CN105038834B - A kind of method that unedible oil fat prepares Determination of Alkane Content fuel oil high with waste plastic copyrolysis - Google Patents
A kind of method that unedible oil fat prepares Determination of Alkane Content fuel oil high with waste plastic copyrolysis Download PDFInfo
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- CN105038834B CN105038834B CN201510440217.9A CN201510440217A CN105038834B CN 105038834 B CN105038834 B CN 105038834B CN 201510440217 A CN201510440217 A CN 201510440217A CN 105038834 B CN105038834 B CN 105038834B
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
A kind of method that unedible oil fat prepares Determination of Alkane Content fuel oil high with waste plastic copyrolysis, as follows：(1) waste plastics cutting and crushing is less than 100 cm into area2Fragment；(2) by waste plastics and unedible oil fat in mass ratio 1:1~1:The ratio mixing of 10 mixing；(3) mixed material is sent into cracking reactor, the air gone out in reactor with nitrogen displacement, heat up, heating rate is 5 ~ 300 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, open agitating device, continue to heat up, at 350 ~ 600 DEG C, the reaction time is 2 ~ 90 min to cracking reaction temperature control, after cleavage reaction product is through gas, solid separation, gas condensation is the fuel oil of Determination of Alkane Content high.The characteristics of present invention is fine and close for plastic construction, the serious problem of cracking process coking, makes full use of grease to the swelling effect of plastics, and glycerol residue discharges free state hydrogen atom under specific cracking condition in grease.Oil productivity more than 85% is obtained, wherein Determination of Alkane Content is up to the liquid fuel of 74% stable high-quality.
Description
Technical field
The invention belongs to Environmental Chemical Engineering and new energy chemical field.
Background technology
Bio-fuel is with recyclability and zero-emission, at present, animal oil relative to fossil fuel biggest advantage
Fat and vegetable fat（Both are triglycerides）It is the primary raw material for obtaining bio-fuel.Triglycerides is by warm such as thermal crackings
Chemical means can obtain renewable fuel oil, and production process has considerable hydrogen to have more than needed.At the same time in municipal solid rubbish, agricultural
There are large quantity of exhaust gas plastics in production, because it is difficult to be formed white pollution by biological decomposition in nature.The main component of plastics
It is olefin polymerization, the waste plastic high temperature pyrolysis or catalytic pyrolysis carried out prepare unsaturated hydrocarbons and study more, many feelings
Manufacture fuel gas can only be laid particular emphasis under condition.Such as Chinese patent 20132002196.3, discloses a kind of plastic resourceization continuous
Gasification cracking multi-effect furnace.This is that, due to olefin polymerization compact structure, plastic cracking belongs to random radical reaction, cracking reaction
Often with the priority that is fractured into of C-H bond, a large amount of coke are as a result produced, liquid product yield is low, and resulting a small amount of splits
Unstable containing the unsaturated hydrocarbons such as a large amount of alkene, aromatic hydrocarbons, property in solution oil, antioxidative stabilizer is poor.Therefore need to split plastics
Solution oil carries out hydrotreating, and Chinese invention 200810225614.4 discloses a kind of waste-plastic pyrolysis oil hydrogenation production high-quality bavin
The method of oily blend component.
Research on preparing fuel oil using non-edible animal grease and vegetable fat cracking is reported more.Chinese invention
The 201210397793.6 a kind of methods for preparing liquid fuel there is provided USY catalytic pyrolysis bio-oil, reaction temperature 400~
500 DEG C, declare that triglycerides cleavage rate can reach more than 90%, liquid fuel yield can reach more than 80%, and product is concentrated on
Between C8~C10.Yang Ning etc. carries out catalysis and splits with down-flow fluidized bed using ECT as reactor, with super stable molecular sieve equilibrium catalyst to vegetable oil
Solution research, within the temperature range of 460~560 DEG C, liquid yield is more than 90%, and cracking gasoline octane number reaches 90, and oxygen,
Sulphur, nitrogen and other heavy metals and ash content are not all detected, and the content of aromatic hydrocarbons and alkene is respectively 39.74% and 30.79%（Yang Ning, Wei
Fly, Li Qiang's down-flow fluidized bed using ECT catalytic cracking vegetable oil prepares the small-sized Hot-state experiment of clean gasoline [C] // Chinese Petroleum Society (CPS) the
Five petroleum refining Annual Conferences, 2005：633 - 656.）, show that oil splitting prepares the technology relative maturity of HC fuel.
However, non-edible animal grease and vegetable fat crack the report for then rarely having research work at present with plastics jointly.
