CN104449885B - A kind of method utilizing waste plastics to prepare light Fuel - Google Patents
A kind of method utilizing waste plastics to prepare light Fuel Download PDFInfo
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- CN104449885B CN104449885B CN201410645074.0A CN201410645074A CN104449885B CN 104449885 B CN104449885 B CN 104449885B CN 201410645074 A CN201410645074 A CN 201410645074A CN 104449885 B CN104449885 B CN 104449885B
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- 239000004033 plastic Substances 0.000 title claims abstract description 62
- 229920003023 plastic Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000446 fuel Substances 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 239000003921 oil Substances 0.000 claims abstract description 74
- 235000019198 oils Nutrition 0.000 claims abstract description 74
- 238000009833 condensation Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 230000005494 condensation Effects 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 20
- 239000008158 vegetable oil Substances 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 230000032050 esterification Effects 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000007781 pre-processing Methods 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 235000014593 oils and fats Nutrition 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 230000036571 hydration Effects 0.000 claims description 10
- 238000006703 hydration reaction Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003925 fat Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 15
- 238000011069 regeneration method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- -1 alcohols hydrocarbon Chemical class 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 235000019197 fats Nutrition 0.000 description 6
- 239000000383 hazardous chemical Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000000567 combustion gas Substances 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 241000720974 Protium Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000010762 marine fuel oil Substances 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
Abstract
The present invention relates to a kind of method utilizing waste plastics to prepare light Fuel, comprise the following steps: S1: waste plastics is carried out depolymerization liquefaction, obtain plastics depolymerization liquefaction oil；S2: select liquid and the vegetable oil residue of semi liquid state, carries out the pre-heat treatment to it, and preheating temperature is 70～90 DEG C；S3: described plastics depolymerization liquefaction oil and the vegetable oil residue after the pre-heat treatment are pumped in raw oil preprocessing furnace and carry out pretreatment, carries out condensation through condensation recycling can simultaneously and reclaims；S4: the oils and fats reclaimed through condensation is input in pre-ester retort carry out esterification, then by dividing discharge containing sour water in pre-ester retort liquid, then carries out processed；S5: carry out rectification process, after the condensation of the most water cooled heat exchanger, form light Fuel finished product.The beneficial effects of the present invention is, it is provided that a kind of energy-conserving and environment-protective, technological process be simple and economic benefit and the good method utilizing waste plastics to prepare light Fuel of social benefit.
Description
Technical field
The present invention relates to a kind of method utilizing waste plastics to prepare light Fuel.
Background technology
Human being's production life discharge abandoned biomass resource the abundantest, including house refuse, changing food waste, plant rubbish,
Industry rubbish etc., comprises various energy type goods and materials in these rubbish, such as waste plastics, vegetable oil residue, the petrochemical industry dregs of fat, plant waste
Thing and plant processing waste etc..Due in these compositions containing relatively higher energy, if can not properly recycle, then because of
These compositions mainly exist with organic-biological matter molecular structure, in naturally clearing up by produce serious contaminants air ambient with
Water environment, contaminated land resource, destroy human living space, serious, also will directly threaten the safety of human survival with healthy；
If able to properly recycle, considerable energy products will be brought to the mankind, such as hydration catalysis waste plastics, vegetable oil residue, useless machine
Oil etc. are containing refining regeneration light Fuel, bio-oil materials, combustion gas, electric energy etc. by debirs, and be beneficial to man survival and development
Rising industry.
2010, whole nation oil product total flow about 300,000,000 tons, wherein vehicle fuel oil and fishing boat oilconsumption about 13000
Ten thousand tons.Specify in the works with national oil substituted pesticides in the works in national strategy new industry, to the year two thousand thirty, domestic petroleum
Fuel oil consumption will have 30% use regeneration light alcohols hydrocarbon hybrid fuel substitute, according to current domestic car, marine fuel oil consumption and
Fuel oil consumption development trend is estimated, to the year two thousand thirty, and the domestic compound combustion of regeneration light alcohols hydrocarbon at least forming about 50,000,000 tons
The market demand of material (including biodiesel and biogasoline etc.).
