CN104611060B - A kind of method that waste plastics and Gao Fang component produce clean fuel oil - Google Patents
A kind of method that waste plastics and Gao Fang component produce clean fuel oil Download PDFInfo
- Publication number
- CN104611060B CN104611060B CN201310540462.8A CN201310540462A CN104611060B CN 104611060 B CN104611060 B CN 104611060B CN 201310540462 A CN201310540462 A CN 201310540462A CN 104611060 B CN104611060 B CN 104611060B
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction
- catalyst
- component
- waste plastics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method utilizing waste plastics and Gao Fang component to produce clean fuel oil.After high virtue component mixes with converting plastic waste to oil, first passing through heat scission reaction district, heat scission reaction district uses the mode combined with constant temperature method that gradually heats up；Obtaining cracking gas and enter back into catalytic reaction zone, contact generation catalytic reaction with catalyst therein, gained reaction effluent carries out gas-liquid separation, obtains gaseous product and liquid phase oil product.The inventive method can make waste plastics and Gao Fang component be fully used, and improves light-weight fuel oil yield and reaches more than 85%, and gained diesel quality is good.
Description
Technical field
The present invention relates to a kind of high virtue component and the processing method of waste plastics, particularly relate to one waste plastics and Gao Fang
The method that component produces clean fuel oil by thermal cracking/catalysis/hydrogenation combination technique.
Background technology
World petroleum resource is the deficientest at present, and price is the most raised；On the other hand, carrying along with people's living standard
Height, the most vigorous to cleaning motor transport demand for fuel.This contradiction so that refinery reduces discharging synergy and necessitates, and will not yet fill
Divide the refinery's accessory substance utilized to be converted into clean fuel oil and there is realistic meaning.
Ethylene bottom oil is ethylene cracking material raw material and product pyrocondensation product, its initial boiling point in steam-cracking process
At 170～260 DEG C, the end point of distillation is more than 600 DEG C, generally 600～700 DEG C, belongs to heavy distillat scope.Ethylene bottom oil is the most double
The mixture of the above condensed-nuclei aromatics of ring, wherein, arene content is up to more than 90%, and density (20 DEG C) is more than 1.0 g/cm3, sulphur and
The impurity contents such as nitrogen are low, are substantially free of metal impurities.
At present, ethylene bottom oil is mainly used as heavy oil or carbon black raw material is sold, and added value is relatively low.In order to improve economy
Benefit, each oil plant develops multiple method of comprehensive utilization, extract the most from which naphthalene and series of products thereof, the light component of utilization (<
300 DEG C) synthesizing petroleum resin, tar heavy oil produce carbon fibre asphalt and carbon fiber, produce activated carbon etc. more than 540 DEG C of heavy distillat.
Still having some intermediate oils not to be fully used in said method, overall economic efficiency needs to be further improved.
Method disclosed in CN102041091A, CN101724423A, CN101724458A and CN101724448A is first will
Ethylene bottom oil is divided into gently, weighs two cuts, then uses fixed bed hydrogenation to process technique production clean fuel oil, and these methods all exist
The problems such as light diesel fuel poor product quality, work flow length.
Use waste plastics and oil product mixing raw material through cracking fuel oil patent CN1434100A, this method solve useless
Plastics, heavy oil, the Utilizing question of waste oil, but it is high to there is cracking initial temperature, and in liquid oil, light-end products such as gasoline, diesel oil evaporates
Divide the problems such as yield is low, and its described heavy oil be the long-chain macromolecule amount high viscosity oil produced in process of oil production,
Different from the high virtue component of indication of the present invention.
CN102703101A discloses the processing method of a kind of ethylene bottom oil.Raw materials used for ethylene bottom oil and waste plastics or
Plastic oil mixture, uses pyrolysis, is catalyzed the step processing method that two reaction zones carry out reacting simultaneously, and this step processing method is complete
Cheng Caiyong gradually heats up the mode without flat-temperature zone, and heat cracking reaction district heating rate is fast, about 90 DEG C/hr.This step is processed
Method makes two kinds of raw materials not yet be sufficiently mixed just to be rapidly heated；Simultaneously because higher heating rate, make just to have mixed is former
Material not yet has enough time to react and just directly generates coke produced, and two aspects act on jointly, cause residue yield higher, and product liquid is received
Rate is on the low side, the most about about 80wt%.
Summary of the invention
For deficiency of the prior art, the invention provides one and produce clean fuel oil with waste plastics and Gao Fang component
Method, gained light Fuel product yield is high, quality is good.
A kind of method utilizing waste plastics and Gao Fang component to produce clean fuel oil of the present invention, including herein below:
(1), after high virtue component mixes with converting plastic waste to oil, initially enter heat scission reaction district and react；
(2) step (1) gained cracked gas enters catalytic reforming reaction zone, contacts with catalyst therein and carries out catalysis and change
Qualitative response；
(3) step (2) gained reaction effluent enters separator after cooling and carries out gas-liquid separation, respectively obtains gas and produces
Thing and liquid phase oil product.
The method according to the invention, wherein can also include step (4): step (3) gained liquid phase oil product mixes with hydrogen
After, passing sequentially through hydrofining reaction district and hydrocracking reaction district, gained isocrackate is separated and is fractionated, and obtains gas
Body, naphtha cut and diesel oil distillate.
