CN101591550A - Utilize waste polymer containing heteroatoms through cracking to prepare the method for fuel oil - Google Patents
Utilize waste polymer containing heteroatoms through cracking to prepare the method for fuel oil Download PDFInfo
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Abstract
The method that the present invention openly utilizes waste polymer containing heteroatoms through cracking to prepare fuel oil is to contain heteroatoms waste polymer, 10-250 part solvent, 0.1-10 part phase-transfer catalyst and 0.1-100 part basic cpd with 100 parts earlier to mix together, and is heated to 60-260 ℃ of reaction 10-120 minute; After then solvent being separated from reaction product, to remain solid product and catalyzer and count 1 by weight: the proportioning of 0.01-0.2 adds in the cracking reactor, at cracking pressure is under the 30-760mmHg, be heated to 200-700 ℃ of scission reaction 5-60 minute, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.The present invention is because before catalytic pyrolysis, adopted the degrading solvent method efficiently to remove heteroatoms earlier, thereby not only solved the problem that direct employing pyrolysis method exists effectively, help obtaining to have high-grade clean fuel oil, but also catalyzer is easily poisoned when having avoided thermo-cracking, life-span is short, problems such as regenerability difference.
Description
Technical field
The invention belongs to waste polymer and reclaim preparation fuel oil technical field, be specifically related to a kind of two-step approach of using, be that solvent edman degradation Edman and catalytic cracking solution are received back and forth and contained the novel method of heteroatoms waste polymer with the preparation fuel oil: earlier under the condition of gentleness, remove assorted element (N, Br, Cl, S etc.) in the system, will remove heteroatomic polymkeric substance again and carry out catalytic pyrolysis to produce fuel oil by degrading solvent.
Background technology
Energy and environment are the two principal themes that cause that the world today shows great attention to.Along with polymkeric substance in people's production, life widespread use and a large amount of waste polymers of thereupon bringing not only cause serious environmental to pollute, also cause the significant wastage of social resources simultaneously.
In order to eliminate the environmental pollution that waste polymer brings, make full use of these physical resources, at present, its method of handling roughly is divided into following four kinds: landfill method, burning method, regeneration method and thermochemical cycle.What wherein be considered to most worthy is thermochemical cycle, and this method is that waste polymer is carried out thermal destruction under inert atmosphere, finally obtains corresponding monomer or petroleum chemicals.
But waste polymer is a very complicated system, and it contains assorted element usually, as N, Br, Cl, S etc.As mainly by the waste polymer that electronic and electrical equipment produced of high-impact polystyrene (HIPS) and acrylonitrile-butadiene-styrene terpolymer preparations such as (ABS), in the cracked oil of its generation because of containing itrogenous organic substance, when acting as a fuel, it can produce HCN when using, objectionable impuritiess such as NOx can't be used the fuel oil that makes.In addition, because this series products all has higher requirement to flame retardant resistance, in order to reach fire-retardant purpose, all having added a certain amount of fire retardant man-hour mostly adding, is many with halogen-containing flame retardant wherein, as Polybrominated biphenyl, tetrabromo-bisphenol etc., thereby make bromine content in the goods up to 4-7wt%.Can produce hydrogen halide on the one hand when these contain the waste polymer cracking of halogen, severe corrosion equipment also can produce halogenous organic compound on the other hand, thereby the liquid that its cracking is generated acts as a fuel and can generate toxic gas when using.Therefore, brought great difficulty, become the technical barrier that solution is badly in need of in this field to these recovery that contain heteroatomic polymkeric substance.