Summary of the invention
In view of the above-mentioned problems in the prior art, present invention is primarily targeted at the defect solving prior art, the present invention
A kind of method utilizing waste plastics to prepare light Fuel is provided.
The invention provides a kind of method utilizing waste plastics to prepare light Fuel, comprise the following steps:
S1: use low-temperature catalyzed dissolving method to carry out depolymerization liquefaction waste plastics, obtain plastics depolymerization liquefaction oil；
S2: select liquid and the vegetable oil residue of semi liquid state, carries out the pre-heat treatment to it, and preheating temperature is 70～90 DEG C；
S3: described plastics depolymerization liquefaction oil and the vegetable oil residue after the pre-heat treatment are pumped in raw oil preprocessing furnace and carry out
Pretreatment, carries out condensation through condensation recycling can simultaneously and reclaims, described plastics depolymerization liquefaction oil and the percent mass of described vegetable oil residue
Ratio is 70～90: 10～30；
S4: to through condensation reclaim oils and fats be input in pre-ester retort carry out esterification, the time of esterification be 1.8～
2.2 hours, by pre-ester retort liquid divides discharge containing sour water after then standing 0.2～0.8 hour, then carry out processed, with
Time the oil after processed divided be input in rectification conservation tank store；
S5: being divided by the oil being stored in rectification conservation tank and be input in rectifying column carry out rectification process, the temperature of rectification process is
340～380 DEG C, after the oily lease making after rectification process is crossed the condensation of stainless steel foil water cooling heat exchanger simultaneously, form light Fuel and become
Product.
Optionally, waste plastics is used low-temperature catalyzed dissolving method to carry out depolymerization liquefaction by described step S1 to concretely comprise the following steps: will
Waste plastics is sent in dissolving tank after pulverizing, and adds acid catalyst and solvent, carries out depolymerization dissolving, simultaneously by molten under the conditions of 110 DEG C
Solve liquid to be delivered in evaporator be evaporated forming liquefaction oil with recycling design, then liquefaction oil is carried out filtration treatment.
Optionally, one or more during described solvent is phenol, ether, chlorobenzene, carbon tetrachloride.
Optionally, in described step S3, pretreatment concretely comprises the following steps: with vegetable oil residue, plastics depolymerization liquefaction oil is being kept a constant temperature
Under the conditions of degree, to be pumped in preprocessing furnace heating, within 200 DEG C, complete moisture evaporation, evaporation between 220～380 DEG C
Oil vapour and steam issue unboiled water conjunction catalytic reaction in the effect of catalyst.
Optionally, the mass percent of plastics depolymerization liquefaction oil and described vegetable oil residue described in described step S3 is 80: 20.
Optionally, the oils and fats reclaimed through condensation in described step S4 is input in pre-ester retort carry out the concrete step of esterification
Suddenly it is: after hydration catalytic reaction, in the lubricant component that condensation is reclaimed, saturated fatty acid content is about 4～5%, oil condensation reclaimed
Divide and be input in pre-ester retort, under the conditions of 70～75 DEG C, in pre-ester retort, input methanol and the concentrated sulphuric acid of concentration 98%,
Methanol input quantity is the 30% of saturated fatty acid content, and concentrated sulphuric acid addition is the 3% of methanol total amount.
Optionally, the concretely comprising the following steps of processed in described step S4: pour in tap water cleaning liquid in pre-fat retort
Sour composition, repeatedly clean 2～4 times, each water consumption is the 10～20% of esterification oil product total amount, quiet clean every time after
Put 10～20 minutes, then use separatory funnel will contain sour water and divide discharge.
Optionally, in described step S4, the time of esterification is 2 hours, by pre-ester retort liquid after then standing 0.5 hour
Body divides discharge containing sour water.
