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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- CN102039155A CN102039155A CN 201010558121 CN201010558121A CN102039155A CN 102039155 A CN102039155 A CN 102039155A CN 201010558121 CN201010558121 CN 201010558121 CN 201010558121 A CN201010558121 A CN 201010558121A CN 102039155 A CN102039155 A CN 102039155A
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Abstract
The invention relates to a catalyst for the catalytic reforming of waste-plastic pyrolysis oil and a preparation method thereof, which is characterized in that the yield of light oil is improved through carrying out modification on the acidity of HZSM-5 (H zeolite socony mobile-five), and the grade of oil can be improved through utilizing the selectivity of a special channel structure of an HZSM-5 molecular sieve toaromatic hydrocarbon. The modification method is as follows: loading metallic and non-metallic oxides by adopting an isovolumetric immersion method, wherein the oxides comprise zinc oxide, nickel oxide, zirconium oxide, magnesium oxide, gallium oxide and phosphorus oxide, the modified oxides are used exclusively or two types of composite modified oxides are used, and the oxide content is 0.5-10.0wt%. The catalyst has the advantages that the requirement for the source of waste plastics is not high, the operation is flexible, and the operation cost is low, therefore, the catalyst is especially suitable for treating urban and rural rubbishes, the final yield of light oil reaches over 70 percent, and the selectivity to a gasoline fraction aromatic hydrocarbon is as high as 50 percent.
Description
Technical field
The present invention relates to a kind of cracking waste plastics oil catalyst for performing catalytic reforming and preparation method thereof, the catalyst that uses the inventive method to prepare, light oil (boiling point＜350 ℃) yield accounts for cracking waste plastics oil more than 75%, and the gasoline fraction selectivity reaches more than 50%.
Background technology
Whole world plastics consumption figure has surpassed 200,000,000 tons, and China's consumption figure in 2009 surpasses 6,000 ten thousand tons, and the consumption figure of plastic products is also increasing year by year.The plastics life cycle is generally shorter, and in the face of huge waste plastics amount like this, processing method is very crucial.
A large amount of waste or used plastics serious harm existent environment of people is referred to as " white garbage ", and white garbage also is the environmental improvement difficult problem that national governments have a headache most.Waste plastics recovery cracking system fuel oil or industrial chemicals are the most promising, if technology maturation, this can handle a large amount of waste plastics on the one hand and not bring environmental problem, and this also meets the sustainable development of present energy resource on the other hand.Waste plastics thermal cracking system oil, the oil product position is low, and the product carbon number distribution is wide.Therefore, cracking waste plastics system fuel oil, catalyst are emphasis.
Have many over past ten years about utilizing the method report of cracking waste plastics made fuel oil, domesticly many cracking waste plastics made fuel oil devices have also been set up, but prior art exists following obvious deficiency: it all is gap or the operating process of half gap still formula that cracking waste plastics is vaporized into oily technology, and catalyst is often directly applied mechanically the catalyst of crude oil pyrolysis.Though cracking waste plastics and crude oil pyrolysis have many similarities, all be with the hydrocarbon structure of big molecule littler molecular structure of Pintsch process-be degraded under oxygen free condition, yet, crude oil is formed with the waste plastics chemical property and is had very big-difference, it is comparatively complicated that crude oil is formed structure, though and the waste plastics molecular weight is bigger, constituent structure is comparatively single, and this has just caused the very big difference of crude oil and this two 2 course of reaction of cracking waste plastics.Many industrialized units have been arranged now both at home and abroad, but have some problems: 1. mostly the catalyst that is used for cracking waste plastics now is the oil catalytic cracking catalyst, as USY, REY etc., it is little molecule that these catalyst only can make macromolecular cleavage, and gasoline, diesel yield are low.2. the waste plastics preliminary treatment requires height, can increase the waste plastics recovery cost, and preliminary treatment is as cleaning the problem of water treatment of also can bringing.In addition, mostly the existing waste plastics that reclaims is to transport directly to factory processes, and its tangible industrial thermal cracking oil is collected focuses on meeting reduction cost of transportation.