In the inventive method, the waste plastics described in step (1) is polyethylene (PE), polypropylene (PP) and polystyrene
(PS) one or more in.
In the inventive method, described high virtue component refers to that petroleum chemical enterprise is produced such as ethylene bottom oil, ethene C9 component, catalysis
Cracking externally extracting oil, MIP diesel oil and coal chemical technology produced high temperature coal-tar heavy benzol, naphtalene oil, washing oil and carbolineum, shale oil, oil
One or more in sand pitch 150～600 DEG C of cuts.Wherein said high virtue component with the mixing quality ratio of waste plastics is
0.1～10, preferably 1～5.
In the inventive method, in step (1), the operating condition in heat scission reaction district is: reaction pressure (absolute pressure) is 0
～5MPa；Reaction temperature uses and gradually rises the mode of operation combining constant temperature.Described heat scission reaction includes three below rank
Section, reacting initial temperature section is 100～200 DEG C, and heating rate is 1～10 DEG C/h；Medium temperature section is 300～400 DEG C, heats up
Speed is 0～15 DEG C/hr, the most again medium temperature section constant temperature 0.5～10h；With, reaction terminating temperature section is 450～580 DEG C,
Heating rate in this temperature section is 20～50 DEG C/hr.Temperature-rise period between these three temperature section, to heating rate not
Limit and requirement.
In the inventive method, the reaction temperature of described catalytic reaction zone is 60～350 DEG C.Catalytic reaction zone can also be adopted
With gradually heating up and combining the mode of operation of constant temperature.Typically can carry out constant temperature method at 200～230 DEG C of temperature sections, during constant temperature
Between be 0.5～10h, in this temperature section, heating rate is generally 0～5 DEG C/hr.The described permanent hot arc of catalytic reaction zone operation can
To use automatic electric temperature control method.
In the inventive method, in step (2) catalyst used by catalytic reforming reaction zone be HY zeolite, Ni-REY zeolite,
HZSM-5 zeolite, HC-1 molecular sieve catalyst and amorphous silica-alumina SiO2-Al2O3In any one or two or more.Step
(2) consumption of described catalyst is general waste plastics and the 0.5% of Gao Fang component weight～2.0%.
The routine operation that gas-liquid separation is this area in the inventive method, described in step (3).
In the inventive method, in step (4), the cut point of naphtha and diesel oil distillate is generally 130～155 DEG C, naphtha
Cut is used as cracking stock returning ethylene cracker through further hydrofinishing Posterior circle, and diesel oil distillate is generally as bavin
Oil blend component dispatches from the factory.
In the inventive method, described heat scission reaction district is generally located on two different reactors with catalytic reaction zone
In, connected by pipeline between two reactors.
In the inventive method, step (3) gained gaseous product can be as fuel gas through collecting, and gained naphtha cut can
To go ethylene cracker to make cracking stock, diesel oil distillate dispatches from the factory as qualified diesel product.
In the inventive method, the hydrofining reaction district described in step (4) and hydrocracking reaction district can be same
In individual reactor, it is also possible to respectively in different reactors.Described hydrofining reaction district loads the most successively and adds
Hydrogen guard catalyst and Hydrobon catalyst, described hydrocracking reaction district filling hydrocracking catalyst.Hydrofinishing
The admission space ratio of catalyst and hydrocracking catalyst is 1～3:1, and the loadings of hydrogenation protecting catalyst typically constitutes from hydrogenation essence
The 5%～40% of Catalyst packing volume processed.
In the inventive method, described hydrofining reaction district and hydrocracking reaction district all use fixed bed hydrogenation work
Skill.Described hydrofining reaction district and hydrocracking reaction district typically use one-stage serial technique.Described hydrofinishing is anti-
The operating condition answering district is: mean temperature 350～390 DEG C, hydrogen dividing potential drop 10.0～16.0MPa, hydrogen to oil volume ratio 900:1～
1500:1, volume space velocity 0.3～3.0 h during liquid-1.The operating condition in described hydrocracking reaction district is: mean temperature 350～
390 DEG C, hydrogen dividing potential drop 10.0～16.0MPa, hydrogen to oil volume ratio is 900:1～1500:1, volume space velocity 0.3～3.0h during liquid-1。
In the inventive method, the Hydrobon catalyst that described hydrofining reaction district uses is conventional hydrofinishing
Catalyst or pretreating catalyst by hydrocracking.Hydrobon catalyst is typically with group VIB and/or group VIII metal as activity
Component, with the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus as carrier, group VIB metal is generally Mo and/or W, and
VIII race's metal is generally Co and/or Ni.On the basis of the weight of catalyst, group VIB tenor is calculated as 10wt% with oxide
～35wt%, group VIII metal content is calculated as 3wt%～15wt% with oxide.The physical property of catalyst is as follows: specific surface area is
100～350m2/ g, pore volume is 0.15～0.60mL/g.Alternative commercial catalysts has Fushun Petrochemical Research Institute
(FRIPP) develop 3936,3996, FF-16, FF-26 etc..