Optionally, in described step S5, the temperature of rectification process is 360 DEG C.
The present invention has the following advantages and beneficial effect: the present invention provides a kind of method utilizing waste plastics to prepare light Fuel, should
The Technology of method is advanced and applicable, and public work scheme meets production requirement, the method the light Fuel product market prepared is wide
Wealthy, can produce good through numerous benefit and social benefit simultaneously；Meanwhile, this utilizes the method that waste plastics prepares light Fuel,
During production, environment will not be produced pollution, energy-conserving and environment-protective.
Detailed description of the invention
Below with reference to specific embodiment, the present invention is further illustrated.
A kind of method utilizing waste plastics to prepare light Fuel of the embodiment of the present invention, comprises the following steps: S1: adopt waste plastics
Carry out depolymerization liquefaction with low-temperature catalyzed dissolving method, obtain plastics depolymerization liquefaction oil；S2: select liquid and the vegetable oil residue of semi liquid state,
It is carried out the pre-heat treatment, and preheating temperature is 70～90 DEG C；S3: by described plastics depolymerization liquefaction oil and planting after the pre-heat treatment
Thing oil foot is pumped in raw oil preprocessing furnace and carries out pretreatment, carries out condensation through condensation recycling can simultaneously and reclaims, described plastics solution
The mass percent of poly-liquefaction oil and described vegetable oil residue is 70～90: 10～30；S4: the oils and fats reclaimed through condensation is input to
Carrying out esterification in pre-ester retort, the time of esterification is 1.8～2.2 hours, will be pre-after then standing 0.2～0.8 hour
Ester retort liquid divides discharge containing sour water, then carries out processed, the oil after processed is divided simultaneously and be input to rectification
Conservation tank stores；S5: the oil being stored in rectification conservation tank is divided and is input in rectifying column carry out rectification process, at rectification
The temperature of reason is 340～380 DEG C, after the oily lease making after rectification process is crossed the condensation of stainless steel foil water cooling heat exchanger simultaneously, is formed
Light Fuel finished product.
A kind of method utilizing waste plastics to prepare light Fuel that the embodiment of the present invention provides, specifically includes following technological process:
First: prepared by raw oil
1), plastics depolymerization liquefaction
Waste plastics is petroleum chemicals, various types of olefins be polymerized, and therefore to refine light-weight fuel oil with waste plastics for raw material, needs
Reverse for waste plastics depolymerization is liquefied；Use low-temperature catalyzed dissolving means to complete the depolymerization liquefaction of waste plastics, obtain waste plastics depolymerization liquid
Carburetion, then with the vegetable oil residue mixed refining light Fuel such as Palmic acid carburetion, detailed process is: after being pulverized by waste plastic directly
Send in dissolving tank, use acid catalyst and solvent, dissolve under the conditions of 110 DEG C, dissolution rate about 80%, then dissolve liquid defeated
Delivering to evaporate in evaporator recycling design, volume recovery is 95%, and evaporation process uses decompression distillation means, protects in evaporation process
Hold temperature of liquid and be not less than 100 DEG C；Finally before liquefaction oil enters preprocessing furnace, liquefaction oil is filtered, leach and do not liquefy
Residue, liquefaction oil is directly entered in preprocessing furnace, and the non-liquefied residue leached uses thermal decomposition vaporization PROCESS FOR TREATMENT, produces renewable energy
Source combustion gas；The solvent that plastics liquefaction uses is double solvents, and main component includes phenol, ether, chlorobenzene, carbon tetrachloride etc., makes
Create the Essential Environment of plastics depolymerization liquefaction by the temperature of acid catalyst and 110 DEG C, then solvent plays the function that depolymerization is dissolved, and promotees
Enter plastics liquefaction；Plastics depolymerization liquefaction oil accounts for 80% ratio in the raw oil in this project.