Summary of the invention
A kind of cracking waste plastics oil catalyst for performing catalytic reforming and Preparation Method thereof are provided order of the present invention.Cracking waste plastics oil is without pretreated cracking waste plastics gained, directly cracking waste plastics oil input fixed bed reactors is carried out catalytic reforming, and liquid product yield and grade behind the upgrading improve greatly.
In order to solve the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind of plastic cracking oil catalyst for performing catalytic reforming, catalyst consists of metal or nonmetal oxide modified HZSM-5 molecular sieve, described metal or nonmetal oxide are in zinc oxide, nickel oxide, zirconia, magnesia, gallium oxide or the phosphorous oxide one to two kind, and metal or nonmetal oxide content are 0.5～10.0wt.%.
Among the present invention, described metal or nonmetal oxide content are 0.5～5.0wt.%.
The preparation method of the plastic cracking oil catalyst for performing catalytic reforming that the present invention proposes, adopt the incipient impregnation method, 30g moulding HZSM-5 molecular sieve be impregnated in 42ml nitrate solution or the phosphoric acid solution, leave standstill 1.8-2.2h under the normal temperature, put into 75-85 ℃ of oven for drying moisture, be warming up to 115-125 ℃ of dry 1.8-2.2h then, place 530-560 ℃ of Muffle furnace roasting 3.8-4.2h at last, promptly make modified catalyst.
Among the present invention, when using two kinds of nitrate solutions or phosphoric acid solution, dipping adopts co-impregnation or step impregnation method, co-impregnation impregnated in the HZSM-5 molecular sieve in two kinds of mixed nitrate solutions or the phosphoric acid solution exactly, and step impregnation method is exactly that the HZSM-5 molecular sieve be impregnated in the different nitrate solution or phosphoric acid solution successively.
Catalyst of the present invention has following remarkable achievement:
1. under the modified catalyst effect, the yield of light oil height can account for more than 75% of cracking waste plastics oil, and aromatics yield can account for more than 50% of gasoline fraction.
2. waste plastics is without preliminary treatment, and directly cracking makes cracked oil.
3. cracking waste plastics oil focuses on, and can reduce the directly cost of transportation of waste plastics.
4. compare with existing catalyst, the HZSM-5 modified catalyst can improve yield of light oil, and arenes selectivity is good, and because the pore structure of HZSM-5 molecular sieve uniqueness, anti-carbon deposit performance is good.Catalyst for performing catalytic reforming requires low, applied widely to the waste plastics source, provide an effective way for handling town and country rubbish, and cost of material is low, utilizes this catalyst that considerable income can be provided.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1
The preparation of catalyst for performing catalytic reforming: 30g moulding HZSM-5 molecular sieve adds the medium volume dipping of 42ml nickel nitrate solution, leave standstill 2h under the normal temperature, put into 80 ℃ of oven for drying moisture, be warming up to 120 ℃ of dry 2h then, place 550 ℃ of Muffle furnace roasting 4h promptly to get the nickel oxide modified HZSM-5 catalyst at last.Nickel nitrate palpus addition accounts for the 5.0wt.% of carrier in nickel oxide.
Catalyst is used for cracking waste plastics oil catalytic reforming technology: get the 4.0g catalyst and place small stationary bed bioreactor stage casing, temperature programming to 400 ℃ constant temperature, the stable back charging of question response actuator temperature, charging flow velocity 0.0.6ml/min, after collecting the liquid product distillation, get yield of light oil by chromatography and account for 64.5% of cracking waste plastics oil, aromatics yield accounts for 31.0% of gasoline fraction.
Embodiment 2
The preparation of catalyst for performing catalytic reforming: 30g moulding HZSM-5 molecular sieve adds 42ml nickel nitrate and the medium volume dipping of zinc nitrate mixed solution, leave standstill 2h under the normal temperature, put into 80 ℃ of oven for drying moisture, be warming up to 120 ℃ of dry 2h then, place 550 ℃ of Muffle furnace roasting 4h promptly to get nickel oxide and the composite modified HZSM-5 catalyst of zinc oxide at last.Nickel nitrate palpus addition accounts for the 5.0wt.% of carrier in nickel oxide; The zinc nitrate addition accounts for the 1.0wt.% of carrier in zinc oxide.
