondary amine, in particular a secondary amine.
- good results have been achieved in particular with volatile amines. According to the inventors, without being bound to a theory, this can be explained by the fact that volatile amines enable a faster transition into the gas phase and thus better mixing with the hydrocarbon stream and that the high nucleophilicity of secondary amines leads to a faster flow of the leads to substitution reactions.
- the at least one nitrogen compound is therefore preferably a secondary amine.
- the nitrogen compound has a boiling point of less than 260°C, preferably less than 200°C, even more preferably less than 150°C, in particular less than 130°C. It is particularly preferred if the at least one nitrogen compound is a secondary amine with a boiling point of less than 260°C, preferably less than 200°C, even more preferably less than 150°C, in particular less than 130°C.
- volatile secondary amines preferably dimethylamine, diethylamine, dibutylamine and morpholine, in particular morpholine, have proven to be particularly suitable nitrogen compounds. Mixtures of primary amines, e.g. ethanolamine, with volatile secondary amines.
- the halide ions can preferably be separated off by washing with an aqueous washing solution. Due to their water solubility, halide ions or salts formed from them, e.g. amine hydrochloride, can migrate into the water phase and be separated out via it.
- the washing can be carried out, for example, in a mechanical mixer, in a static mixer and/or in a mixer-settler. Mixer-settlers have proven to be particularly well suited in this context, since the mixing of oil phase and aqueous washing solution and the subsequent settling process for separating the phases and separation of the cleaned oil phase can take place in a continuous process.
- the aqueous washing solution is a basic aqueous washing solution, preferably wherein the pH of the aqueous washing solution is at least 7.5, preferably at least 8, even more preferably at least 9, even more preferably at least 10, even more preferably at least 12, most preferably at least 13.
- the halide ions are separated off by distillation. This enables the halide ions to be removed particularly easily and at the same time thoroughly, since salts of the halide ions can simply be deposited in the bottom of the distillation.
- the process according to the invention makes it possible to obtain hydrocarbon products with a particularly low content of organically bound halogen.
- the hydrocarbon product contains less than 200 ppm, preferably less than 150 ppm, even more preferably less than 100 ppm, even more preferably less than 75 ppm, even more preferably less than 50 ppm, even more preferably less than 30 ppm, even more preferably less than 20 ppm, even more preferably less than 10 ppm, most preferably less than 5 ppm organically bound halogen, preferably organically bound halogen according to DIN EN 14077:2004-03.
- the hydrocarbon product is less than 200 ppm, preferably less than 150 ppm, even more preferably less than 100 ppm, even more preferably less than 75 ppm, even more preferably less than 50 ppm, even more preferably less than 30 ppm, even more preferably less than 20 ppm, even more preferably less than 10 ppm, most preferably less than 5 ppm of organically bound chlorine.
- Organically bound halogen or organically bound chlorine is preferably determined in accordance with DIN EN 14077:2004-03 or ASTM D7359:20140701.
- ppm parts per million on a mass basis (ppmw) unless otherwise indicated. 1 ppm as used herein corresponds to 0.0001% by weight.
- figure 1 shows a process flow diagram of a preferred embodiment of the process according to the invention.
- the hydrocarbon mixture 1 is a melt obtained from plastic material, preferably containing from 0.1 to 5% by weight of PVC.
- the plastic material is compacted in an extruder 7, degassed and melted.
- the plastic melt emerging from the extruder 7 is mixed in a static mixer 8 with an external solvent 9, preferably heavy oil, and/or with already pyrolyzed plastic material, which is returned as recycling stream 10, in order to reduce the viscosity of the plastic melt.
- the hydrocarbon mixture 1 thus obtained is heated in a depolymerization reactor 11, preferably to a temperature between 400° C. and 440° C., with the plastic material being depolymerized.
- a gaseous hydrocarbon stream 2 containing pyrolyzed plastic material is then recovered as the top product of a column 12 .
- the gaseous hydrocarbon stream 2 is subsequently produced with a composition 3 containing at least one nitrogen compound brought into contact to obtain a gaseous mixture 4.
- the temperature of the gaseous hydrocarbon stream 2 when brought into contact with the composition 3 is preferably at least 300°C.
- the composition 3 can be metered into the hot hydrocarbon stream 2 in liquid form, with the composition 3 evaporating rapidly, which enables thorough mixing with the hydrocarbon stream 2, in particular when the composition 3 is an aqueous composition.
- a gas stream 13 can be separated from the gaseous mixture 4 in a further column 14 .
- the material flow 15 obtained from this is mixed with an aqueous scrubbing solution 6 in a mixing zone of a mixer-settler 16, with chloride ions passing into the water phase.
- the cleaned oil phase is separated from the water phase in a settling zone of the mixer-settler 16. The water phase is removed as waste stream 17 and the oil phase is obtained as hydrocarbon product 5.
- Example 1 Production of synthetic crude oil with reduced content of organically bound halogen.
- test runs for the production of synthetic crude oil were carried out essentially as in figure 1 carried out as described.