2), vegetable oil residue
In vegetable oil residue, main component is satisfied fatty acid, is that refining biodiesel class currently mainly selects Palmic acid carburetion, its shape
State has liquid, semi liquid state, mastic three kinds at normal temperatures, and we mainly select liquid and semi liquid state two kinds, in order to keep Petiolus Trachycarpi to be acidified
The mobility of oil, needs to preheat to Palmic acid carburetion, and preheating temperature is 80 DEG C, is then fed in preprocessing furnace refining；Vegetable oil residue
(Palmic acid carburetion) raw oil mass percent in the present embodiment accounts for the ratio of 20%.
The second, raw oil heat treatment
The purpose of raw oil pretreatment is to shorten the strand of regeneration light Fuel, thus reduces the freezing point of product, produces performance close
In the regeneration light Fuel of-No. 10 diesel oil, thus solve domestic existing freezing point of biodiesel height, be difficult to asking for vehicle fuel
Topic；Liquefaction oil and Palmic acid carburetion that raw oil is produced by waste plastics depolymerization liquefaction form.Plastics depolymerization liquefaction oil has only completed plastics
Preliminary depolymerization, is not depolymerization completely, and therefore the liquefaction oil molecular weight after depolymerization is relatively big, and molecular chain length reaches as high as
About C40, the target of oil refining is regeneration light Fuel (biodiesel mixed oil), and the molecular weight lengths of diesel oil is up to C18 (weight
Diesel oil), it is therefore necessary to the further depolymerization chain rupture of plastics depolymerization liquefaction oil, make the molecular chain length of depolymerization liquefaction oil be completely converted into C17
Below；The Palmic acid carburetion selected is mainly composed of satisfied fatty acid, and wherein free fatty average content reaches 85.9%, fatty acid
Carbon chain lengths reaches about C32.Palmic acid carburetion to be used refining regeneration light Fuel, it is necessary first to the long-chain fat in raw material
Fat acid changes into below 16 carbon (increasing an ester group during esterification)；The pretreatment of raw oil mainly by hydration catalytic reaction, promotees
The conversion making Long carbon chain is C17 following component, to meet process goal.Wherein: hydration catalytic reaction description of the process, plastics solution
Poly-liquefaction oil and Palmic acid carburetion, under the conditions of keeping uniform temperature, to be pumped in preprocessing furnace heating, complete water within 200 DEG C
Point evaporation, between 220～380 DEG C, oil vapour and the steam of evaporation issue unboiled water in the effect of catalyst and close catalytic reaction, C17 with
On composition be transformed into the composition of below C16, including fatty acid, fatty alcohol, oleic acid, alkene and alkane.In condensation removal process,
Creating a small amount of uncondensable imflammable gas, toatl proportion is about the 5.3% of raw oil weight；Condensation reclaim fatty acid, fatty alcohol,
Oleic acid, alkane, olefin liquid total amount are about the 80～84% of raw oil weight, residue 10～14% composition evaporation residual liquid, mainly by
The macromolecule component that in hydration catalytic process, the condensation reaction of association generates, can be as industry heavy oil；Hydration catalytic reaction mainly exists
Suitably under temperature conditions, complete the processes such as the division of long strand, hydrogen migration at catalyst surface, and make a small amount of oil, hydrocarbon molecule
Further contracting with become bigger molecule, and discharge unnecessary protium；Steam in hydration catalytic reaction main provide protium and
Hydroxyl ion；The combustion gas main component produced in course of reaction is propylene, butylene, butane etc., is directly used in production and application, and purposes is
Burning produces steam, not as product, but the fuel consumed in whole course of reaction；General bureau's safety supervision is supervised total according to national security
(2013) No. 136 files of Room pipe three letter " producing writing a letter in reply of the relevant issues such as hazardous chemical security clearance about chemical test equipment " are " raw
The hazardous chemical produced in product is only used as raw material and the most for sale, is not belonging to claim hazardous chemical safety production permit
Scope " instruction, during this project construction produce combustion gas, be only used for produce in supplementary energy, the most for sale, therefore accord with