At present, the research of investigator in this field has both at home and abroad obtained certain progress.As aspect the catalytic pyrolysis dehalogenation, adopted in system, to add single catalyst or composite catalyst, and be aided with technical measures such as different atmosphere (nitrogen, ammonia or air) and contact mode.What single catalyst adopted is metal oxide and its esters.Metal oxide comprises: alkaline earth metal oxide such as MgO, CaO, BaO etc.; Transition metal oxide such as Fe
2O
3, Co
2O
3, Ni
2O
3, La
2O
3, CeO
2, Nd
2O
3, TiO
2Deng; Other main group metal oxide compound such as Al
2O
3, (L.Tiikma, L.Johannes, H.Luik, J.Anal.Appl.Pyrolysis, 2006,206 (75): 205 such as PbO; Y.Masuda, J.Anal.Appl.Pyrolysis, 2006,160 (77): 159; J.Wootthikanokkhan, A.Jaturapiree, V.Meeyoo, J.Polym.Environ.2003,11 (1): 1).What composite catalyst mainly adopted is load carbon catalyzer and load oxide catalyst, as Ca-C, Fe-C, Ca-Zn, NiMo/Al
2O
3, (N.S.Vrandecic, I.Klaric, T.Kovacic, J.Thermal Anal.Calorimetry, 2003,74 (1): 171 such as metalloscene catalyst and compound solid-acid FSZ; S.L.Gupte, N.Agarwal, G.Madras, K.Nagaveni, M.S.Hegde.J.Appl.Polym.Sci., 2003,90 (13): 3532; T.Bhaskar T.Matsui, J.Kaneko, Greem Chem., 2002,4 (4): 372; M.Brebu, E.Jakab, Y.Sakata, J.Anal.Appl.Pyrolysis, 2007,79 (1-2), 346); M.Brebu, M.A.Uddin, A.Muto, Y.Sakata, C.Vasile, J.Anal.Appl.Pyrolysis, 2002,63 (1): 43).Although obtained certain progress by the pyrolysis method recovery, well remove heteroatomic effect but still can not reach, make the fuel oil that makes can't satisfy the standard of fuel oil.In addition, catalyzer exists easily poisons, and the life-span is short, problems such as regenerability difference, and this has become current obstruction cracking process and has reclaimed the key issue that contains the heteroatoms waste polymer.
In polymer recovery, except passing through pyrolysis method, existing investigator also attempts adopting the degrading solvent method to carry out the dehalogenation reaction, and also adopt some subsidiary conditions to carry out simultaneously, as microwave (M.Ito, K.Ushida, N.Nakao, Polym.Degrad.Stab., 2006,91 (8): 1694), overcritical (A.J.M.Lagadec, S.B.Hawthorne, Envioron.Sci.﹠amp; Tech., 2002,36 (6): 1337) etc.Adopt degrading solvent method dehalogenation can not only effectively avoid pyrolysis method need add efficient catalytic agent and complicated catalysis dehalogenation technology, and because degrading solvent method and unlike thermo-cracking, follow free radical reaction course dehalogenation, but carry out with ionic species, thereby its dehalogenation reaction activation energy is significantly less than thermo-cracking dehalogenation reaction activation energy, makes dehalogenation easier.As Mihai Brebu etc. (M.Brebu, T.Bhaskar, A.Muto, Y.Sakata, Chemosphere, 2006,64:1021) adopt the debrominate of hot alkaline solution method, obtained higher debrominate rate; (M.Saburo such as Saburo Moriwaki, M.Motoi, T.Hideki, Appl.Thermal Eng., 2006,26 (7): 745) studied the dechlorination situation of PVC in commercial microwave oven, found that microwave absorbing subsidiary such as gac and iron can promote PVC dechlorination and decomposition effectively, the dechlorination rate of discarded PVC can reach more than 90% under microwave condition.
Although the degrading solvent method has above advantage, main chain is not contained heteroatomic polymkeric substance, adopt degrading solvent method polymer pyrolysis effectively; And, then needing higher temperature and pressure if will make the further cracking of polymkeric substance generate micromolecular compound, this needs special reaction unit to bear high temperature and high pressure.On the other hand, higher to remove the then required reaction times of heteroatomic degree longer if will reach under the condition of gentleness, and efficient is lower; And, then need higher temperature and pressure again if will rapidly and efficiently remove heteroatoms, conversion unit is had relatively high expectations.
Summary of the invention
The objective of the invention is the problem at the prior art existence, a kind of method of utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil is provided, this method can improve efficient and the quality product for preparing fuel oil from waste polymer containing heteroatoms through cracking.