In the inventive method, described hydrocracking reaction district can use one or more hydrocracking catalyst of routine
Agent, typically with VI B race and/or group VIII metal as active component, group VIB metal is generally Mo and/or W, group VIII metal
Generally Co and/or Ni.Carrier is the two or more in aluminum oxide, silicon-containing alumina, molecular sieve, it is preferred to use containing amorphous
Sial and the hydrocracking catalyst that molecular sieve is main acidic components.The present invention recommends the following (weight with catalyst of composition
On the basis of): Y molecular sieve or beta-molecular sieve 10%～40%, amorphous silica-alumina 20%～60%, group VIB hydrogenation active component is with oxidation
The content of thing meter is 15%～40%, and the VIIIth race's hydrogenation active component content in terms of oxide is 1%～10%, and surplus is aperture oxygen
Change aluminium.The physical property of hydrocracking catalyst is as follows: specific surface is 180～300m2/ g, pore volume is 0.25～0.45mL/g.
Such as: FC-14 that optional Fushun Petrochemical Research Institute (FRIPP) researches and develops, ZHC-02, the business such as 3974 are hydrocracked and urge
Agent.
In the inventive method, the hydrogenation protecting catalyst that described hydrofining reaction district uses can use conventional residual oil to add
Hydrogen protective agent or residuum hydrogenating and metal-eliminating catalyst, typically with VI B race and/or group VIII metal as active component, with aluminum oxide
Or silicon-containing alumina is carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With catalysis
The weight meter of agent, active metallic content is calculated as 0.5wt%～18wt% with oxide, preferably: group VIB tenor is with oxide
Being calculated as 0.5wt%～15wt%, group VIII metal content is calculated as 0.5wt%～8wt% with oxide, and shape can be hollow cylinder
Body, spherical, clover or bunge bedstraw herb shape etc..Hydrogenation protecting catalyst can select FZC-103 that FRIPP researches and develops, FZC-200,
FZC-100 and FZC-102B residual oil hydrocatalyst.
Compared with prior art, the method for the present invention has the advantage that
1, the inventive method exists for current waste plastics and ethylene bottom oil mixing raw material pyrolysis catalytic light-weight fuel oil
The problem such as light oil yield is low, use two step processing methods, suitable pyrolysis reaction region temperature and catalysis can be controlled respectively
Reaction zone temperature, makes liquid product yield significantly improve to more than 85%.
2, the inventive method uses two step processing methods, controls the intensification speed of heat scission reaction district differential responses section the most respectively
Rate, particularly controls initial reaction section and the heating rate of middle temperature conversion zone, the most melt-blended to guarantee two kinds of raw materials.This Shen
Inventor please finds, for waste plastics is such as vinyon, because it is the macromolecular compound that molecule determines, the most molten
Change and need to carry out at a certain temperature, and could be sufficiently mixed with the high virtue component of liquid phase after only it is completely melt.Therefore
In the methods of the invention, slower heating rate should be used in heat scission reaction process initial reaction section, to avoid because rising as far as possible
Temperature speed is too fast, causes its fusing that is not able to do in time, mixes and react and just directly generate residue.And carry out at middle temperature conversion zone
Constant temperature or control the slower heating rate of middle-temperature section, then can ensure that the two kinds of raw material haptoreactions fully mixed, keep away
Exempt to make because heating rate is too fast raw material also have not enough time to reaction and be generated as residue.The cracking gas that heat scission reaction district obtains enters
Second step catalytic reaction zone, uses electric control temperature mode to make this reaction zone in suitable range of reaction temperature, it can be ensured that catalysis
Agent gives full play to its catalytic upgrading activity, and ensures the reaction time of abundance.Aspects above acts on jointly so that side of the present invention
The level of residue of method significantly reduces, and light Fuel yield reaches 95%, improves more than about 5 percentage points than existing method, and this is for useless
For plastics and Gao Fang component prepare fuel oil technology, a huge progress beyond doubt.
3, this method mixes in appropriate proportions with by waste plastics and Gao Fang component, hot cracked, catalytic reaction, obtain gas,
Liquid, solid three-phase product, wherein liquid product whole fraction oil hydrotreating, obtain naphtha cut and diesel oil two cut, naphtha evaporates
Point ethylene unit can be gone to be used as cracking stock, diesel oil distillate is qualified diesel product, and the method has that operation is simple, lightweight
Fuel oil yield is high, the advantage of good product quality.
4, waste plastics and Gao Fang component are mixed by the inventive method in appropriate proportions, use first heat scission reaction, be catalyzed
The method of reaction, wherein heat scission reaction and catalytic reaction all use the method slowly, gradually heated up by low temperature, can make
The unsaturated hydrocarbons such as a certain amount of virtue alkene in get Gao Fang component are the most first polymerized, and generate polyarylene hydrocarbon macromolecule chemical combination
Thing, along with the raising of reaction temperature, there occurs the thermal cracking/catalytic reaction process of similar polystyrene plastics, simultaneously at poly-virtue
In the complex reaction system that alkene macromolecular compound is parallel with polycyclic aromatic hydrocarbon, staggered, some intermediate products are likely to mutually reciprocal
Should, generate virtue unsaturated hydrocarbons and the polycyclic hydro carbons such as alkene again, so go round and begin again, move in circles that it is the biggest to make in high virtue component
Most compounds has all participated in thermal cracking, catalytic reaction, thus the raw material of about more than 95% can be made all to be converted into lightweight combustion
Material, such as fuel gas and light-weight fuel oil, has reached procedure of processing simple, the purpose that conversion ratio is high.If initial temperature is too high
Polycondensation reaction can occur, make amount of coke increase, light Fuel yield declines, and is unfavorable for the production of light Fuel.
