CN106350092B - The method of the low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire and carbon black - Google Patents
The method of the low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire and carbon black Download PDFInfo
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- CN106350092B CN106350092B CN201610883816.2A CN201610883816A CN106350092B CN 106350092 B CN106350092 B CN 106350092B CN 201610883816 A CN201610883816 A CN 201610883816A CN 106350092 B CN106350092 B CN 106350092B
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- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/482—Preparation from used rubber products, e.g. tyres
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses the method for a kind of low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire and carbon black, including (1) to isolate steel wire by damaged tire and be broken into the waste rubber grain of 5~30 mesh；(2) waste rubber grain and catalyst nickel chloride are added in pyrolysis furnace, thermal cracking is carried out in the case where temperature is 400~550 DEG C, pressure is 0.01~0.01MPa；(3) high-temperature oil gas produced in cracking process and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, isolates high-temperature oil gas and thin carbon black, high-temperature oil gas condenses to obtain fuel oil into fractionating column；(4) the cracking slag coarse carbon black produced in cracking process is discharged from pyrolysis furnace slag-drip opening, and by being ground into thin carbon black, carbon black products are mixed to get with thin carbon black in step (3).The present invention takes the mode that catalysis pyrolysis is carried out at the same time, and can reduce the activation energy of reaction, improves the quality and yield of pyrolysis oil product.
Description
Technical field
It is low-temperature catalyzed more particularly, to a kind of automobile damaged tire the present invention relates to a kind of rubber pyrolysis technology field
The method of thermal cracking made fuel oil and carbon black.
Background technology
With continuing to increase for China's automobile volume of holding, the waste tire quantity produced after motor vehicle liquidation is growing day by day, gives up
Tire accumulating amount is big, if handling not in time except land occupation can also pollute environment.Have at present for damaged tire several
Processing method：(1) renovate, tyre rebuilding meets the requirement of the feature of environmental protection and economy, but reclaimed rubber is compared to natural rubber
It has been be short of that, renovation number is usually no more than twice；(2) burn, tire can supply daily life after broken as fuel
Use, this method is simple, but due to that can produce substantial amounts of pernicious gas in burning process, it is in feature of environmental protection side
Face does not have advantage；(3) thermal cracking, thermal cracking are to handle a kind of new industrial technology route of waste tire, its energy oil recovery,
The products such as coal gas, carbon black, due to high financial profit, can realize maximum resource utilization and enjoy people to favor, but at present
Cracking technology there are reaction rate is slow, cracking temperature is high, pyrolysis oil quality and the shortcomings such as yield is low.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of low-temperature catalyzed heat of automobile damaged tire
The method for cracking made fuel oil and carbon black, this method take the mode that catalysis pyrolysis is carried out at the same time, and can reduce the activation energy of reaction,
Pyrolytic reaction speed is improved, improves the quality and yield of pyrolysis oil product.
The low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire of the present invention and the method for carbon black, comprise the following steps：
Step (1)：Damaged tire is isolated into steel wire and is ground into the waste rubber grain of 5~30 mesh, by rubber pulverizing into thin
Particle can be such that rubber grain is fully contacted with catalyst, and cracking reaction fully carries out, and crush carefully destroy rubber very much big
The molecular structure of molecular substance, optimal grain graininess are 5~30 mesh；
Step (2)：Waste rubber grain and catalyst nickel chloride are added in pyrolysis furnace, temperature for 400~550 DEG C,
Pressure is to carry out thermal cracking under -0.01~0.01MPa；
Step (3)：The high-temperature oil gas produced in cracking process and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into height
Wet solid separator, isolates high-temperature oil gas and thin carbon black, and high-temperature oil gas condenses to obtain fuel oil into fractionating column；
Step (4)：The cracking slag coarse carbon black produced in cracking process is discharged from pyrolysis furnace slag-drip opening, by being ground into thin charcoal
It is black, it is mixed to get carbon black products with thin carbon black in step (3).
Beneficial effects of the present invention：The present invention uses pyrolysis and catalytic pyrolysis at the same time during damaged tire cracking gas, oil
Carry out, the catalyst that wherein catalytic pyrolysis uses is nickel chloride, cracking reaction temperature can be made to reduce by 50~100 DEG C, reaction activation
25~40kJ/mol can be reduced, the reaction rate of cracking has been lifted, and the quality and yield for being pyrolyzed oil product also slightly improve, oil product
Yield is promoted to 42~52% by existing 35~45%, and the yield of carbon black is 33~40%；The catalyst that the present invention uses is used
To measure less, cost of material is low, has larger economic value, simultaneously as catalyst amount is few, it is miscellaneous in obtained carbon black products
Matter is also corresponding less, and carbon black mass is high.
