CN102039155A - Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof - Google Patents
Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof Download PDFInfo
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- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 title abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 3
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005336 cracking Methods 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052755 nonmetal Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000003502 gasoline Substances 0.000 abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种废塑料裂解油催化改质催化剂及其制备方法，使用本发明方法制备得到的催化剂，轻质油(沸点＜350℃)收率占废塑料裂解油75%以上，汽油馏分选择性达50%以上。The invention relates to a catalyst for catalytic upgrading of waste plastic cracking oil and a preparation method thereof. The catalyst prepared by the method of the invention has a yield of light oil (boiling point <350°C) accounting for more than 75% of waste plastic cracking oil, and gasoline fraction selection Sexuality is more than 50%.
背景技术Background technique
全球塑料消费量已超2亿吨，中国2009年消费量超过6000万吨，塑料制品的消费量还在逐年增加。塑料使用周期一般较短，面对如此巨大的废塑料量，处理方法十分关键。Global plastic consumption has exceeded 200 million tons, China's consumption in 2009 exceeded 60 million tons, and the consumption of plastic products is still increasing year by year. The use cycle of plastics is generally short, and in the face of such a huge amount of waste plastics, the treatment method is very critical.
大量的废旧塑料严重危害人类的生存环境，被称之为“白色垃圾”，白色垃圾也是各国政府最头痛的环境治理难题。废塑料回收裂解制燃油或化工原料最有发展前景，如果技术成熟，这将能一方面处理大量废塑料且不带来环境问题，另一方面这也符合现在的资源能源的可持续发展。废塑料热裂解制油，油品位低，产物碳数分布广。因此，废塑料裂解制燃油，催化剂是重点。A large number of waste plastics seriously endanger the living environment of human beings, and are called "white garbage". White garbage is also the most troublesome environmental governance problem for governments of all countries. Recycling and pyrolysis of waste plastics to make fuel oil or chemical raw materials has the most development prospects. If the technology is mature, it will be able to deal with a large amount of waste plastics without causing environmental problems. On the other hand, it is also in line with the sustainable development of current resources and energy. Waste plastic pyrolysis to oil, the oil grade is low, and the carbon number of the product is widely distributed. Therefore, the catalyst is the focus of waste plastic pyrolysis to fuel oil.
近十年来有许多关于利用废塑料裂解制燃料油的方法报道，国内也建立了不少废塑料裂解制燃料油装置，但现有技术存在着以下明显不足：废塑料裂解汽化成油工艺都为间隙或半间隙釜式操作过程，催化剂往往直接套用原油裂解的催化剂。虽然废塑料裂解和原油裂解有许多相似之处，都是将大分子碳氢结构在无氧条件下高温裂解-降解成更小的分子结构，然而，原油组成与废塑料化学性质存在很大差异，原油组成结构较为复杂，而废塑料虽分子量更大，但成分结构较为单一，这就造成了原油与废塑料裂解这两二反应过程的很大差别。现在国内外已经有不少工业化装置，但存在一些问题：1.现在用于废塑料裂解的催化剂多是石油催化裂解催化剂，如USY、REY等，这些催化剂仅能使大分子裂解为小分子，汽油、柴油收率低。2.废塑料预处理要求高，会增加废塑料回收成本，预处理如清洗还会带来水处理的问题。另外，现有回收废塑料多是直接运输到工厂处理，其实在工业上将热裂解油收集起来集中处理会降低运输成本。In the past ten years, there have been many reports on the method of using waste plastics to crack fuel oil, and many waste plastics cracking and fuel oil plants have been established in China. In the gap or semi-gap kettle operation process, the catalyst is often directly applied to the catalyst of crude oil cracking. Although there are many similarities between waste plastic cracking and crude oil cracking, both are high-temperature cracking-degradation of macromolecular hydrocarbon structures under anaerobic conditions into smaller molecular structures, however, there are great differences in the chemical properties of crude oil and waste plastics , the composition structure of crude oil is relatively complex, while waste plastic has a larger molecular weight, but its composition structure is relatively simple, which causes a big difference between the two reaction processes of crude oil and waste plastic cracking. There are already many industrialized devices at home and abroad, but there are some problems: 1. Most of the catalysts used for cracking waste plastics are petroleum catalytic cracking catalysts, such as USY, REY, etc. These catalysts can only crack large molecules into small molecules. Gasoline and diesel yields are low. 2. The pretreatment requirements of waste plastics are high, which will increase the cost of waste plastics recycling, and pretreatment such as cleaning will also bring about water treatment problems. In addition, most of the existing recycled waste plastics are directly transported to factories for processing. In fact, collecting pyrolysis oil for centralized processing in the industry will reduce transportation costs.