The method of utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil that present method provides is the two-step approach that adopts, promptly earlier under the condition of gentleness, remove assorted element in the system by the degrading solvent method, to remove the further catalytic pyrolysis of polymkeric substance behind the heteroatoms again to produce fuel oil, its concrete steps are as follows:
Earlier contain heteroatoms waste polymer, 10-250 part solvent, 0.1-10 part phase-transfer catalyst and 0.1-100 part basic cpd and mix together, and be heated to 60-260 ℃ of reaction 10-120 minute 100 parts; After then solvent being separated from reaction product, to remain solid product and catalyzer and count 1 by weight: the proportioning of 0.01-0.2 adds in the cracking reactor, at cracking pressure is under the 30-760mmHg, be heated to 200-700 ℃ of scission reaction 5-60 minute, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Wherein non-condensable gases is mainly low molecular hydrocarbon class material, and use can directly act as a fuel; Resulting fuel oil can further obtain various oil products (gasoline, diesel oil, mink cell focus) or important organic chemical industry's product by known chemical separating method; The residue that the reaction cracking generates can obtain carbon black by known method.
Cracking reactor used during above method cracking is for chemical reactor commonly used, as tank reactor, fixed-bed reactor or fluidized-bed reactor.
Above method directly contacts with solid product at the cracking process reacting middle catalyst, or contacts with the splitting gas of solid product cracking generation.
The used solvent of above method is a water, 1, at least a in 4-dioxane, methyl alcohol, ethanol, acetone, toluene, chloroform, methyl-sulphoxide, dimethyl formamide, tetrahydrofuran (THF), acetonitrile and the hexamethylphosphoramide.
The used phase-transfer catalyst of above method is an ethylene glycol, triglycol, glycerol, tetramethylolmethane, polyoxyethylene glycol, the polypropylene glycol polytetrahydrofuran, tetrahydrofuran (THF)-propylene oxide copolymerization glycol, dodecyl dimethyl benzyl ammonium chloride, the two octadecyl Dimethyl Ammonium of bromination, octadecyl dimethyl hydroxyethyl ammonium nitrate, tetra methylol sulfuric acid phosphorus, the semi-annular jade pendant Thiacalixarene, to tertiary butyl aromatic hydrocarbons, 1-alkyl-3-Methylimidazole hexafluorophosphate, 1-alkyl-3-methyl imidazolium tetrafluoroborate, chlorination 1-butyl-3-Methylimidazole villaumite, hydroxide 1-butyl-3-methylimidazole salt, chlorination 1-allyl group-3-Methylimidazole, at least a in hydroxide 1-(2-hydroxyethyl)-3-Methylimidazole and chlorination 1-(2-the hydroxyethyl)-3-Methylimidazole.
The used basic cpd of above method is at least a in lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, sodium methylate, potassium ethylate, potassium tert.-butoxide, phenyl lithium and the lithium diisopropyl amido.
The used catalyst for cracking of above method is at least a in type ZSM 5 molecular sieve, Y zeolite, X type molecular sieve, amorphous aluminum silicate, carclazyte, polynite, magnesium oxide, calcium oxide, ferric oxide, iron-carbon composite oxides, calcium-carbon composite oxides and the metallocene catalyst.
Compared with the prior art the present invention has following positively effect:
1, since the present invention before adopting catalytic pyrolysis, adopted the degrading solvent method efficiently to remove heteroatoms earlier, thereby solved a series of problems such as organic compound that contain heteroatoms (nitrogen, halogen, sulphur etc.) that can generate large amount of complex when direct employing pyrolysis method recovery contains the heteroatoms spent high molecular material effectively, help obtaining to have high-grade clean fuel oil.
2, since the present invention when adopting the degrading solvent method to remove heteroatoms, in reaction system, added phase-transfer catalyst efficiently, thereby both guaranteed to react and under mild conditions, to have carried out, can have the high heteroatomic efficient that removes again simultaneously, also avoided using expensive high temperature high voltage resistant reaction unit, had more security and economy.
3, because the present invention removes the heteroatoms in the polymkeric substance before catalytic pyrolysis, thereby catalyzer is easily poisoned when having avoided thermo-cracking, the life-span is short, problems such as regenerability difference.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the content of the invention described above to the present invention, still belongs to protection scope of the present invention.
Embodiment 1
Earlier contain heteroatoms waste polymer, 250 part 1 with 100 parts, 4-dioxane, 10 parts of triglycols, 100 parts of potassium hydroxide mix together, and are heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, to remain solid product and catalyst oxidation iron in 1: 0.2 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 500 ℃ of scission reactions 30 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 86.9%, and the fuel oil results of elemental analyses sees Table.
