CN1190269C - Catalyst for cracking waste plastics to generate fuel - Google Patents
Catalyst for cracking waste plastics to generate fuel Download PDFInfo
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- CN1190269C CN1190269C CNB031179355A CN03117935A CN1190269C CN 1190269 C CN1190269 C CN 1190269C CN B031179355 A CNB031179355 A CN B031179355A CN 03117935 A CN03117935 A CN 03117935A CN 1190269 C CN1190269 C CN 1190269C
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Abstract
The present invention provides a catalyst for producing fuel oil by cracking waste plastics. The present invention is characterized in that the catalyst is DeLaZSM-5 by modifying ZSM-5 zeolite molecular sieves according to the method disclosed by the present invention, or is composed of the active components of at least two kinds of metal oxide loaded on a carrier, and takes the weight of the catalyst as reference. The present invention is a composite cracking catalyst with the purity of 5 to 50%. The present invention has high catalytic activity, short reaction time and low cracking temperature when the present invention is used for cracking waste plastics, and can greatly lower production cost. The fuel oil produced by the present invention has high integrative yield more than 80%, pure colors and good quality. Gasoline can reach the national standard of 70# to 90# gasoline. Diesel oil can reach the national standard of 0# to-35# diesel oil. The cracking catalyst containing the metal oxide provided by the present invention has catalytic cracking functions and dehalogenation functions, can make oil products obtained have no organic halogen, and can not discharge halogenated hydrogen gas which erodes apparatus in the process of cracking.
Description
One, technical field
The invention belongs to catalyst technical field, be specifically related to a kind of cracking waste plastics that is used for to produce the catalyst of fuel oil.
Two, background technology
The needs of environmental protection are not only in the processing of waste or used plastics, also utilize for reasonable resources simultaneously again and have opened up an important channel.The processing of waste or used plastics at present roughly is divided into following four kinds of methods: landfill method, burning method, regeneration method and chemical cycle method.Wherein the chemical cycle method is to utilize light, heat, radiation, chemical reagent etc. to make the waste or used plastics depolymerization become monomer or oligomer.Catabolite is that monomer can be used for synthetic new polymer, and catabolite is that oligomer can be used as oil product, and can not cause atmosphere pollution in the production process, so this kind technology is considered to the most promising waste plastics recovery method.
The main mode of chemical cycle method is to utilize heat energy that waste plastics is carried out cracking.Cracking process is divided into thermal cracking and catalytic pyrolysis.Because the catalytic cracking reaction temperature is low, the added value of product height be the emphasis of studying both at home and abroad at present, and the effect of catalytic pyrolysis is owing to the catalyst that depends primarily on use, so actual the concentrating on the catalyst of emphasis of research.
At present, using in treatment of waste plastics has solid acid catalyst comparatively widely, and that wherein the most frequently used is amorphous aluminosilicate (SA) (H.Ohkita; R.Nishiyama; Y.Tochihara, et al.Ind.Eng.Chem.Res.1993,32:3112); Various types of molecular sieve zeolites, as HZSM-5, USY, REY and CaX (G.Manos, A.Garforth, J.Dwyer, Ind.Eng.Chem.Res.2000,39:1198); (Y.Uemichi such as Uemichi; Y.Kashiwaya; A.Ayame.et al.Chem.Lett.1984,41) active carbon that adopts.There is document to report some new catalysts successively in the recent period, as MCM-41, SAPO-37, KFS-16, (the J.Aguada such as catalyst for cracking that discard in H-gallosilicate, cross-linked montmorillonite, using natural clinoptilolite and the oil factory, J.L.Sctelo, D.P.Serrano, et al.Energy.Fuels, 1997,11:1225; G.J.T.Fernandes, V.J.Fernandes, Jr.A.S.Araujo, Catalysis.Today, 2002,75:233; Y.Sakata; M.A.Uddin; A.Muto, et al.J.Anal.Appl.Pyrolysis.1997,43:15; Y.Uemichi, T.Suzuki.Chem.Lett.1999,1137-1138; G.Manos, I.Y.Yusof, N.H.Gangas, et al.Energy.Fuels.2002,16 (2): 485; J.R.Kim, Y.A.Kim, J.-H.Yoon, et al.Polym.Degrad.Stab.2002,75:287.S.C.Cardona, A.corma.Appl.Catal B Environ, 2000,25:151).In addition, (S.Nishio.Ind.Eng.Chem.Res.1995 34:4514), and takes by weighing certain catalytic pyrolysis effect for Z.Zhang, T.Hirose to also have bibliographical information to adopt solid base catalyst.