发明内容Contents of the invention
本发明的目地提供一种废塑料裂解油催化改质催化剂及其备方法。废塑料裂解油是不经预处理的废塑料裂解所得，直接将废塑料裂解油输入固定床反应器进行催化改质，改质后的液态产物收率和品位大大提高。The object of the present invention is to provide a waste plastic cracking oil catalytic upgrading catalyst and its preparation method. Waste plastic pyrolysis oil is obtained by pyrolysis of waste plastics without pretreatment. The waste plastic pyrolysis oil is directly input into a fixed bed reactor for catalytic reforming, and the yield and grade of liquid products after reforming are greatly improved.
为了解决上述技术问题，本发明采取的技术方案如下：一种塑料裂解油催化改质催化剂，催化剂组成为金属或非金属氧化物改性HZSM-5分子筛，所述金属或非金属氧化物是氧化锌、氧化镍、氧化锆、氧化镁、氧化镓或氧化磷中一至两种，金属或非金属氧化物含量为0.5～10.0wt.%。In order to solve the above-mentioned technical problems, the technical scheme adopted by the present invention is as follows: a catalyst for plastic cracking oil catalytic modification, the catalyst is composed of metal or non-metal oxide modified HZSM-5 molecular sieve, and the metal or non-metal oxide is oxidized One or two of zinc, nickel oxide, zirconium oxide, magnesium oxide, gallium oxide or phosphorus oxide, and the content of metal or non-metal oxide is 0.5-10.0wt.%.
本发明中，所述金属或非金属氧化物含量为0.5～5.0wt.%。In the present invention, the content of the metal or non-metal oxide is 0.5-5.0wt.%.
本发明提出的塑料裂解油催化改质催化剂的制备方法，采用等体积浸渍方法，将30g成型HZSM-5分子筛浸渍于42ml硝酸盐溶液或磷酸溶液中，常温下静置1.8-2.2h，放入75-85℃烘箱烘干水分，然后升温至115-125℃干燥1.8-2.2h，最后置于530-560℃马弗炉焙烧3.8-4.2h，即制得改性催化剂。The preparation method of the plastic cracking oil catalytic modification catalyst proposed by the present invention adopts the equal-volume impregnation method, immersing 30g of shaped HZSM-5 molecular sieves in 42ml of nitrate solution or phosphoric acid solution, standing at room temperature for 1.8-2.2h, putting Dry the water in an oven at 75-85°C, then raise the temperature to 115-125°C to dry for 1.8-2.2 hours, and finally place it in a muffle furnace at 530-560°C for 3.8-4.2 hours to prepare the modified catalyst.
本发明中，当使用两种硝酸盐溶液或磷酸溶液时，浸渍采用共浸渍法或分步浸渍法，共浸渍法就是将HZSM-5分子筛浸渍于两种混合硝酸盐溶液或磷酸溶液中，分步浸渍法就是将HZSM-5分子筛依次浸渍于不同的硝酸盐溶液或磷酸溶液中。In the present invention, when two kinds of nitrate solutions or phosphoric acid solutions are used, the impregnation adopts a co-impregnation method or a step-by-step impregnation method, and the co-impregnation method is to impregnate the HZSM-5 molecular sieve in two kinds of mixed nitrate solutions or phosphoric acid solutions, respectively The one-step impregnation method is to impregnate HZSM-5 molecular sieves in different nitrate solutions or phosphoric acid solutions sequentially.
本发明的催化剂具有如下显著成果：Catalyst of the present invention has following remarkable achievement:
1.改性催化剂作用下，轻质油收率高，可占废塑料裂解油的75%以上，芳烃收率可占汽油馏分的50%以上。1. Under the action of the modified catalyst, the yield of light oil is high, which can account for more than 75% of waste plastic cracking oil, and the yield of aromatic hydrocarbons can account for more than 50% of gasoline fraction.