Conjunction presents specifies, is not belonging to apply for the scope of hazardous chemical safety production permit；Catalyst is mainly composed of nickel salt and chromic salts
SZM type molecular sieve composite catalyst, is processed into cellular granule with powder metallurgy means, and the hole in granule is 300～500 nanometers,
To ensure that the oil gas passed through is entirely the strand of below 17 carbon；Strands more than 18 carbon refluxes back in pyrolysis furnace；Wherein:
The catalytic reaction equation of satisfied fatty acid is as follows:
CH3·(CH2)n·COOH+H2O-CH3·(CH2)1/3-1/2n·COOH+CnH2n+CnH2n+2；
The catalytic reaction formula of plastics depolymerization liquefaction oil is as follows:
(CnH2n)m+H2O-CxH2x+CxH2xOH+CxH2X+2,
Wherein, X is less than 17, and reaction completes under middle temperature, normal pressure and catalyst action, is responded and all occurs at catalyst surface, and water steams
By admission pressure directly into catalytic tower after gas entrance system, reaction condition is gentle, does not constitute crack reacting condition.In the reaction, companion
Occur with condensation reaction, generate side-product industry heavy oil.Catalyst in use degradation failure, the general out-of-service time is work 1.5 ten thousand
Hour, inefficacy rear catalyst can regenerate, and regeneration means are attached most importance to and newly sintered, and catalyst can regenerate 5 times.
3rd, esterification
After catalytic reaction, in the lubricant component that condensation is reclaimed, saturated fatty acid content is about 4～5%, divides input by the oil that condensation is reclaimed
In pre-ester retort, under the conditions of 70～75 DEG C, inputting methanol and the concentrated sulphuric acid of concentration 98% in pre-ester retort, methanol is defeated
Enter that amount is saturated fatty acid content 30%, concentrated sulphuric acid addition is the 3% of methanol total amount；Reaction equation is as follows:
RCOOH+CH3OH→RCOOCH3+H2O。
This reaction total time is about 2 hours, after having reacted, fatty acid methyl ester about about 5%.After having reacted, by anti-for pre-fat
Answer the liquid in tank to stand half an hour, then use separatory funnel liquid will to divide discharge containing sour water, then rush in pre-fat retort
Entering the sour composition in tap water cleaning liquid, repeatedly clean 3 times, each water consumption is the 15% of esterification oil product total amount, every time
Standing 15 minutes after cleaning, then use separatory funnel will contain sour water and divide discharge, make water and process, the oil after dehydration divides input
In rectification conservation tank, prepare rectification.
4th, rectification finished product and production technology explanation
Being divided by oil after dehydration and be input to rectification in rectifying column from rectification conservation tank, rectification temperature is 360 DEG C, after rectification evaporation,
Oil gas through stainless steel foil water cooling heat exchanger condense after, become regeneration light Fuel finished product, yield be rectifying liquid total amount 95% with
On；Rectification residual components is distillation residual liquid, can be used for industry heavy oil, and yield is about 3%；Condensation produces a small amount of can not be cold
Solidifying combustion gas, for system after recovery, yield is less than 2%；Rectifying column uses substantial amounts of stainless steel foil, it is therefore intended that give
Rectification oil vapour is lowered the temperature, and reduces meeting of subsequent condensation device, improves condensation efficiency.Due to main component in regeneration light Fuel finished product
It is the compositions such as fatty acid methyl ester, fatty alcohol, alkane, alkene and oleic acid, the most qualitative for alcohol hydrocarbon hybrid fuel, it is also possible to as
Regeneration biological diesel oil mixed oil uses.Foundation national security supervision general bureau's safety supervision total Room (2012) No. 101 files of pipe three letter " about
Writing a letter in reply of vehicle fuel production operation permission and supervision problem " " vehicle fuel (such as methanol gasoline, alcohol hydrocarbon hybrid fuel etc.) wouldn't
Including the regulation of hazardous chemical safety in production administrative permission scope in, the product of this project construction belongs to regeneration, and " light alcohols hydrocarbon is combined car
With fuel ", it is not belonging to hazardous chemical safety in production tolerance band.