Embodiment 2
Earlier containing heteroatoms waste polymer, 50 parts of ethanol, 0.5 part of polyoxyethylene glycol, 0.5 part of potassium tert.-butoxide with 100 parts mixes together, and is heated to 60 ℃ of reactions 120 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer iron-carbon composite oxides and ferric oxide (Fe-C: ferric oxide=1: 1, weight ratio) in 1: 0.05 proportioning adding cracking reactor, under cracking pressure 500mmHg, be heated to 450 ℃ of scission reactions 40 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 72.6%, and the fuel oil results of elemental analyses sees Table.
Embodiment 3
Earlier containing heteroatoms waste polymer, 50 parts of ethanol, 200 parts of water, 10 parts of polyoxyethylene glycol, 30 parts of magnesium hydroxides, 30 parts of potassium hydroxide, 40 parts of sodium hydroxide with 100 parts mixes together, and is heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer X type molecular sieve in 1: 0.1 proportioning adding cracking reactor, under cracking pressure 30mmHg, be heated to 200 ℃ of scission reactions 60 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 63.8%, and the fuel oil results of elemental analyses sees Table.
Embodiment 4
Earlier contain heteroatoms waste polymer, 50 part 1 with 100 parts, 4-dioxane, 1 part of triglycol, 4 parts of polyoxyethylene glycol, 50 parts of potassium hydroxide mix together, and are heated to 260 ℃ of reactions 10 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer amorphous aluminum silicate and iron-carbon composite oxides (amorphous aluminum silicate: iron-carbon composite oxides=1: 1, weight ratio) in 1: 0.05 proportioning adding cracking reactor, under cracking pressure 200mmHg, be heated to 350 ℃ of scission reactions 50 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 72.7%, and the fuel oil results of elemental analyses sees Table.
Embodiment 5
Earlier containing heteroatoms waste polymer, 50 parts of methyl alcohol, 10 parts of ethylene glycol, 50 parts of hydrated bartas with 100 parts mixes together, and is heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer calcium-carbon composite oxides and iron-carbon composite oxides (calcium-carbon composite oxides: iron-carbon composite oxides=1: 1, weight ratio) in 1: 0.2 proportioning adding cracking reactor, under cracking pressure 200mmHg, be heated to 350 ℃ of scission reactions 50 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 71.5%, and the fuel oil results of elemental analyses sees Table.
Embodiment 6
Earlier containing heteroatoms waste polymer, 100 parts of methyl-sulphoxides, 1 part of tetra methylol sulfuric acid phosphorus, 50 parts of sodium hydroxide, 50 parts of potassium hydroxide with 100 parts mixes together, and is heated to 200 ℃ of reactions 10 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer amorphous aluminum silicate in 1: 0.02 proportioning adding cracking reactor, under cracking pressure 500mmHg, be heated to 450 ℃ of scission reactions 40 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 77.9%, and the fuel oil results of elemental analyses sees Table.
Embodiment 7
Earlier containing heteroatoms waste polymer, 10 parts of chloroforms, 5 parts of tetramethylolmethanes, 5 parts of lithium hydroxides with 100 parts mixes together, and is heated to 120 ℃ of reactions 60 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer bis cyclopentadienyl zirconium dichloride in 1: 0.05 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 550 ℃ of scission reactions 30 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 84.7%, and the fuel oil results of elemental analyses sees Table.
Embodiment 8
Earlier with 100 parts contain the heteroatoms waste polymer, 150 parts of toluene, 0.1 part of hydroxide 1-(2-hydroxyethyl)-3-Methylimidazole, 0.1 part of phenyl lithium mix together, and are heated to 100 ℃ of reactions 60 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer Y zeolite in 1: 0.01 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 600 ℃ of scission reactions 10 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 78.8%, and the fuel oil results of elemental analyses sees Table.
Embodiment 9
Earlier containing heteroatoms waste polymer, 200 parts of water, 2 parts of triglycols, 2 parts of polyoxyethylene glycol, 1 part of polypropylene glycol polytetrahydrofuran, 100 parts of calcium hydroxides with 100 parts mixes together, and is heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer polynite in 1: 0.05 proportioning adding cracking reactor, under cracking pressure 200mmHg, be heated to 350 ℃ of scission reactions 50 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 76.2%, and the fuel oil results of elemental analyses sees Table.