Though existing catalyst is various in style, also obtained corresponding catalytic pyrolysis effect separately, however the service test result who carries out from the inventor, still there is following problem in above-mentioned catalyst:
1, activity of such catalysts is lower, and the reaction time is long, the reaction temperature height, and oil quality is not high, yield is low.
2, the function singleness of catalyst only has the function of catalytic pyrolysis, when handling complicated component, when wherein containing the waste plastics of halogen, not only can emit hydrogen halide, etching apparatus in the cracking process; The oil product that cracking is generated contains more organic halogen material, does not reach the standard of fuel oil.
Three, summary of the invention
The objective of the invention is the deficiency at existing cracking waste plastics catalyst, a kind of high lytic activity that has is provided, the reaction time is short, and reaction temperature is low, can improve the catalyst of the efficient and the product quality of cracking waste plastics system fuel oil.
Another object of the present invention provide a kind of have high lytic activity and dehalogenation function simultaneously be used for cracking waste plastics to produce the catalyst of fuel oil.
Be used for cracking waste plastics to produce the catalyst of fuel oil for what the last purpose of the present invention provided, it is characterized in that this catalyst prepares by the following method, promptly in the ZSM-5 zeolite molecular sieve, add the Na of 0.1～2M by 1: 1～100 weight ratio
2CO
3Solution was in 40-120 ℃ of reaction 2～10 hours; Leave standstill after the reaction and incline and supernatant liquor, add the Na of 0.1～2M again by 1: 1～100 weight ratio again
2CO
3Solution in 40～120 ℃ of reactions 2～10 hours, filters, with 100～3000 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; In the solid of drying, add 10～1000 parts of deionized waters then,, filter in 40～120 ℃ of reactions 2～10 hours, with 100～3000 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; Dried solid again in 300～600 ℃ of activation 8～24 hours, is promptly made DeZSM-5; With the DeZSM-5 that makes 10-100 part 0.1～2MLaCl
3, down carried out ion-exchange 5～60 minutes in 40～120 ℃ with the radiation of 2450MHz microwave, exchange is afterwards washed La to the cleaning solution with boiling water
3+Detection is zero, then in 120 ℃ dry 12 hours down, again in 300～600 ℃ down activation promptly made DeLaZSM-5 in 5～24 hours.
Wherein the ZSM-5 zeolite molecular sieve can be any in HZSM-5 zeolite molecular sieve or the NaZSM-5 zeolite molecular sieve.
Be used for cracking waste plastics to produce the catalyst of fuel oil for what another purpose of the present invention provided, it is characterized in that this catalyst is is that active component constitutes to be carried on the carrier by at least a metal oxide, with the catalyst weight is benchmark, and its content is 5～50%.
Wherein metal oxide is raw materials such as employing nitrate, in the preparation feedback process, generate, be specially zinc oxide, cupric oxide, iron oxide, nickel oxide, magnesia, oxidation Cobalt, manganese oxide, vanadium oxide, titanium oxide, calcium oxide, barium monoxide, lanthana, aluminium oxide, silica.Carrier is DeLaZSM-5, silica, activated carbon, aluminium oxide, silicon aluminium microsphere, CaX, NaY, USY, NaZSM-5, HZSM-5, MCM-41, SAPO-37, KFS-16, any in H-gallosilicate, using natural clinoptilolite, kaolin, imvite, the cross-linked montmorillonite.