Catalyst is used for cracking waste plastics oil catalytic reforming technology: get the 4.0g catalyst and place small stationary bed bioreactor stage casing, temperature programming to 400 ℃ constant temperature, the stable back charging of question response actuator temperature, charging flow velocity 0.0.6ml/min, after collecting the liquid product distillation, get yield of light oil by chromatography and account for 75.2% of cracking waste plastics oil, aromatics yield accounts for 44.1% of gasoline fraction.
Embodiment 3
The preparation of catalyst for performing catalytic reforming: 30g moulding HZSM-5 molecular sieve adds the medium volume dipping of 42ml zirconium nitrate solution, leave standstill 2h under the normal temperature, put into 80 ℃ of oven for drying moisture, be warming up to 120 ℃ of dry 2h then, place 550 ℃ of Muffle furnace roasting 4h promptly to get the zirconia modified HZSM-5 catalyst at last.Zirconium nitrate palpus addition accounts for 0. 5 wt.% of carrier in zirconia.Again the zirconia modified HZSM-5 is carried out the nickel oxide modification, method of operating is identical.The load capacity of nickel oxide is 5.0wt.%.
Catalyst is used for cracking waste plastics oil catalytic reforming technology: get the 4.0g catalyst and place small stationary bed bioreactor stage casing, temperature programming to 400 ℃ constant temperature, the stable back charging of question response actuator temperature, charging flow velocity 0.0.6ml/min, after collecting the liquid product distillation, get yield of light oil by chromatography and account for 75.6% of cracking waste plastics oil, aromatics yield accounts for 51.8% of gasoline fraction.
Claims (4)
1. cracking waste plastics oil catalyst for performing catalytic reforming, it is characterized in that: catalyst consists of metal or nonmetal oxide modified HZSM-5 molecular sieve, the metal of modification or nonmetal oxide are in zinc oxide, nickel oxide, zirconia, magnesia, gallium oxide or the phosphorous oxide one to two kind, and metal or nonmetal oxide content are 0.5～10.0wt.%.
2. cracking waste plastics oil catalyst for performing catalytic reforming according to claim 1 is characterized in that described metal or nonmetal oxide content are 0.5～5.0wt.%.
3. the preparation method of a cracking waste plastics as claimed in claim 1 oil catalyst for performing catalytic reforming, it is characterized in that: adopt the incipient impregnation method, 30g moulding HZSM-5 molecular sieve be impregnated in 42ml nitrate solution or the phosphoric acid solution, leave standstill 1.8-2.2h under the normal temperature, put into 75-85 ℃ of oven for drying moisture, be warming up to 115-125 ℃ of dry 1.8-2.2h then, place 530-560 ℃ of Muffle furnace roasting 3.8-4.2h at last, promptly make modified catalyst.
4. the preparation method of cracking waste plastics oil catalyst for performing catalytic reforming according to claim 3, it is characterized in that: when using two kinds of nitrate solutions or phosphoric acid solution, dipping adopts co-impregnation or step impregnation method, co-impregnation impregnated in the HZSM-5 molecular sieve in two kinds of mixed nitrate solutions or the phosphoric acid solution exactly, and step impregnation method is exactly that the HZSM-5 molecular sieve be impregnated in the different nitrate solution or phosphoric acid solution successively.
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| CN 201010558121 CN102039155A (en) | 2010-11-25 | 2010-11-25 | Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof |
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| CN 201010558121 CN102039155A (en) | 2010-11-25 | 2010-11-25 | Catalyst for catalytic reforming of waste-plastic pyrolysis oil and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Purification treatment method for distillation 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836778A (en) * | 2006-04-28 | 2006-09-27 | 广东工业大学 | Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate |
-
2010
- 2010-11-25 CN CN 201010558121 patent/CN102039155A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836778A (en) * | 2006-04-28 | 2006-09-27 | 广东工业大学 | Metal modified HZSM-5 molecular screen catalyst and its preparation method and uses in preparing methyl formate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Purification treatment method for distillation 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 |
| 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 |
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Application publication date: 20110504 |