Embodiment 10
Earlier containing heteroatoms waste polymer, 100 parts of acetonitriles, 1 part of 1-alkyl-3-Methylimidazole hexafluorophosphate, 50 parts of magnesium hydroxides with 100 parts mixes together, and is heated to 200 ℃ of reactions 10 minutes; After then solvent being separated from reaction product, to remain solid product and catalyst oxidation iron, iron-carbon composite oxides and polynite (ferric oxide: iron-carbon composite oxides: polynite=4: 3: 3, weight ratio) in 1: 0.05 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 700 ℃ of scission reactions 5 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 82.3%, and the fuel oil results of elemental analyses sees Table.
Embodiment 11
Earlier containing heteroatoms waste polymer, 70 parts of acetone, 70 parts of ethanol, 10 parts of tetrahydrofuran (THF)s, 5 parts of glycerol, 100 parts of sodium hydroxide with 100 parts mixes together, and is heated to 260 ℃ of reactions 10 minutes; After then solvent being separated from reaction product, to remain solid product and catalyzer Y zeolite in 1: 0.2 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 500 ℃ of scission reactions 30 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 85.1%, and the fuel oil results of elemental analyses sees Table.
Comparative Examples 1
Containing the heteroatoms waste polymer with 100 parts joins in the cracking reactor, under cracking pressure 760mmHg, be warming up to 500 ℃ and carried out scission reaction 30 minutes, the gas of its generation passes through condenser, be separated into non-condensable gases and fuel oil, resulting fuel oil yield is 87.4%.The fuel oil results of elemental analyses sees Table.
Comparative Examples 2
Earlier contain heteroatoms waste polymer, 250 part 1 with 100 parts, 4-dioxane, 100 parts of potassium hydroxide mix together, and are heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, to remain solid product and catalyst oxidation iron in 1: 0.2 proportioning adding cracking reactor, under cracking pressure 760mmHg, be heated to 500 ℃ of scission reactions 30 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 80.1%, and the fuel oil results of elemental analyses sees Table.
Comparative Examples 3
Earlier contain heteroatoms waste polymer, 250 part 1 with 100 parts, 4-dioxane, 10 parts of triglycols, 100 parts of potassium hydroxide mix together, and are heated to 160 ℃ of reactions 30 minutes; After then solvent being separated from reaction product, will remain solid product and add in the cracking reactor, and under cracking pressure 760mmHg, be heated to 500 ℃ of scission reactions 30 minutes, the gas of its generation is separated into non-condensable gases and fuel oil by condenser.Gained fuel oil yield is 40.5%, and the fuel oil results of elemental analyses sees Table.
Table
| Cl(wt.％) | Br(wt.％) | N(wt.％) | S(wt.％) | |
| Embodiment 1 | 0.0000 | 0.0000 | 0.0000 | 0.0000 |
| Embodiment 2 | 0.0000 | 0.0000 | 0.0010 | 0.0010 |
| Embodiment 3 | 0.0000 | 0.0000 | 0.0005 | 0.0005 |
| Embodiment 4 | 0.0000 | 0.0000 | 0.0005 | 0.0005 |
| Embodiment 5 | 0.0010 | 0.0005 | 0.1000 | 0.0010 |
| Embodiment 6 | 0.0010 | 0.0005 | 0.1000 | 0.0010 |
| Embodiment 7 | 0.0010 | 0.0005 | 0.0010 | 0.0010 |
| Embodiment 8 | 0.0005 | 0.0005 | 0.1000 | 0.0005 |
| Embodiment 9 | 0.0000 | 0.0000 | 0.0005 | 0.0005 |
| Embodiment 10 | 0.0005 | 0.0005 | 0.1000 | 0.0010 |
| Embodiment 11 | 0.0000 | 0.0000 | 0.0005 | 0.0005 |
| Comparative Examples 1 | 6.5000 | 4.9000 | 0.5000 | 1.0000 |
| Comparative Examples 2 | 2.1000 | 1.2000 | 0.4000 | 0.6000 |
| Comparative Examples 3 | 0.0000 | 0.0000 | 0.0005 | 0.0005 |
Claims (8)
1, a kind of method of utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil, this method is to contain heteroatoms waste polymer, 10-250 part solvent, 0.1-10 part phase-transfer catalyst and 0.1-100 part basic cpd with 100 parts earlier to mix together, and is heated to 60-260 ℃ of reaction 10-120 minute; After then solvent being separated from reaction product, to remain solid product and catalyzer and count 1 by weight: the proportioning of 0.01-0.2 adds in the cracking reactor, at cracking pressure is under the 30-760mmHg, be heated to 200-700 ℃ of scission reaction 5-60 minute, the gas of its generation passes through condenser, be separated into non-condensable gases and fuel oil
The umber of the above material is weight part.
2, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 1, the used solvent of this method is a water, 1, at least a in 4-dioxane, methyl alcohol, ethanol, acetone, toluene, chloroform, methyl-sulphoxide, dimethyl formamide, tetrahydrofuran (THF), acetonitrile and the hexamethylphosphoramide.
3, the method of utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 1 and 2, the used phase-transfer catalyst of this method is an ethylene glycol, triglycol, glycerol, tetramethylolmethane, polyoxyethylene glycol, the polypropylene glycol polytetrahydrofuran, tetrahydrofuran (THF)-propylene oxide copolymerization glycol, dodecyl dimethyl benzyl ammonium chloride, the two octadecyl Dimethyl Ammonium of bromination, octadecyl dimethyl hydroxyethyl ammonium nitrate, tetra methylol sulfuric acid phosphorus, the semi-annular jade pendant Thiacalixarene, to tertiary butyl aromatic hydrocarbons, 1-alkyl-3-Methylimidazole hexafluorophosphate, 1-alkyl-3-methyl imidazolium tetrafluoroborate, chlorination 1-butyl-3-Methylimidazole villaumite, hydroxide 1-butyl-3-methylimidazole salt, chlorination 1-allyl group-3-Methylimidazole, at least a in hydroxide 1-(2-hydroxyethyl)-3-Methylimidazole and chlorination 1-(2-the hydroxyethyl)-3-Methylimidazole.
4, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 1 and 2, the used basic cpd of this method are at least a in lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, sodium methylate, potassium ethylate, potassium tert.-butoxide, phenyl lithium and the lithium diisopropyl amido.
5, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 3, the used basic cpd of this method are at least a in lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, sodium methylate, potassium ethylate, potassium tert.-butoxide, phenyl lithium and the lithium diisopropyl amido.
6, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 1 and 2, the used catalyst for cracking of this method are at least a in type ZSM 5 molecular sieve, Y zeolite, X type molecular sieve, amorphous aluminum silicate, carclazyte, polynite, magnesium oxide, calcium oxide, ferric oxide, iron-carbon composite oxides, calcium-carbon composite oxides and the metallocene catalyst.
7, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 3, the used catalyst for cracking of this method are at least a in type ZSM 5 molecular sieve, Y zeolite, X type molecular sieve, amorphous aluminum silicate, carclazyte, polynite, magnesium oxide, calcium oxide, ferric oxide, iron-carbon composite oxides, calcium-carbon composite oxides and the metallocene catalyst.
8, the method for utilizing waste polymer containing heteroatoms through cracking to prepare fuel oil according to claim 5, the used catalyst for cracking of this method are at least a in type ZSM 5 molecular sieve, Y zeolite, X type molecular sieve, amorphous aluminum silicate, carclazyte, polynite, magnesium oxide, calcium oxide, ferric oxide, iron-carbon composite oxides, calcium-carbon composite oxides and the metallocene catalyst.
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| CN116240042A (en) * | 2023-03-11 | 2023-06-09 | 中国石油化工股份有限公司 | Method and device for producing olefin by catalytic pyrolysis of waste plastics |
| CN116651493A (en) * | 2023-07-25 | 2023-08-29 | 上海大学 | Catalyst for recycling waste lithium batteries, preparation method and application |
| CN116651493B (en) * | 2023-07-25 | 2023-10-10 | 上海大学 | Catalyst for recycling waste lithium batteries, preparation method and application |
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