5, the present invention is the relatively low waste plastics of added value and Gao Fang component provides a kind of processing side improving its economy
Method, under the present situation of crude supply growing tension, reduces discharging synergy to refinery useful.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.
Detailed description of the invention
With specific embodiment, the method for the present invention is described further below in conjunction with the accompanying drawings.
As it is shown in figure 1, a kind of waste plastics of the present invention and Gao Fang component produce the technique stream of the method for clean fuel oil
Journey is as follows: high virtue component 1 and mixing with waste plastics 2, is introduced into heat scission reaction district 3, carries out pyrolytic reaction.Gained cracking gas 4
Enter catalytic reforming reaction zone 5 through pipeline, contact generation catalytic reaction with catalyst therein.Gained modification reaction effluent
6 condensed devices 7 condensation after enter separator 8, separated after obtain gaseous product 9 and liquid phase oil product 10, in course of reaction produce
Residue stay in pyrolysis reaction zone 3, described residue can use as solid fuel.Described gaseous product 9 can through collecting
As fuel gas, after liquid phase oil product 10 mixes with hydrogen 19, carry out hydrofinishing by hydrotreating reactor 11 and hydrogenation splits
Changing reaction, gained isocrackate 12 enters piece-rate system 13 and carries out gas-liquid separation, and the outer row of gas 14, liquid product 15 enters
Fractionating system 16, is fractionated into obtaining naphtha cut 17 and diesel oil distillate 18, and naphtha cut 17 can remove ethylene cracker
Making ethylene cracking material, diesel oil distillate 18 goes out device as product.
This method will be further described by the following examples, it is not limited to this.
Used by the embodiment of the present invention, hydrocracking catalyst preparation is as follows:
1, containing amorphous silica-alumina and the preparation of the hydrocracking catalyst of Y zeolite: A1, A2.
(1) hydrocracking catalyst A1:
By amorphous silica-alumina (specific surface area 520 m2/ g, SiO235wt%, pore volume 1.2mL/g) and Y molecular sieve (SiO2/
Al2O3Mol ratio is 9, lattice constant 2.432nm, specific surface area 650m2/ g, infrared acidity 0.45mmol/g), add after mixing
(being added prepared by dust technology peptization by the little porous aluminum oxide of pore volume 0.42mL/g) adhesive roll agglomerating after, put in banded extruder squeeze
After bar shaping, it is dried 10 hours at 110 DEG C, 4 hours prepared carriers of 500 DEG C of activation, then by Mo-Ni co-impregnation immersion stain, then
It is dried 12 hours at 110 DEG C, and 500 DEG C activate 3 hours.Catalyst finally consists of: amorphous silica-alumina 48wt%, Y molecular sieve
15wt%, aluminum oxide 12wt%, nickel oxide 5wt%, molybdenum oxide 20wt%.Specific surface area of catalyst 220m2/ g, pore volume 0.35mL/g.
(2) hydrocracking catalyst A2:
By amorphous silica-alumina (specific surface area 490m2/ g, SiO245wt%, pore volume 1.0mL/g) and Y molecular sieve (SiO2/Al2O3
Mol ratio is 12, lattice constant 2.436nm, specific surface area 680m2/g, infrared acidity 0.41mmol/g), add after mixing (by
The little porous aluminum oxide of pore volume 0.42mL/g adds the preparation of dust technology peptization) adhesive roll agglomerating after, put in banded extruder squeeze
After bar shaping, it is dried 10 hours at 110 DEG C, after 4 hours prepared carriers of 500 DEG C of activation, then by W-Ni co-impregnation immersion stain, so
After 110 DEG C be dried 12 hours, and 500 DEG C activate 3 hours.Catalyst finally consists of: amorphous silica-alumina 45wt%, Y molecular sieve
13wt%, aluminum oxide 12wt%, nickel oxide 6.5wt%, tungsten oxide 22.5wt%.Specific surface area of catalyst 210m2/ g, pore volume
0.31mL/g。
2, the preparation of the hydrocracking catalyst B1 containing amorphous silica-alumina and beta-molecular sieve.
By beta-molecular sieve (SiO2/Al2O3Mol ratio is 40, specific surface area 580m2/ g, infrared acidity 0.21mmol/g), nothing
Amorphous silicon-alumina (specific surface area 450m2/g, SiO255wt%, pore volume 0.9mL/g) mix, add dilute by concentration 3.3wt%
Salpeter solution peptization little porous aluminum oxide (specific surface area 240m2/ g, pore volume is 0.42mL/g) adhesive that obtains, continues kneading
Until becoming paste, extruded moulding, being obtained shaping bar and being dried at 110 DEG C 12 hours, 500 DEG C of activation prepare activation in 4 hours
After carrier.Impregnate the carrier of above-mentioned preparation again with W-Ni co-impregnated solution, then be dried 8 hours at 110 DEG C, and 500 DEG C activate 3 hours.
Catalyst finally consists of: β zeolite 25wt%, amorphous silica-alumina 25wt%, aluminum oxide 20wt%, nickel oxide 7.5wt%, tungsten oxide
22.5wt%.Specific surface area of catalyst 235m2/ g, pore volume 0.32mL/g.