- Plastic mixtures to which 0.5% by weight or 1% by weight PVC was added and which contained between 5 and 250 ppm bromine were used as the starting material.
- the plastic mixtures were as in figure 1 described extruded and cracked at a temperature between 400 ° C and 440 ° C.
- a gaseous hydrocarbon stream was removed as overhead product from a column downstream of the depolymerization reactor.
- an amine composition metered into the hydrocarbon stream.
- the temperature of the hydrocarbon stream when it was metered in was 370.degree.
- a solution of 10% by weight ethanolamine in water was used as the amine composition.
- the metered amount of the amine composition was 3 kg/h with a feed rate of 80 kg/h.
- the product obtained was washed and the content of organically bound chlorine and bromine in the organic phase was determined.
- Example 2 Comparative experiments with different nitrogen compounds.
- Example 3 Comparative experiments with different nitrogen compounds at higher temperatures.
- Example 2 In order to investigate the effect of the different nitrogen compounds at higher temperatures, the experiments described in Example 2 were carried out at a higher temperature.
- the starting material was placed in a pressure vessel with the respective amine (2% by weight) at room temperature and heated to 300° C. for 10 min. After cooling, the organic phase was washed with water and analyzed.
- nitrogen compound degree of substitution boiling point Result organically bound chlorine [ppm]) ethanolamine primary 170oC 15 dimethylamine secondary 7°C 2 morpholine secondary 129°C 4 diethanolamine secondary 269°C 8th
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EP21203750.1A EP4170003A1 (de) | 2021-10-20 | 2021-10-20 | Verfahren zur herstellung eines kohlenwasserstoffprodukts |
CN202280066073.3A CN118019828A (zh) | 2021-10-20 | 2022-10-20 | 用于生产烃产物的方法 |
PCT/EP2022/079152 WO2023067035A1 (de) | 2021-10-20 | 2022-10-20 | Verfahren zur herstellung eines kohlenwasserstoffprodukts |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6060631A (en) | 1997-06-23 | 2000-05-09 | Uop Llc | Process for the conversion of plastic to produce a synthetic crude oil |
US6329496B1 (en) * | 1998-07-29 | 2001-12-11 | Nippon Steel Corporation | Method for processing chlorine-containing organic compounds |
WO2012149590A1 (de) | 2011-05-05 | 2012-11-08 | Omv Refining & Marketing Gmbh | Verfahren und vorrichtung zur energieeffizienten aufbereitung sekundärer lagerstätten |
CN105001910B (zh) * | 2015-06-30 | 2016-09-28 | 洛阳瑞泽石化工程有限公司 | 一种组合式加氢处理轮胎裂解油的方法 |
CN112283712A (zh) * | 2020-10-21 | 2021-01-29 | 深圳市捷晶能源科技有限公司 | 一种含氯含溴固体废物热解系统 |
-
2021
- 2021-10-20 EP EP21203750.1A patent/EP4170003A1/de not_active Withdrawn
-
2022
- 2022-10-20 WO PCT/EP2022/079152 patent/WO2023067035A1/de active Application Filing
- 2022-10-20 CN CN202280066073.3A patent/CN118019828A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6060631A (en) | 1997-06-23 | 2000-05-09 | Uop Llc | Process for the conversion of plastic to produce a synthetic crude oil |
US6329496B1 (en) * | 1998-07-29 | 2001-12-11 | Nippon Steel Corporation | Method for processing chlorine-containing organic compounds |
WO2012149590A1 (de) | 2011-05-05 | 2012-11-08 | Omv Refining & Marketing Gmbh | Verfahren und vorrichtung zur energieeffizienten aufbereitung sekundärer lagerstätten |
CN105001910B (zh) * | 2015-06-30 | 2016-09-28 | 洛阳瑞泽石化工程有限公司 | 一种组合式加氢处理轮胎裂解油的方法 |
CN112283712A (zh) * | 2020-10-21 | 2021-01-29 | 深圳市捷晶能源科技有限公司 | 一种含氯含溴固体废物热解系统 |
Non-Patent Citations (2)
Title |
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BREBU ET AL: "Effect of flame retardants and Sb"2O"3 synergist on the thermal decomposition of high-impact polystyrene and on its debromination by ammonia treatment", JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, ELSEVIER BV, NL, vol. 79, no. 1-2, 19 April 2007 (2007-04-19), pages 346 - 352, XP022062380, ISSN: 0165-2370, DOI: 10.1016/J.JAAP.2007.02.003 * |
HINZ B ET AL: "Dehalogenation of pyrolysis products", JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, 1 January 1994 (1994-01-01), Amsterdam, pages 35 - 46, XP055907103, Retrieved from the Internet <URL:https://www.researchgate.net/publication/229288424_Dehalogenation_of_pyrolysis_products> [retrieved on 20220330], DOI: 10.1016/0165-2370(94)00800-0 * |
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CN118019828A (zh) | 2024-05-10 |
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