Embodiment
With reference to specific embodiment, the present invention will be described in detail, and the description of this part is only exemplary and explains
Property, there should not be any restriction effect to protection scope of the present invention.
A kind of low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire of the present invention and the method for carbon black, including following step
Suddenly：
Step (1)：Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh；
Step (2)：Waste rubber grain and catalyst nickel chloride are added in pyrolysis furnace, temperature for 400~550 DEG C,
Pressure is to carry out thermal cracking under -0.01~0.01MPa, and tiny structure and minute-pressure are conducive to the stabilization of system, beneficial to follow-up serialization
Production；Tire is high molecular hydrocarbon, separates out aromatic naphtha at 200 DEG C first, and then natural rubber components start heat
Cracking, last butadiene rubber, butadiene-styrene rubber starts to decompose, with the heating of pyrolysis furnace, in damaged tire the macromolecular chain of rubber by
Step fracture, produces cracked gas, cracked oil, carbon black etc.；
Step (3)：The high-temperature oil gas produced in cracking process and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into height
Wet solid separator, isolates high-temperature oil gas and thin carbon black, and high-temperature oil gas condenses to obtain fuel oil into fractionating column；By continuous
The mode of cracking discharging is collected fuel oil and fuel gas product storage, and fuel oil can be converted into the oily of high value and again
The chemical products wanted, fuel gas can be directly used as fuel.
Step (4)：The cracking slag coarse carbon black produced in cracking process is discharged from pyrolysis furnace slag-drip opening, by being ground into thin charcoal
It is black, it is mixed to get carbon black products with thin carbon black in step (3).Carbon black products are collected by way of continuous cracking discharging
Storage.
In above-mentioned technical proposal, in the step (2), nickel chloride accounts for the 0.3%~0.8% of waste rubber grain weight.Chlorine
When changing the content that nickel adds and being less than 0.3%, the catalytic action unobvious of cracking, during more than 0.8%, impurity component increases in carbon black
More therefore optimal additions is 0.3%~0.8%.
In above-mentioned technical proposal, in the step (3), thermal cracking temperature is 450~550 DEG C, and the time of thermal cracking is 30
~40min.
Nickel chloride is a kind of magnesium-yttrium-transition metal compound, can be produced as catalyst in catalytic cracking reaction unstable
Intermediate product, makes reaction activity reduce by 25~40kJ/mol, reaction temperature is than existing heat scission reaction temperature (500 DEG C of ＞)
50~100 DEG C are reduced, reaction difficulty reduces, and reaction rate and oil product yield can then get a promotion, and fuel oil yield is by existing
35~45% had bring up to 42~52%, and the yield of oil product is slightly lifted, and carbon black yield is 33~40%, the carbon black that will be obtained
Product carries out screening detection, and the oversized particles content by 20 mesh (sieve diameter is 840 μm) is that 0,500 μm of residue on sieve contents are small
In 0.001%, carbon black products quality is high, has higher economic value.
Embodiment 1
Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh, the nickel chloride for adding 0.3% mixes therewith
Close, be then added in pyrolysis furnace, thermal cracking 30min, cracking are carried out in the case where temperature is 400 DEG C, pressure is 0MPa~0.01MPa
During the high-temperature oil gas that produces and thin carbon black discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, isolate height
Warm oil gas and thin carbon black, high-temperature oil gas condense to obtain fuel oil into fractionating column, thick in the cracking slag produced in cracking process
Carbon black is discharged from pyrolysis furnace slag-drip opening, and by being ground into thin carbon black, carbon black products are mixed to get with foregoing thin carbon black.Pyrolysis product
Yield be：Fuel oil 42%, carbon black 36%.
Embodiment 2
Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh, the nickel chloride for adding 0.5% mixes therewith
Close, be then added in pyrolysis furnace, carry out thermal cracking 35min in the case where temperature is 450 DEG C, pressure is -0.01MPa~0MPa, split
The high-temperature oil gas and thin carbon black produced in solution preocess is discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, is isolated
High-temperature oil gas and thin carbon black, high-temperature oil gas condense to obtain fuel oil into fractionating column, in the cracking slag produced in cracking process
Coarse carbon black is discharged from pyrolysis furnace slag-drip opening, and by being ground into thin carbon black, carbon black products are mixed to get with foregoing thin carbon black.Cracking production
The yield of thing is：Fuel oil 49%, carbon black 33%.
Embodiment 3
Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh, the nickel chloride for adding 0.8% mixes therewith
Close, be then added in pyrolysis furnace, thermal cracking 40min, cracking process are carried out in the case where temperature is 520 DEG C, pressure is -0.01MPa
The high-temperature oil gas of middle generation and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, isolate high temperature oil
Gas and thin carbon black, high-temperature oil gas condense to obtain fuel oil into fractionating column, the coarse carbon black in the cracking slag produced in cracking process
Discharged from pyrolysis furnace slag-drip opening, by being ground into thin carbon black, carbon black products are mixed to get with foregoing thin carbon black.Pyrolysis product
Rate is：Fuel oil 52%, carbon black 35%.