In the embodiment of the present invention, used by embodiment 1 and embodiment 2, high virtue component is Gao Fang used by ethylene bottom oil, embodiment 3
Component is high temperature coal-tar 180～500 DEG C of cuts, and both character are listed in table 1, and waste plastics used by embodiment 1 is polyethylene, implements
Waste plastics as used by 2 is polypropylene, and waste plastics used by embodiment 3 is polystyrene.Described heat scission reaction district and catalytic reforming
Reaction zone is positioned at two reactors, is connected by pipeline between two reactors.Described liquid product whole fraction oil hydrotreating
Reaction zone and hydrocracking reaction district use one-stage serial technique, hydrofining reaction district from top to bottom load hydrogenation protecting agent and
Hydrobon catalyst, hydrocracking reaction district is built-in fills out hydrocracking catalyst.Hydrotreating liquid product is separated, distillation
Obtain naphtha and diesel oil distillate, cut point 150 DEG C.
Embodiment 1
Ethylene bottom oil and polyethylene mixing raw material thermal cracking/catalytic reaction process conditions, gained gaseous product, liquid produce
Thing, the yield of three kinds of products of residue and full cut character are shown in Table 2.Catalytic reforming reaction zone used catalyst is that HC-1 molecular sieve is urged
Agent, catalyst amount is the 1.5wt% of ethylene bottom oil, and described whole fraction oil hydrotreating/hydrocracking process condition is shown in Table 3, its
In, hydrogenation protecting agent, Hydrobon catalyst, the volume ratio of hydrocracking catalyst are 10:60:30.React final gained vapour
Oil distillate and diesel oil distillate character are shown in Table 4.
Embodiment 2
Compared with Example 1, catalytic reforming reaction zone used catalyst is ZSM-5 molecular sieve catalyst, and consumption is with implementing
Example 1.Described whole fraction oil hydrotreating/hydrocracking process condition is shown in Table 3, wherein, hydrogenation protecting agent, Hydrobon catalyst,
The volume ratio of hydrocracking catalyst is 15:50:35, and reaction result is shown in Table 4.
Embodiment 3
Compared with Example 1, catalytic reforming reaction zone used catalyst is HC-1 molecular sieve catalyst and ZSM-5 molecular sieve
Catalyst, two kinds of catalyst volumes are than for 1:1, and catalyst amount is with embodiment 1.Described whole fraction oil hydrotreating/be hydrocracked
Process conditions are shown in Table 3, and wherein, hydrogenation protecting agent, Hydrobon catalyst, the volume ratio of hydrocracking catalyst are 10:60:
30, reaction result is shown in Table 4.
Comparative example 1
Compared with Example 1, pyrolysis and catalytic reforming reaction are carried out in a step simultaneously, and pyrolysis reaction region temperature is
160 ~ 520 DEG C, the reaction time is 4 hours (90 DEG C/hr of heating rate), and other operation is with embodiment 1.Reaction result is shown in Table 4.
Comparative example 2
Compared with Example 1, heat is borrowed and catalytic reforming reaction is carried out, i.e. by Pyrolysis in a step simultaneously
Answering the mode directly heated up in district, making pyrolysis reaction region temperature is 160 ~ 520 DEG C, and the reaction time is 8 hours (average rate heating rates 45
DEG C/hr, not temperature-gradient method), other operation is with embodiment 1.Reaction result is shown in Table 4.
Table 1 high virtue constitutive property.
| Crude title | Ethylene bottom oil | High temperature coal-tar 170～600 DEG C of cuts |
| Density (20 DEG C), kg m-3 | 1090.5 | 1235.1 |
| S, μ g g-1 | 355 | 5600 |
| N, μ g g-1 | 187 | 10256 |
| Four components, wt% | ||
| Saturated point | 2.57 | 1.0 |
| Fragrance point | 45.50 | 53.2 |
| Colloid | 29.93 | 43.5 |
| Asphalitine | 22.01 | 2.3 |
| Boiling range, DEG C | ||
| IBP/10%/30% | 165/216/246 | 185/286/326 |
| 50%/70%/90% | 315/371/402 | 345/381/462 |
Table 2 thermal crackings/Catalytic processes condition and product property.
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| High virtue component/waste plastics | 1:1 | 5:1 | 1:5 |
| Heat scission reaction condition | |||
| Initial temperature section, DEG C | 100-120 | 120-140 | 150-180 |
| Heating rate, DEG C/hr | 10 | 5 | 1 |
| Medium temperature section, DEG C | 300~360 | 320~380 | 350 |
| Heating rate, DEG C/hr | 12 | 8 | 0 |
| Reaction time | 5(middle-temperature section) | 7.5(middle-temperature section) | 4(middle-temperature section) |
| Final temperature section, DEG C | 490～570 | 480～550 | 470～520 |
| Heating rate, DEG C/hr | 20 | 50 | 30 |
| Reaction pressure, MPa | 0.11 | 0.11 | 0.11 |
| Catalytic reaction condition | |||
| Reaction temperature section, DEG C | 200-210 | 220 | 220-230 |
| Heating rate, DEG C/hr | 2 | 0 | 4 |
| Product yield, wt% | |||
| Gaseous product | 9.9 | 9.8 | 8.9 |
| Product liquid | 85. 8 | 85. 4 | 87. 0 |
| Wherein diesel oil distillate | |||
| Residue | 4. 3 | 4.8 | 4. 1 |
| Liquid product character | L1 | L2 | L3 |
| Density (20 DEG C), g/cm3 | 0.8618 | 0.8540 | 0.8693 |
| Sulfur content, μ g/g | 141 | 135 | 150 |
| Nitrogen content, μ g/g | 97 | 85 | 103 |
| Boiling range, DEG C | |||
| IBP～EBP | 65～366 | 60～365 | 66～367 |
Table 2-continues comparative example process conditions and product property.