The advantage on unedible oil fat some physicochemical properties can be made full use of, fine and close for plastic construction, cracking process coking is serious
Problem, make full use of grease to the swelling effect of plastics, and glycerol residue discharges under specific cracking condition in grease
The characteristics of free state hydrogen atom, the activation energy of plastic cracking is reduced, shorten the cracking reaction time, improve the saturation of pyrolysis product
Degree, as critical problem.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, particularly waste plastic thermal cracking preparation fuel efficiency is low
Problem.A kind of method that utilization unedible oil fat cracks the fuel oil for preparing Determination of Alkane Content high jointly with waste plastics is provided, drop
Low cracking reaction activation energy, lifting both copyrolysis fuel oil total yields, while improving the quality of fuel oil.
The present invention is to be achieved by the steps of.
（1）Waste plastics cutting and crushing is less than 100 cm into area2Fragment.
（2）By waste plastics and unedible oil fat in mass ratio 1: 1~1:The ratio mixing of 10 mixing.
（3）Mixed material is sent into cracking reactor, the air gone out in reactor with nitrogen displacement heats up, heating rate
It is 5 ~ 300 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, opens agitating device, continues to heat up, cracking reaction temperature
At 350 ~ 600 DEG C, the reaction time is 5 ~ 90 min for control, cleavage reaction product through gas, it is solid separate after, the condensed liquid of gas
Body is the fuel oil of Determination of Alkane Content high.
Heretofore described unedible oil fat refers to the plant of discarded plant grease, discarded animal oil and non-consumption
Thing grease.
Waste plastic of the present invention refers to discarded low density polyethylene (LDPE), discarded high density polyethylene (HDPE), discarded
Polypropylene, discarded polyvinyl chloride and discarded polystyrene.
Cracking reactor of the present invention is high-pressure bottle, stainless steel.
Liquid product yield is up to 74% up to more than 85%, wherein Determination of Alkane Content in pyrolysis product obtained in the present invention
More than, it is less than 0.5mg/100ml by the liquid fuel antioxidative stabilizer total insoluble substance of rectifying（GB252-200 detection methods）.
The present invention is to utilize grease thermal conductance good and swelling effect to plastics first, reduces the activation of plastic cracking
Can, shorten the cracking reaction time, control pyrogenetic reaction is reached, improve the purpose of liquid fuel yield.
Next to that the characteristics of discharging free state hydrogen atom under specific cracking condition using glycerol residue in grease, promotes
The positively charged fragment that long chain polymeric olefin cracking is formed, is hydrogenated with and is settled out in time, suppresses terminal olefine, how unsaturated
The formation of hydrocarbon, aromatic hydrocarbons, the hydrogen-carbon ratio of waste plastics advantage higher, and the ingenious knot of unedible oil fat chemical reaction activity advantage
Close, realize unedible oil fat and waste plastic and have complementary advantages in liquid fuel conversion process.Exploitation high-quality liquid fuel, most
Unedible oil fat renewable biomass resources are possibly make use of greatly, waste cooking oil backflow dining table is prevented, is also to solve waste plastics
Problem of environmental pollution provide innovative approach, while for food security and environmental protection provide a feasible technology.
Outstanding advantages of the present invention are.
（1）Using grease thermal conductance is good and swelling effect to plastics, the activation energy of plastic cracking is reduced, shorten cracking
In the reaction time, control pyrogenetic reaction is reached, improve the purpose of liquid fuel yield.
（2）The characteristics of discharging free state hydrogen atom under specific cracking condition using glycerol residue in grease, promotes length
The positively charged fragment that chain polymerization olefin cracking is formed, is hydrogenated with and is tended towards stability in time, suppresses terminal olefine, how unsaturated
The formation of hydrocarbon, aromatic hydrocarbons, lifts oil quality.
（3）This invention is skilful the hydrogen-carbon ratio of waste plastics advantage higher, and unedible oil fat chemical reaction activity advantage
Wonderful combination, realizes unedible oil fat and waste plastic and has complementary advantages in liquid fuel conversion process.The liquid combustion of exploitation high-quality
Material, maximum possible make use of unedible oil fat renewable biomass resources, prevent waste cooking oil from flowing back dining table, also solve useless
The problem of environmental pollution of plastics, while for food security and environmental protection provide a feasible technology, with prominent society
Meeting, environment and economic benefit, its exploitation prospect are bright.
Specific embodiment
The present invention will be described further by following examples.
Embodiment 1.
（1）30 grams discarded of LDPE: Low-density polyethylene plastics is cut into area for 4 cm2Subquadrate fragment.
（2）By step（1）Discarded LDPE: Low-density polyethylene plastics fragment and wilson dogwood oil in mass ratio 1:1 mixing.