The preparation method specifically can adopt any of coprecipitation, infusion process, microwave solid reaction process, and these methods are
Prior art.
The present invention compared with prior art, its advantage is:
1, since cracking waste plastics catalyst provided by the invention active high, have an excellent catalytic pyrolysis function, thereby when being used for cracking waste plastics not only the reaction time short, only need 10～60 minutes, and cracking temperature is low, under 100～300 ℃, get final product, greatly reduce production cost.
2, contain the metal oxide catalyst for cracking except that having the catalytic pyrolysis function owing to provided by the invention, also has the dehalogenation function simultaneously, not only can make the organic halogen content of the oil product that obtains behind the cracking waste plastics is zero, and also can not emit hydrogen halide, etching apparatus in the cracking process.
3, use the comprehensive yield height of producing behind the cracking waste plastics catalyst provided by the invention of fuel oil, all more than 80%, and color is pure, and is superior in quality, and gasoline can reach the national standard of 70～90# gasoline, and diesel oil can reach 0～-national standard of 35# diesel oil.
Four, the specific embodiment
Provide embodiment below so that the present invention is carried out concrete description.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment one:
(1) preparation of catalyst DeLaZSM-5: the Na that in 10 parts of HZSM-5 zeolite molecular sieves, adds 10 parts of 0.8M
2CO
3Solution was in 80 ℃ of reactions 4 hours; Leave standstill after the reaction and incline and supernatant liquor, add the Na of 10 parts of 0.8M more again
2CO
3Solution in 80 ℃ of reactions 4 hours, filters, with 100 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; In the solid of drying, add 10 parts of deionized waters then,, filter in 80 ℃ of reactions 2 hours, with 100 parts of deionized waters washings, in 120 ℃ dry 12 hours down, and activate 24 hours down in 360 ℃, promptly make DeZSM-5.With the DeZSM-5 that makes with 10 parts of 0.8M LaCl
3Carried out ion-exchange 30 minutes with the radiation of 2450MHz microwave down in 100 ℃.Wash La to the cleaning solution with boiling water
3+Detection is zero, then in 120 ℃ dry 12 hours down, again in 600 ℃ down activation promptly made DeLaZSM-5 in 5 hours.
(2) cracking waste plastics oil-producing technique: waste plastics is cleaned, pulverizes, after the drying, presses waste plastics weight and add 5% above-mentioned catalyst for cracking, drop in the reactor, be warming up to 300 ℃ then and carry out cracking reaction.The fuel oil that generates during reaction and carries out categorised collection by the boiling point of product to oil product outside pipeline transfers out still.Wherein 160-180 ℃ product is collected as gasoline, and 350-380 ℃ product is collected as diesel oil.The cracking product adopts sodium hydroxide solution to carry out the alkali cleaning processing, the concentrated sulfuric acid carries out pickling processes after condenser is cooled to 25 ℃ successively.Add weight ratio in the gasoline after processing and be 5% dimethyl carbonate and modulate, improve octane number.Add earlier weight ratio in the diesel oil after processing and be 0.1% cetane number improver, and then to add weight ratio be that 2 ‰ diesel pour inhibitor carries out pour point depression and handles.
Embodiment two:
(1) preparation of catalyst DeLaZSM-5: the Na that in 10 parts of NaZSM-5 zeolite molecular sieves, adds 500 parts of 2M
2CO
3Solution was in 120 ℃ of reactions 2 hours.Leave standstill after the reaction and incline and supernatant liquor, add the Na of 500 part of 2 M more again
2CO
3Solution in 120 ℃ of reactions 2 hours, filters, with 1500 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; In the solid of drying, add 500 parts of deionized waters then,, filter in 120 ℃ of reactions 2 hours, with 1500 parts of deionized waters washings, in 120 ℃ dry 12 hours down, and activate 10 hours down in 450 ℃, promptly make DeZSM-5; With the DeZSM-5 that makes with 50 parts of 2M LaCl
3Down carried out ion-exchange 5 minutes with the radiation of 2450MHz microwave in 80 ℃, exchange is afterwards washed La to the cleaning solution with boiling water
3+Detection is zero, then in 120 ℃ dry 12 hours down, again in 300 ℃ down activation promptly made DeLaZSM-5 in 24 hours.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that the above-mentioned catalyst for cracking of pressing waste plastics weight adding 20%, and all the other are identical with embodiment one, do not state so omit.