2.废塑料不用预处理，直接裂解制得裂解油。2. Waste plastics are directly cracked to produce pyrolysis oil without pretreatment.
3.废塑料裂解油集中处理，可降低废塑料直接运输的成本。3. Centralized treatment of waste plastic pyrolysis oil can reduce the cost of direct transportation of waste plastics.
4.与现有催化剂相比，HZSM-5改性催化剂可提高轻质油收率，芳烃选择性好，且由于HZSM-5分子筛独特的孔结构，抗积炭性能好。催化改质催化剂对废塑料来源要求低，适用范围广，为处理城乡垃圾提供了一条有效途径，原料成本低，利用此催化剂可提供可观的收益。4. Compared with existing catalysts, HZSM-5 modified catalyst can increase the yield of light oil, has good selectivity for aromatics, and has good anti-coking performance due to the unique pore structure of HZSM-5 molecular sieve. Catalytic upgrading catalyst has low requirements on the source of waste plastics and has a wide range of applications. It provides an effective way to deal with urban and rural garbage. The cost of raw materials is low, and the use of this catalyst can provide considerable benefits.
具体实施方式Detailed ways
下面通过实施例进一步说明本发明。The present invention is further illustrated below by way of examples.
实施例1Example 1
催化改质催化剂的制备：30g成型HZSM-5分子筛加入42ml硝酸镍溶液中等体积浸渍，常温下静置2h，放入80℃烘箱烘干水分，然后升温至120℃干燥2h，最后置于550℃马弗炉焙烧4h即得氧化镍改性HZSM-5催化剂。硝酸镍须加入量以氧化镍计，占载体的5.0wt.%。Preparation of catalytic modification catalyst: Add 30g of shaped HZSM-5 molecular sieve to 42ml of nickel nitrate solution for medium volume impregnation, let it stand at room temperature for 2 hours, put it in an oven at 80°C to dry the water, then raise the temperature to 120°C for 2 hours, and finally place it at 550°C The nickel oxide modified HZSM-5 catalyst was obtained by calcining in a muffle furnace for 4 hours. The amount of nickel nitrate to be added is calculated as nickel oxide, accounting for 5.0wt.% of the carrier.
催化剂用于废塑料裂解油催化改质工艺：取4.0g催化剂置于小型固定床反应器中段，程序升温至400℃恒温，待反应器温度稳定后进料，进料流速0.0.6ml/min，收集液态产物蒸馏后，通过色谱分析得轻质油收率占废塑料裂解油的64.5%，芳烃收率占汽油馏分的31.0%。The catalyst is used in the catalytic upgrading process of waste plastic cracking oil: take 4.0g of catalyst and place it in the middle of a small fixed-bed reactor, program the temperature to 400°C, and feed the material after the temperature of the reactor is stable. The feed flow rate is 0.0.6ml/min. After the liquid product was collected and distilled, the yield of light oil accounted for 64.5% of waste plastic pyrolysis oil, and the yield of aromatics accounted for 31.0% of gasoline fraction through chromatographic analysis.
实施例2Example 2
催化改质催化剂的制备：30g成型HZSM-5分子筛加入42ml硝酸镍和硝酸锌混合溶液中等体积浸渍，常温下静置2h，放入80℃烘箱烘干水分，然后升温至120℃干燥2h，最后置于550℃马弗炉焙烧4h即得氧化镍和氧化锌复合改性HZSM-5催化剂。硝酸镍须加入量以氧化镍计，占载体的5.0wt.%；硝酸锌加入量以氧化锌计，占载体的1.0wt.%。Preparation of catalytic modification catalyst: Add 30g of shaped HZSM-5 molecular sieve to 42ml of nickel nitrate and zinc nitrate mixed solution for medium volume impregnation, let it stand at room temperature for 2h, put it in an oven at 80°C to dry the water, then raise the temperature to 120°C for 2h, and finally Place it in a muffle furnace at 550°C for 4 hours to obtain the composite modified HZSM-5 catalyst of nickel oxide and zinc oxide. The amount of nickel nitrate to be added is calculated as nickel oxide, accounting for 5.0wt.% of the carrier; the amount of zinc nitrate added is calculated as zinc oxide, accounting for 1.0wt.% of the carrier.