Embodiment 4
Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh, the nickel chloride for adding 0.8% mixes therewith
Close, be then added in pyrolysis furnace, thermal cracking 30min, cracking process are carried out in the case where temperature is 550 DEG C, pressure is -0.01MPa
The high-temperature oil gas of middle generation and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, isolate high temperature oil
Gas and thin carbon black, high-temperature oil gas condense to obtain fuel oil into fractionating column, the coarse carbon black in the cracking slag produced in cracking process
Discharged from pyrolysis furnace slag-drip opening, by being ground into thin carbon black, carbon black products are mixed to get with foregoing thin carbon black.Pyrolysis product
Rate is：Fuel oil 50%, carbon black 36%.
Embodiment 5
Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh, the nickel chloride for adding 0.8% mixes therewith
Conjunction, is then added in pyrolysis furnace, the progress thermal cracking 35min in the case where temperature is 550 DEG C, pressure is 0.01MPa, in cracking process
The high-temperature oil gas of generation and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into high-temperature gas-solid separator, isolate high-temperature oil gas
With thin carbon black, high-temperature oil gas condenses to obtain fuel oil into fractionating column, the coarse carbon black in the cracking slag produced in cracking process from
Pyrolysis furnace slag-drip opening is discharged, and by being ground into thin carbon black, carbon black products are mixed to get with foregoing thin carbon black.The yield of pyrolysis product
For：Fuel oil 47%, carbon black 40%.
The above described is only a preferred embodiment of the present invention, any limit not is made to the technical scope of the present invention
System, therefore any subtle modifications, equivalent variations and modifications that every technical spirit according to the present invention makees above example,
Still fall within the range of technical scheme.
Claims (2)
1. the method for a kind of low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire and carbon black, it is characterised in that including following step
Suddenly：
Step (1):Damaged tire is isolated into steel wire and is broken into the waste rubber grain of 5~30 mesh；
Step (2):Waste rubber grain and catalyst nickel chloride are added in pyrolysis furnace, are 520~550 DEG C, pressure in temperature
The 0.8% of waste rubber grain weight is accounted for for progress thermal cracking and catalytic pyrolysis, the nickel chloride under -0.01MPa；
Step (3):The high-temperature oil gas produced in cracking process and thin carbon black are discharged by the fuel-displaced gas port of pyrolysis furnace, into High Temperature Gas
Solid separator, isolates high-temperature oil gas and thin carbon black, and high-temperature oil gas condenses to obtain fuel oil into fractionating column；
Step (4)：The cracking slag coarse carbon black produced in cracking process is discharged from pyrolysis furnace slag-drip opening, by being ground into thin carbon black,
Carbon black products are mixed to get with thin carbon black in step (3).
2. the method for the low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire as claimed in claim 1 and carbon black, its feature exist
In：In the step (2), the time of thermal cracking is 30~40min.
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| CN201610883816.2A CN106350092B (en) | 2016-10-10 | 2016-10-10 | The method of the low-temperature catalyzed thermal cracking made fuel oil of automobile damaged tire and carbon black |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107556785A (en) * | 2017-09-15 | 2018-01-09 | 四川宏图普新微波科技有限公司 | A kind of preparation method of regeneration hard carbon black used for rubber reinforcement |
| KR102453460B1 (en) * | 2018-04-18 | 2022-10-11 | 알렉산더 텝리츠키 | Methods for obtaining carbon-containing materials from recyclable tires and/or rubber products |
| CN109096798B (en) * | 2018-08-24 | 2020-10-20 | 大连理工大学 | Micro-oxidation activation method for waste tire pyrolytic carbon black |
| CN111303928A (en) * | 2020-03-30 | 2020-06-19 | 安徽省克林泰迩再生资源科技有限公司 | Micro-negative pressure cracking system and cracking method for rubber thermal cycle heating |
| CN114196456A (en) * | 2021-12-13 | 2022-03-18 | 格林美(武汉)城市矿山产业集团有限公司 | Preparation method of derived fuel of scrap car crushing residue |
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| CN1560196A (en) * | 2004-03-11 | 2005-01-05 | 王恩明 | Technology process of producing diesel oil by waste tyre |
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|---|---|---|---|---|
| CN1560196A (en) * | 2004-03-11 | 2005-01-05 | 王恩明 | Technology process of producing diesel oil by waste tyre |
| CN105349170A (en) * | 2015-12-05 | 2016-02-24 | 袁显兰 | Method for catalytic cracking of waste tires |
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