| Scheme | Comparative example 1 | Comparative example 2 |
| High virtue component/waste plastics | 1:1 | 1:1 |
| Pyrolysis catalytic reaction condition | ||
| Reacting initial temperature, DEG C | 160 | 160 |
| Reaction terminating temperature, DEG C | 520 | 520 |
| Heating rate, DEG C/hr | 90 | 45 |
| Reaction time, hr | 4 | 8 |
| Reaction pressure, MPa | 0.11 | 0.11 |
| Product yield, wt% | L4 | L5 |
| Gaseous product | 10.6 | 10.7 |
| Product liquid | 80.9 | 81.3 |
| Residue | 8.5 | 8.0 |
| Liquid product character | L4 | L5 |
| Density (20 DEG C), g/cm3 | 0.9020 | 0.882 |
| Sulfur content, μ g/g | 152 | 156 |
| Nitrogen content, μ g/g | 99 | 82 |
| Boiling range, DEG C | ||
| IBP～EBP | 68～372 | 64～370 |
Table 3 hydrogenation of total effluent treatment process condition.
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Raw material | L1 | L2 | L3 | L4 | L5 |
| Hydrogenation protecting agent | FZC-103 | FZC-103 | FZC-103 | FZC-103 | FZC-103 |
| Hydrobon catalyst | 3936 | 3936 | 3936 | 3936 | 3936 |
| Hydrocracking catalyst | A1 | A2 | B1 | A1 | A1 |
| Process conditions | |||||
| Hydrogen dividing potential drop, MPa | 15.0 | 16.0 | 14.0 | 15.0 | 15.0 |
| Hydrofinishing temperature, DEG C | 365 | 370 | 385 | 365 | 365 |
| It is hydrocracked temperature, DEG C | 375 | 380 | 390 | 375 | 375 |
| Volume space velocity during liquid, h-1 | 0.8/0.8 | 0.6/0.6 | 1.0/1.0 | 0.8/0.8 | 0.8/0.8 |
| Hydrogen to oil volume ratio | 1200 | 1300 | 1500 | 1200 | 1200 |
Table 4 diesel oil distillate and naphtha cut character.
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Diesel oil distillate | |||||
| Yield, wt% | 60.1 | 66.6 | 58.3 | 55.1 | 56.2 |
| Density (20 DEG C), g/cm3 | 0.8510 | 0.8506 | 0.8403 | 0.8674 | 0.8646 |
| Sulfur content, μ g/g | 9 | 8 | 6 | 10 | 9 |
| Condensation point/DEG C | ＜-32 | ＜-32 | ＜-33 | ＜-35 | ＜-34 |
| Boiling range/DEG C | |||||
| 50%/90%/ 95% | 200/272/305 | 195/256/304 | 193/252/301 | 202/275/308 | 201/270/306 |
| Cetane number | 46.4 | 46.5 | 47.2 | 40.3 | 41.8 |
| Naphtha cut | |||||
| Yield, wt% | 26.6 | 19.7 | 29.6 | 26.6 | 25.9 |
| Density (20 DEG C), g/cm3 | 0.7506 | 0.7483 | 0.7401 | 0.7686 | 0.7282 |
| Sulfur content, μ g/g | 6 | 6 | 5 | 7 | 6 |
In the present embodiment, the yield of naphtha cut and diesel oil distillate is all to be former with high virtue component and waste plastic mixture
Expect calculated.
By table 4 it will be seen that height virtue component and waste plastics are used two-step method, first carry out thermal cracking, then carry out catalysis and change
Qualitative response, and combine the method being hydrocracked, gained light Fuel yield is 94.5%～95.9%, is far longer than employing one-step method
Pyrolysis/catalysis is in conjunction with the method for hydrogenation, and the yield of the inventive method gained diesel oil distillate is high and quality is good simultaneously, and this illustrates this
The part that in inventive method, light Fuel yield increases is mainly derived from the increase of diesel yield.
Claims (14)
1. the method producing clean fuel oil by waste plastics and Gao Fang component, including herein below:
(1), after high virtue component mixes according to the weight ratio of 0.1～10 with converting plastic waste to oil, initially enter heat scission reaction district and carry out instead
Should；Described heat scission reaction includes that three below stage, reacting initial temperature section are 100～200 DEG C, heating rate be 1～
10℃/h；Medium temperature section is 300～400 DEG C, and heating rate is 0～15 DEG C/h；Reaction terminating temperature section is 450～580 DEG C,
Heating rate is 20～50 DEG C/h；
(2) step (1) gained cracked gas enters catalytic reforming reaction zone, contacts with catalyst therein that to carry out catalytic reforming anti-
Should；
(3) step (2) gained reaction effluent enters separator after cooling and carries out gas-liquid separation, respectively obtain gaseous product and
Liquid phase oil product；
Described high virtue component is selected from ethylene bottom oil, ethene C9 component, catalytic pyrolysis externally extracting oil, MIP diesel oil, high temperature coal-tar
One or more in heavy benzol, naphtalene oil, washing oil, carbolineum, shale oil, oil sands bitumen 150～600 DEG C of cuts.