（3）By step（2）Mixed material sends into cracking reactor, and the air gone out in reactor with nitrogen displacement heats up, rises
Warm speed is 20 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, opens agitating device, continues to heat up, and cracking is anti-
Answer temperature control at 400 DEG C, the reaction time is 20 min, condensable in gaseous product after cleavage reaction product is through gas, solid separation
Liquid obtain liquid fuel oil 51.3 grams.74% is up to through analyzing wherein Determination of Alkane Content, the liquid fuel by rectifying is anti-oxidant
Stability total insoluble substance is less than 0.5mg/100ml（GB252-200 detection methods）.
Embodiment 2.
（1）30 grams discarded of high-density polyethylene plastics is cut into area for 3 cm2Subquadrate fragment.
（2）By step（1）Discarded high-density polyethylene plastics fragment and wilson dogwood oil in mass ratio 1:1.5 mixing.
（3）By step（2）Mixed material sends into cracking reactor, and the air gone out in reactor with nitrogen displacement heats up, rises
Warm speed is 25 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, agitating device is opened, by cracking reaction temperature control
At 450 DEG C, the reaction time is 18 min, and after cleavage reaction product is through gas, solid separation, condensable liquid is obtained in gaseous product
64 grams of liquid fuel oil.76% is up to through analyzing wherein Determination of Alkane Content, the liquid fuel antioxidative stabilizer by rectifying is always insoluble
Thing is less than 0.6mg/100ml（GB252-200 detection methods）.
Embodiment 3.
（1）30 grams discarded of polypropylene plastics is cut into area for 2 cm2Subquadrate fragment.
（2）By step（1）Discarded polypropylene plastics fragment and wilson dogwood oil in mass ratio 1:2 mixing.
（3）By step（2）Mixed material sends into cracking reactor, and the air gone out in reactor with nitrogen displacement heats up, will
Heating rate is 30 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, opens agitating device, cracking reaction temperature control
At 500 DEG C, the reaction time is 17 min, and after cleavage reaction product is through gas, solid separation, condensable liquid is obtained in gaseous product
77 grams of liquid fuel oil.75.2% is up to through analyzing wherein Determination of Alkane Content, it is total not by the liquid fuel antioxidative stabilizer of rectifying
Molten thing is less than 0.56mg/100ml（GB252-200 detection methods）.
Presently preferred embodiments of the present invention is these are only, but the scope that the present invention is implemented is not intended to be limited thereto.
Claims (2)
1. a kind of method that unedible oil fat prepares Determination of Alkane Content fuel oil high with waste plastic copyrolysis, it is characterized in that by following step
Suddenly：
（1）Waste plastics cutting and crushing is less than 100 cm into area2Fragment；
（2）By waste plastics and unedible oil fat in mass ratio 1: 1~1:The ratio mixing of 10 mixing；
（3）Mixed material is sent into cracking reactor, the air gone out in reactor with nitrogen displacement, heat up, heating rate be 5 ~
300 DEG C/min, when temperature of charge is warmed up to up to 150 DEG C, agitating device is opened, continue to heat up, cracking reaction temperature control
At 350 ~ 600 DEG C, the reaction time is 2 ~ 90 min, after cleavage reaction product is through gas, solid separation, gas is condensed；
Described unedible oil fat is the vegetable fat of discarded plant grease, discarded animal oil or non-consumption.
2. the method that unedible oil fat according to claim 1 prepares Determination of Alkane Content fuel oil high with waste plastic copyrolysis,
It is characterized in that described waste plastic is discarded low density polyethylene (LDPE), discarded high density polyethylene (HDPE), discarded polypropylene, useless
The polyvinyl chloride or discarded polystyrene abandoned.
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| CN108102682A (en) * | 2018-01-23 | 2018-06-01 | 南京绿帝环保能源科技有限公司 | A kind of common cracking catalysis device of waste oil waste plastics |
| CN108949210A (en) * | 2018-07-31 | 2018-12-07 | 乳源东阳光氟树脂有限公司 | A kind of operation method of monomer pyrolysis furnace |
| CN111100662B (en) | 2018-10-29 | 2021-07-02 | 中国石油化工股份有限公司 | Continuous operation method for microwave pyrolysis of waste plastics |
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| CN101684410A (en) * | 2008-09-25 | 2010-03-31 | 李艺 | New technology and equipment for continuous oil refining from liquid raw materials and discarded plastics and tires |
| US8858783B2 (en) * | 2009-09-22 | 2014-10-14 | Neo-Petro, Llc | Hydrocarbon synthesizer |
| CN202116509U (en) * | 2011-07-06 | 2012-01-18 | 刘志伟 | Computer controlled device for producing gasoline, diesel and natural gas by waste plastics, rubber and waste oil |
| CN104479717A (en) * | 2014-11-10 | 2015-04-01 | 东南大学 | Method used for improving bio oil quality via co-catalysis of waste polyolefin plastic with biomass |
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