催化剂用于废塑料裂解油催化改质工艺：取4.0g催化剂置于小型固定床反应器中段，程序升温至400℃恒温，待反应器温度稳定后进料，进料流速0.0.6ml/min，收集液态产物蒸馏后，通过色谱分析得轻质油收率占废塑料裂解油的75.2%，芳烃收率占汽油馏分的44.1%。The catalyst is used in the catalytic upgrading process of waste plastic cracking oil: take 4.0g of catalyst and place it in the middle of a small fixed-bed reactor, program the temperature to 400°C, and feed the material after the temperature of the reactor is stable. The feed flow rate is 0.0.6ml/min. After the liquid product was collected and distilled, the yield of light oil accounted for 75.2% of waste plastic pyrolysis oil, and the yield of aromatics accounted for 44.1% of gasoline fraction through chromatographic analysis.
实施例3Example 3
催化改质催化剂的制备：30g成型HZSM-5分子筛加入42ml硝酸锆溶液中等体积浸渍，常温下静置2h，放入80℃烘箱烘干水分，然后升温至120℃干燥2h，最后置于550℃马弗炉焙烧4h即得氧化锆改性HZSM-5催化剂。硝酸锆须加入量以氧化锆计，占载体的0. 5 wt.%。再对氧化锆改性HZSM-5进行氧化镍改性，操作方法相同。氧化镍的负载量为5.0wt.%。Preparation of catalytic modification catalyst: Add 30g of shaped HZSM-5 molecular sieve to 42ml of zirconium nitrate solution for medium volume impregnation, let it stand at room temperature for 2 hours, put it in an oven at 80°C to dry the water, then raise the temperature to 120°C for 2 hours, and finally place it at 550°C The zirconia-modified HZSM-5 catalyst was obtained by calcining in a muffle furnace for 4 hours. Zirconium nitrate must be added in zirconia, accounting for 0.5 wt.% of the carrier. Then carry out nickel oxide modification to zirconia modified HZSM-5, the operation method is the same. The loading amount of nickel oxide was 5.0 wt.%.
催化剂用于废塑料裂解油催化改质工艺：取4.0g催化剂置于小型固定床反应器中段，程序升温至400℃恒温，待反应器温度稳定后进料，进料流速0.0.6ml/min，收集液态产物蒸馏后，通过色谱分析得轻质油收率占废塑料裂解油的75.6%，芳烃收率占汽油馏分的51.8%。The catalyst is used in the catalytic upgrading process of waste plastic cracking oil: take 4.0g of catalyst and place it in the middle of a small fixed-bed reactor, program the temperature to 400°C, and feed the material after the temperature of the reactor is stable. The feed flow rate is 0.0.6ml/min. After the liquid product was collected and distilled, the yield of light oil accounted for 75.6% of waste plastic pyrolysis oil, and the yield of aromatics accounted for 51.8% of gasoline fraction through chromatographic analysis.