The most in accordance with the method for claim 1, it is characterised in that also include step (4): step (3) gained liquid phase oil product with
After hydrogen mixing, passing sequentially through hydrofining reaction district and hydrocracking reaction district, gained isocrackate is separated and divides
Evaporate, obtain gas, naphtha cut and diesel oil distillate.
The most in accordance with the method for claim 1, it is characterised in that the reaction pressure 0～5MPa in described heat scission reaction district.
4. according to the method described in claim 1 or 2, it is characterised in that described waste plastics is polyethylene, polypropylene and polyphenyl
One or more in ethene.
5. according to the method described in claim 1 or 2, it is characterised in that in step (1), described high virtue component and waste plastics
Mixing quality ratio be 1～5.
6. according to the method described in claim 1 or 2, it is characterised in that the reaction of the catalytic reforming reaction zone described in step (2)
Temperature is 60～350 DEG C.
The most in accordance with the method for claim 6, it is characterised in that in step (2), employing gradually heats up and combines the behaviour of constant temperature
Making mode, react 0.5～10h at 200～230 DEG C of temperature sections, heating rate is 0～5 DEG C/h.
8. according to the method described in claim 1 or 2, it is characterised in that catalysis used by catalytic reforming reaction zone in step (2)
Agent is HY zeolite, Ni-REY zeolite, HZSM-5 zeolite, HC-1 molecular sieve catalyst and amorphous silica-alumina SiO2-Al2O3In appoint
Anticipate one or more.
The most in accordance with the method for claim 8, it is characterised in that the consumption of step (2) described catalyst is waste plastics and height
The 0.5%～2.0% of virtue component weight.
The most in accordance with the method for claim 2, it is characterised in that in step (4), the cut point of naphtha and diesel oil distillate is
130～155 DEG C.
11. according to the method described in claim 1 or 2, it is characterised in that described heat scission reaction district and catalytic reaction zone set
Put in two different reactors, connected by pipeline between two reactors.
12. in accordance with the method for claim 2, it is characterised in that the hydrofining reaction district operating condition described in step (4)
For: mean temperature 350～390 DEG C, hydrogen dividing potential drop 10.0～16.0MPa, hydrogen to oil volume ratio 900:1～1500:1, during liquid, volume is empty
Speed 0.3～3.0h-1；The operating condition in described hydrocracking reaction district is: mean temperature 350～390 DEG C, hydrogen dividing potential drop 10.0～
16.0MPa, hydrogen to oil volume ratio is 900:1～1500:1, volume space velocity 0.3～1.0h during liquid-1。
13. in accordance with the method for claim 2, it is characterised in that the hydrofinishing that described hydrofining reaction district uses
Catalyst is with group VIB and/or group VIII metal as active component, with aluminum oxide, silicon-containing alumina or the siliceous and oxidation of phosphorus
Aluminium is carrier, and on the basis of the weight of catalyst, group VIB tenor is calculated as 10wt%～35wt% with oxide, the VIIIth race
Tenor is calculated as 3wt%～15wt% with oxide；Its character is as follows: specific surface area is 100～350m2/ g, pore volume is 0.15
～0.60mL/g.
14. in accordance with the method for claim 2, it is characterised in that described hydrocracking reaction district uses to be hydrocracked and urges
Agent, with VI B race and/or group VIII metal as active component, carrier be aluminum oxide, silicon-containing alumina, amorphous silica-alumina and point
Son sieve in two or more；On the basis of the weight of catalyst, catalyst contains Y molecular sieve or beta-molecular sieve 10%～40%, without fixed
Shape sial 20%～60%, group VIB hydrogenation active component content in terms of oxide is 15%～40%, the VIIIth race's hydrogenation activity group
Dividing the content in terms of oxide is 1%～10%, and surplus is little porous aluminum oxide；The character of hydrocracking catalyst is as follows: specific surface
It is 180～300m2/ g, pore volume is 0.25～0.45mL/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310540462.8A CN104611060B (en) | 2013-11-05 | 2013-11-05 | A kind of method that waste plastics and Gao Fang component produce clean fuel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310540462.8A CN104611060B (en) | 2013-11-05 | 2013-11-05 | A kind of method that waste plastics and Gao Fang component produce clean fuel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104611060A CN104611060A (en) | 2015-05-13 |
| CN104611060B true CN104611060B (en) | 2016-08-17 |
Family
ID=53145714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310540462.8A Active CN104611060B (en) | 2013-11-05 | 2013-11-05 | A kind of method that waste plastics and Gao Fang component produce clean fuel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104611060B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520168A (en) * | 2015-09-14 | 2017-03-22 | 中国科学院宁波材料技术与工程研究所 | Method and system for producing diesel oil from inferior oil material |