5th, prepared by catalyst
The catalyst used in the embodiment of the present invention is tungsten nickel palladium salt SZM type molecular sieve composite catalyst, and catalyst principle is as follows:
Catalytic reaction and condensation reaction is there is in saturated fat acid vapour on this nickel salt surface；In order to ensure that reacted product can be complete
Full by catalyst channels, and condensation reaction product is intercepted in heating tank, need to tie according to SZM type molecular sieve catalyst
Catalyst is fabricated to the porous small ball that hole is 200-300 nanometer, the powder metallurgy sintered method of processing technology by structure.The catalyst made
For the spheroid of diameter about 5mm, minimum hole is about 200-300 nanometer；In using, when catalyst pores is covered by area carbon
After lid reaches 60%, catalyst failure.After catalyst failure, catalyst is sent in sintering furnace, under oxidizing atmosphere, at 800 DEG C
Under the conditions of sinter 24 hours, area carbon oxidation disappear, catalyst regeneration recover function.
6th, technological process is summed up
The raw oil used in the embodiment of the present invention is waste plastics depolymerization liquefaction oil and the mixture of Palmic acid carburetion, and adding proportion is pressed
Add according to 4: 1.Use hydration means of catalysis to realize raw oil in raw oil pretreatment to react with steam, after condensation
To fatty acid, alkane, fatty alcohol, oleic acid, the mixture of alkene and the uncondensable fuel gas of little strand, follow-up refining
Satisfied fatty acid is reacted with methanol under catalyst action by system, generates fatty acid methyl ester, then produce through rectification refinement
Becoming regeneration light Fuel finished product, the technological process of production is as follows: raw oil-heating evaporation-input steam-profit steam hydration is urged
Change reaction-condensation recovery-pre-ester reaction-Acid precipitation-washing-dehydration-refine-condensation recovery-product.
7th, the component distributing of product
The product that the embodiment of the present invention produces is regeneration light Fuel, is mainly composed of below C18 fatty acid methyl ester, below C17
Satisfied fatty acid, below C17 hydro carbons, fatty alcohol, oleic acid etc., product density is about between 0.81-0.84g/ml, belongs to lightweight
Alcohol hydrocarbon hybrid fuel.
Last it is noted that above-described each embodiment is merely to illustrate technical scheme, it is not intended to limit；
Although the present invention being described in detail with reference to previous embodiment, it will be understood by those within the art that: it still may be used
So that the technical scheme described in previous embodiment to be modified, or wherein part or all of technical characteristic is carried out equivalent；
And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (8)
1. one kind utilizes the method that waste plastics prepares light Fuel, it is characterised in that comprise the following steps:
S1: use low-temperature catalyzed dissolving method to carry out depolymerization liquefaction waste plastics, obtain plastics depolymerization liquefaction oil；
S2: select liquid and the vegetable oil residue of semi liquid state, carries out the pre-heat treatment to it, preheating temperature be 70～
90℃；
S3: described plastics depolymerization liquefaction oil and the vegetable oil residue after the pre-heat treatment are pumped into raw oil pre-
Processing and carry out pretreatment in stove, carry out condensation through condensation recycling can simultaneously and reclaim, described plastics depolymerization is liquefied
The mass percent of oily and described vegetable oil residue is 70～90: 10～30, and wherein, described pretreatment specifically walks
Suddenly it is: by plastics depolymerization liquefaction oil and vegetable oil residue under the conditions of keeping uniform temperature, to be pumped into pretreatment
Stove heats, within 200 DEG C, completes moisture evaporation, the oil vapour evaporated between 220～380 DEG C and water
Steam issues unboiled water conjunction catalytic reaction in the effect of catalyst；