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| CN102658190A (en) * | 2012-03-26 | 2012-09-12 | 张吉照 | Catalyst for waste and old plastic oil refining and preparation method thereof |
| CN103357431A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Catalyst for process of producing vehicle fuel through pyrolysis of waste plastic, as well as preparation method and application thereof |
| CN104549450A (en) * | 2015-01-14 | 2015-04-29 | 天津大学 | Method for preparing loaded molecular sieve catalyst by using catalytic cracking of biomass gasification tar |
| CN108456328A (en) * | 2018-02-11 | 2018-08-28 | 宁波普前环保科技有限公司 | A kind of processing method of waste plastics |
| CN111672317A (en) * | 2020-06-10 | 2020-09-18 | 南京工业大学 | A kind of purification treatment method of rectification still residue |
| CN112251253A (en) * | 2020-09-11 | 2021-01-22 | 南昌大学 | Method for chemical recovery and circulation of waste plastics |
| CN113976095A (en) * | 2021-11-29 | 2022-01-28 | 刘磊 | Preparation method of waste polymethyl methacrylate catalytic cracking catalyst |
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| CN115957828A (en) * | 2022-12-14 | 2023-04-14 | 中国石油大学(北京) | Catalyst for catalytic cracking of waste plastics and preparation method thereof |
| CN116135310A (en) * | 2021-11-18 | 2023-05-19 | 万华化学集团股份有限公司 | Catalyst for recycling waste plastics and preparation method and application thereof |
| CN116493039A (en) * | 2023-03-11 | 2023-07-28 | 中国石油化工股份有限公司 | Catalyst for producing olefin by catalytic pyrolysis of waste plastics and preparation method and application thereof |
| GB2616046A (en) * | 2022-02-25 | 2023-08-30 | Plastic Energy Ltd | A method for the production of a pyrolysis oil from end-of-life plastics |
| EP4379020A1 (en) * | 2022-12-01 | 2024-06-05 | SK Innovation Co., Ltd. | Method and device for converting waste plastic pyrolysis oil into light olefins with high yield |
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| CN1836778A (en) * | 2006-04-28 | 2006-09-27 | 广东工业大学 | A metal-modified HZSM-5 molecular sieve catalyst, its preparation method and its application in the preparation of methyl formate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1836778A (en) * | 2006-04-28 | 2006-09-27 | 广东工业大学 | A metal-modified HZSM-5 molecular sieve catalyst, its preparation method and its application in the preparation of methyl formate |
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| CN102658190A (en) * | 2012-03-26 | 2012-09-12 | 张吉照 | Catalyst for waste and old plastic oil refining and preparation method thereof |
| CN102658190B (en) * | 2012-03-26 | 2014-12-31 | 张吉照 | Catalyst for waste and old plastic oil refining and preparation method thereof |
| CN103357431A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Catalyst for process of producing vehicle fuel through pyrolysis of waste plastic, as well as preparation method and application thereof |
| CN104549450A (en) * | 2015-01-14 | 2015-04-29 | 天津大学 | Method for preparing loaded molecular sieve catalyst by using catalytic cracking of biomass gasification tar |
| CN108456328A (en) * | 2018-02-11 | 2018-08-28 | 宁波普前环保科技有限公司 | A kind of processing method of waste plastics |
| CN111672317A (en) * | 2020-06-10 | 2020-09-18 | 南京工业大学 | A kind of purification treatment method of rectification still residue |
| CN112251253A (en) * | 2020-09-11 | 2021-01-22 | 南昌大学 | Method for chemical recovery and circulation of waste plastics |
| CN114713268A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Molecular sieve catalyst for cracking waste plastic, preparation method thereof and waste plastic cracking method |
| CN114713268B (en) * | 2021-01-06 | 2024-06-25 | 中国石油天然气股份有限公司 | Molecular sieve catalyst for waste plastic pyrolysis, preparation method thereof and waste plastic pyrolysis method |
| CN116135310A (en) * | 2021-11-18 | 2023-05-19 | 万华化学集团股份有限公司 | Catalyst for recycling waste plastics and preparation method and application thereof |
| CN113976095A (en) * | 2021-11-29 | 2022-01-28 | 刘磊 | Preparation method of waste polymethyl methacrylate catalytic cracking catalyst |
| GB2616046A (en) * | 2022-02-25 | 2023-08-30 | Plastic Energy Ltd | A method for the production of a pyrolysis oil from end-of-life plastics |
| WO2023161414A1 (en) | 2022-02-25 | 2023-08-31 | Plastic Energy Limited | A method for the production of a pyrolysis oil from end-of-life plastics |
| EP4379020A1 (en) * | 2022-12-01 | 2024-06-05 | SK Innovation Co., Ltd. | Method and device for converting waste plastic pyrolysis oil into light olefins with high yield |
| CN115957828A (en) * | 2022-12-14 | 2023-04-14 | 中国石油大学(北京) | Catalyst for catalytic cracking of waste plastics and preparation method thereof |
| WO2024184508A1 (en) | 2023-03-09 | 2024-09-12 | Plastic Energy Limited | A method for the production of a pyrolysis oil from end-of-life plastics |
| CN116493039A (en) * | 2023-03-11 | 2023-07-28 | 中国石油化工股份有限公司 | Catalyst for producing olefin by catalytic pyrolysis of waste plastics and preparation method and application thereof |
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