Embodiment three:
(1) preparation of catalyst DeLaZSM-5: the Na that in 10 parts of NaZSM-5 zeolite molecular sieves, adds 1000 parts of 0.1M
2CO
3Solution was in 40 ℃ of reactions 10 hours.Leave standstill after the reaction and incline and supernatant liquor, add the Na of 1000 parts of 0.1M more again
2CO
3Solution in 40 ℃ of reactions 10 hours, filters, with 3000 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; In the solid of drying, add 1000 parts of deionized waters then,, filter in 40 ℃ of reactions 10 hours, with 3000 parts of deionized waters washings, in 120 ℃ dry 12 hours down, and activate 8 hours down in 550 ℃, promptly make DeZSM-5; With the DeZSM-5 that makes with 100 parts of 0.1MLaCl
3Down carried out ion-exchange 5 minutes with the radiation of 2450MHz microwave in 120 ℃, exchange is afterwards washed La to the cleaning solution with boiling water
3+Detection is zero, then in 120 ℃ dry 12 hours down, again in 450 ℃ down activation promptly made DeLaZSM-5 in 15 hours.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that the above-mentioned catalyst for cracking of pressing waste plastics weight adding 10%, and all the other are identical with embodiment one, do not state so omit.
Embodiment four:
(1) coprecipitation prepares compound catalyst for cracking: take by weighing 50 parts of aluminum nitrates and 50 parts of zinc nitrates, with two kinds of nitrate mixed dissolutions in 200 parts of deionized waters; This solution splashed into slowly in the beaker that ammoniacal liquor is housed (amount of ammoniacal liquor with guarantee in precipitation process and afterwards ageing process in PH to remain at 9 or more be a surname) make it to precipitate, to precipitate then and ageing of solution filtered after 16 hours, taking precipitate was dried 72 hours down at 120 ℃, again 250 ℃ of following preheatings 16 hours, at last in 500 ℃ of activation 24 hours, promptly make the compound catalyst for cracking of aluminium oxide-zinc oxide, wherein metal oxide content is 50%, and carrier is 50%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 15% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment five:
(1) coprecipitation prepares compound catalyst for cracking: take by weighing 70 parts of aluminum nitrates and 30 parts of cobalt nitrates, with two kinds of nitrate mixed dissolutions in 500 parts of deionized waters; This solution splashed into slowly in the beaker that ammoniacal liquor is housed (amount of ammoniacal liquor with guarantee in precipitation process and afterwards ageing process in PH remain at more than 9 be advisable) make it precipitation, to precipitate then and ageing of solution filtered after 20 hours, taking precipitate was dried 24 hours down at 120 ℃, again 250 ℃ of following preheatings 10 hours, at last in 500 ℃ of activation 12 hours, promptly make the compound catalyst for cracking of aluminium oxide-cobalt oxide, wherein metal oxide content is 30%, and carrier is 70%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 10% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment six:
(1) coprecipitation prepares compound catalyst for cracking: take by weighing 60 parts of aluminum nitrates, 20 parts of copper nitrates and 20 parts of calcium nitrate, to be dissolved in 200 parts of deionized waters after their mixing, this solution splashed into slowly in the beaker that ammoniacal liquor is housed (amount of ammoniacal liquor with guarantee in precipitation process and afterwards ageing process in PH remain at more than 9 be advisable) make it precipitation, to precipitate then and ageing of solution filtered after 20 hours, get and be deposited in 120 ℃ of following oven dry 24 hours, again 250 ℃ of following preheatings 10 hours, in 500 ℃ of activation 24 hours, promptly make aluminium oxide-cupric oxide-calcium oxide composite catalyst at last.Wherein metal oxide content is 40%, and carrier is 60%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 15% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment seven:
(1) the compound catalyst for cracking of immersion process for preparing: take by weighing 30 parts of ferric nitrates and 70 parts of silica, ferric nitrate is dissolved in 500 parts of deionized waters, then with this solution impregnation to silica, product behind the dipping was dried 24 hours down at 120 ℃, 500 ℃ of activation 24 hours, promptly make the compound catalyst for cracking of iron oxide-silica again.Wherein metal oxide content is 30%, and carrier is 70%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 10% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment eight:
(1) the compound catalyst for cracking of immersion process for preparing: take by weighing 40 parts of copper nitrates and 60 parts of DeLaZSM-5, copper nitrate is dissolved in 500 parts of deionized waters, then with this solution impregnation to DeLaZSM-5, product behind the dipping was dried 24 hours down at 120 ℃, 500 ℃ of activation 48 hours, promptly make the compound catalyst for cracking of cupric oxide-DeLaZSM-5 again.Wherein metal oxide content is 40%, and carrier is 60%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 3% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment nine:
(1) the microwave solid reaction process prepares compound catalyst for cracking: take by weighing 10 parts of magnesia and 90 parts of imvites, mix under the microwave radiation that the back is 2450MHz in operating frequency and shone 30 minutes, promptly make magnesia-montmorillonite Composite catalyst for cracking.Wherein metal oxide content is 10%, and carrier is 90%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 10% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Embodiment ten:
(1) the microwave solid reaction process prepares compound catalyst for cracking: take by weighing 20 parts of calcium oxide and 80 parts of DeLaZSM-5, mixing the back is to shine 30 minutes under the radiation of 2450MHz microwave in operating frequency, promptly makes the compound catalyst for cracking of calcium oxide-DeLaZSM-5.Wherein metal oxide content is 20%, and carrier is 80%.
(2) cracking waste plastics oil-producing technique: present embodiment cracking waste plastics oil-producing technique is except that being the Halogen by the above-mentioned catalyst for cracking of waste plastics weight adding 4% and the waste plastics of processing, and all the other are identical with embodiment one, do not state so omit.
Claims (4)
1, is used for cracking waste plastics to produce the catalyst of fuel oil, it is characterized in that this catalyst prepares by the following method, promptly in the ZSM-5 zeolite molecular sieve, add the Na of 0.1～2mol/l by 1: 1～100 weight ratio
2CO
3Solution was in 40-120 ℃ of reaction 2～10 hours; Leave standstill after the reaction and incline and supernatant liquor, add the Na of 0.1～2mol/l again by 1: 1～100 weight ratio again
2CO
3Solution in 40～120 ℃ of reactions 2～10 hours, filters, with 100～3000 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; In the solid of drying, add 10～1000 parts of deionized waters then,, filter in 40～120 ℃ of reactions 2～10 hours, with 100～3000 parts of deionized waters washings, and in 120 ℃ of dryings 12 hours down; Dried solid is activated 8～24 hours in 300～600 ℃ again; To the 10-100 part 0.1～2mol/l LaCl of the solid after the activation
3, down exchanging 5～60 minutes in 40～120 ℃ with 2450MHz microwave radiation ion, exchange is afterwards washed La to the cleaning solution with boiling water
3+Detection is zero, then in 120 ℃ dry 12 hours down, again in 300～600 ℃ down activation got final product in 5～24 hours.
2, the cracking waste plastics that is used for according to claim 1 to be to produce the catalyst of fuel oil, it is characterized in that ZSM-5 zeolite molecular sieve in this catalyst is any in HZSM-5 zeolite molecular sieve or the NaZSM-5 zeolite molecular sieve.
3, be used for cracking waste plastics to produce the catalyst of fuel oil, it is characterized in that being is carrier with the described catalyst of claim 1, at least a metal oxide of load is an active component on it, is benchmark with the catalyst weight, and its content is 5～50%.
4, the cracking waste plastics that is used for according to claim 3 is characterized in that to produce the catalyst of fuel oil the metal oxide in this catalyst is zinc oxide, cupric oxide, iron oxide, nickel oxide, magnesia, oxidation Cobalt, manganese oxide, vanadium oxide, titanium oxide, calcium oxide, barium monoxide, lanthana, aluminium oxide, silica.
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| CNB031179355A CN1190269C (en) | 2003-05-26 | 2003-05-26 | Catalyst for cracking waste plastics to generate fuel |
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| CNB031179355A CN1190269C (en) | 2003-05-26 | 2003-05-26 | Catalyst for cracking waste plastics to generate fuel |
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Families Citing this family (20)
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| CN101284235B (en) * | 2008-04-28 | 2011-05-25 | 同济大学 | Preparation method of catalyst for catalytic cracking mixed waste plastic |
| GB0909527D0 (en) * | 2009-06-03 | 2009-07-15 | Univ Manchester | Modified zeolites and their use in the recycling of plastics waste |
| CN101591550B (en) * | 2009-07-08 | 2012-09-26 | 四川大学 | Method for preparing fuel oil by utilizing waste polymer containing heteroatoms through cracking |
| CN102517064A (en) * | 2011-12-29 | 2012-06-27 | 华南理工大学 | Method and device for preparing fuel oil by utilizing solar energy to crack waste plastics |
| US8895790B2 (en) | 2013-02-12 | 2014-11-25 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products |
| US9428695B2 (en) | 2013-02-12 | 2016-08-30 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products with product recycle |
| US9447332B2 (en) | 2013-02-12 | 2016-09-20 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products using temperature control |
| CN103409158B (en) * | 2013-09-10 | 2015-09-30 | 山东斯泰普力高新建材有限公司 | A kind of method of shoddy catalytic pyrolysis liquefaction |
| CN105195215A (en) * | 2014-05-30 | 2015-12-30 | 中国科学院大连化学物理研究所 | Multistage porous molecular sieve catalyst and preparation method thereof |
| CN105214716A (en) * | 2014-05-30 | 2016-01-06 | 中国科学院大连化学物理研究所 | A kind of waste plastics conversion hierarchical pore molecular sieve catalyst and preparation method thereof |
| CN104610996A (en) * | 2015-01-30 | 2015-05-13 | 上海逸淳周实业有限公司 | Novel process for refining oil through continuous catalytic cracking and recovery utilization of waste plastics |
| CN106552653A (en) * | 2016-11-16 | 2017-04-05 | 武汉科技大学 | A kind of preparation method of tire thermal cracking catalyst |
| CN108117882B (en) * | 2018-02-11 | 2019-09-17 | 北京石油化工学院 | A method of processing waste plastics and cellulose |
| CN108355711B (en) * | 2018-02-11 | 2019-07-23 | 北京石油化工学院 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN108273558B (en) * | 2018-02-11 | 2019-07-23 | 北京石油化工学院 | Catalytic cracking catalyst and its preparation method and application |
| CN108329514B (en) * | 2018-02-11 | 2019-12-17 | 北京石油化工学院 | Method for processing waste plastics and cellulose |
| CN108219815B (en) * | 2018-02-11 | 2019-09-17 | 北京石油化工学院 | The method for the treatment of of waste plastics and cellulose |
| CN108517223A (en) * | 2018-03-29 | 2018-09-11 | 南京大学连云港高新技术研究院 | A kind of preparation method of low chlorine plastic cracking oil |
| CN111992242B (en) * | 2020-09-04 | 2023-05-16 | 重庆市环卫集团有限公司 | Catalyst for catalytic pyrolysis of waste plastics and preparation method of fuel oil |
| CN112251253A (en) * | 2020-09-11 | 2021-01-22 | 南昌大学 | Method for chemical recovery and circulation of waste plastics |
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2003
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