S4: be input in pre-ester retort carry out esterification, esterification to the oils and fats reclaimed through condensation
Time be 1.8～2.2 hours, then standing will be containing acid in pre-ester retort liquid after 0.2～0.8 hour
Moisture is discharged, and then carries out processed, is divided by the oil after processed simultaneously and be input to rectification deposit
Tank stores；
S5: the oil being stored in rectification conservation tank is divided and is input in rectifying column carry out rectification process, rectification process
Temperature be 340～380 DEG C, the oily lease making after rectification process is crossed stainless steel foil water cooling heat exchanger simultaneously
After condensation, form light Fuel finished product.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
Waste plastics is used low-temperature catalyzed dissolving method to carry out depolymerization liquefaction by described step S1 concretely comprise the following steps: will
Waste plastics is sent in dissolving tank after pulverizing, and adds acid catalyst and solvent, carries out depolymerization under the conditions of 110 DEG C
Dissolve, be delivered to dissolving liquid in evaporator be evaporated forming liquefaction oil with recycling design simultaneously, more right
Liquefaction oil carries out filtration treatment.
The method utilizing waste plastics to prepare light Fuel the most according to claim 2, it is characterised in that
Described solvent is one or more in phenol, ether, chlorobenzene, carbon tetrachloride.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
The mass percent of plastics depolymerization liquefaction oil and described vegetable oil residue described in described step S3 is 80: 20.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
The oils and fats reclaimed through condensation in described step S4 is input in pre-ester retort carry out the concrete of esterification
Step is: after hydration catalytic reaction, in the lubricant component that condensation is reclaimed, saturated fatty acid content is 4～5%,
The oil that condensation is reclaimed is divided and is input in pre-ester retort, under the conditions of 70～75 DEG C, in pre-ester retort
Input methanol and the concentrated sulphuric acid of 98%, methanol input quantity is the 30% of saturated fatty acid content, concentrated sulphuric acid addition
For methanol total amount 3%.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
The concretely comprising the following steps of processed in described step S4: pour in tap water cleaning liquid in pre-fat retort
Sour composition, repeatedly clean 2～4 times, each water consumption is the 10～20% of esterification oil product total amount, often
Stand 10～20 minutes after secondary cleaning, then use separatory funnel will contain sour water and divide discharge.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
In described step S4, the time of esterification is 2 hours, by pre-ester retort liquid after then standing 0.5 hour
Body divides discharge containing sour water.
The method utilizing waste plastics to prepare light Fuel the most according to claim 1, it is characterised in that
In described step S5, the temperature of rectification process is 360 DEG C.
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| CN2172768Y (en) * | 1993-08-28 | 1994-07-27 | 李强 | Deploymerizing still for extracting gasoline and diesel oil from waste plastic oil and vegetable oil foot |
| CN1099766A (en) * | 1993-08-28 | 1995-03-08 | 李强 | Method for extracting gasoline, diesel oil from waste plastics |
| DE102007039887A1 (en) * | 2006-08-25 | 2008-06-12 | Granit Systems S.A. | Process and apparatus for treating waste containing plastic |
| CN101255343A (en) * | 2008-02-26 | 2008-09-03 | 吴浩权 | Method for utilizing waste plastics, slop oil and refining fuel diesel |
| CN101463265A (en) * | 2009-01-16 | 2009-06-24 | 马仲刚 | Method for extracting fuel from waste oil bag, waste throwaway and waste plastic |
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| AT511772B1 (en) * | 2011-05-05 | 2018-03-15 | Omv Refining & Marketing Gmbh | METHOD AND DEVICE FOR THE ENERGY EFFICIENT PREPARATION OF SECONDARY STORES |
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