| CN108970616A (en) * | 2017-05-30 | 2018-12-11 | 镇江杜微人才咨询有限公司 | A kind of preparation method of biomass tar cracking catalyst |
| CN111088058A (en) * | 2019-12-27 | 2020-05-01 | 青岛惠城环保科技股份有限公司 | Method for preparing oil from waste plastics |
| GB2590525B (en) * | 2020-08-14 | 2022-08-31 | Clean Planet Energy | Commercial grade ultra-low sulphur diesel production process from mixed waste plastics pyrolysis oil |
| CN114437752B (en) * | 2020-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Method and system for preparing hydrocarbon products from waste plastics |
| CN116162491A (en) * | 2021-11-25 | 2023-05-26 | 中国科学院宁波材料技术与工程研究所 | Method and system for producing clean fuel oil by pyrolyzing and catalyzing inferior heavy oil |
| CN115093878B (en) * | 2022-07-15 | 2023-12-05 | 中塑汇鑫科技发展有限公司 | Method for preparing naphtha from waste plastics |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175211A (en) * | 1977-03-14 | 1979-11-20 | Mobil Oil Corporation | Method for treatment of rubber and plastic wastes |
| US5569801A (en) * | 1992-08-27 | 1996-10-29 | Fina Research, S.A. | Polymer conversion process |
| CN1178823A (en) * | 1996-10-08 | 1998-04-15 | 伍伟国 | Process for oil refinery from waste material of used petroleum product |
| CN1266879A (en) * | 1999-03-13 | 2000-09-20 | 张洪孝 | Process for producing fuel oil from waste or used plastics |
| CN1434100A (en) * | 2003-03-10 | 2003-08-06 | 湖南大学 | Method for making fuel oil by mixing-cracking waste plastics, waste oil and heavy oil |
| CN102703101A (en) * | 2012-06-29 | 2012-10-03 | 李昌源 | Method for processing ethylene tar |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011038027A1 (en) * | 2009-09-22 | 2011-03-31 | Neo-Petro, Llc | Hydrocarbon synthesizer |
-
2013
- 2013-11-05 CN CN201310540462.8A patent/CN104611060B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175211A (en) * | 1977-03-14 | 1979-11-20 | Mobil Oil Corporation | Method for treatment of rubber and plastic wastes |
| US5569801A (en) * | 1992-08-27 | 1996-10-29 | Fina Research, S.A. | Polymer conversion process |
| CN1178823A (en) * | 1996-10-08 | 1998-04-15 | 伍伟国 | Process for oil refinery from waste material of used petroleum product |
| CN1266879A (en) * | 1999-03-13 | 2000-09-20 | 张洪孝 | Process for producing fuel oil from waste or used plastics |
| CN1434100A (en) * | 2003-03-10 | 2003-08-06 | 湖南大学 | Method for making fuel oil by mixing-cracking waste plastics, waste oil and heavy oil |
| CN102703101A (en) * | 2012-06-29 | 2012-10-03 | 李昌源 | Method for processing ethylene tar |
Non-Patent Citations (3)
| Title |
|---|
| 初始温度对废轮胎热解的影响;付兴民等;《环境工程学报》;20130531;第7卷(第5期);1907-1912 * |
| 升温速率对废塑料热解过程的影响;石耀华等;《节能技术》;20110531;第29卷(第03期);199-203 * |
| 废塑料混合物分段热裂解的研究;李法鸿等;《石油炼制与化工》;20010531;第32卷(第05期);21-54 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104611060A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104611060B (en) | A kind of method that waste plastics and Gao Fang component produce clean fuel oil | |
| CN101724423B (en) | Method for processing ethylene tar | |
| CN101045884B (en) | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil | |
| CN101724448B (en) | Hydro-cracking method for blending ethylene bottom oil | |
| CN102041091B (en) | Method for processing ethylene tar | |
| CN102234542B (en) | Hydrocracking method for blending ethylene tar | |
| CN101724458B (en) | Method for hydrogenating ethylene tar | |
| CN102041075B (en) | Anthracene oil hydrogenation method | |
| CN106520168A (en) | Method and system for producing diesel oil from inferior oil material | |
| CN103805248B (en) | Ethylene bottom oil produces the method for clean fuel oil | |
| CN104611030B (en) | Coking method for producing fuel oil from waste plastics | |
| CN102041073B (en) | Hydrocracking method for anthracene oil | |
| CN103773497B (en) | A kind of method increasing production clean fuel oil | |
| CN103102976B (en) | Treatment method of ethylene tar | |
| CN102234539B (en) | Method for processing ethylene tar | |
| CN103102975B (en) | Method for producing clean fuel oil from ethylene tar | |
| CN103102977B (en) | Method for producing light fuel oil from ethylene tar | |
| CN102041087B (en) | Hydrocracking method of deep cut anthracene oil | |
| CN104560153A (en) | Method for producing clean fuel oil employing ethylene bottom oil and heavy benzol | |
| CN103789037B (en) | Processing method for by-products of ethylene equipment | |
| CN102234538A (en) | Method for hydrotreating ethylene tar | |
| CN103805271B (en) | A kind of working method of ethylene cracker by-product | |
| CN103102978B (en) | Processing method of ethylene tar | |
| CN102041076B (en) | Method for producing light fuel oil by hydrogenating anthracene oil | |
| CN111378494B (en) | Processing method of Fischer-Tropsch synthetic oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |