CN107434979A - A kind of waste plastic oil-refining method - Google Patents
A kind of waste plastic oil-refining method Download PDFInfo
- Publication number
- CN107434979A CN107434979A CN201710675497.0A CN201710675497A CN107434979A CN 107434979 A CN107434979 A CN 107434979A CN 201710675497 A CN201710675497 A CN 201710675497A CN 107434979 A CN107434979 A CN 107434979A
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- Prior art keywords
- molten state
- antichlor
- weak acid
- chloride
- solid
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Classifications
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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
- C10G1/004—Inhibiting of corrosion
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention provides a kind of waste plastic oil-refining method, comprises the following steps：Antichlor is mixed with waste plastics, is added in 350 DEG C of reactors and is mixed and stirred for solvent naphtha jointly；Reactor bottom discharges mixed material；The mixed material is filtered by filter immediately while hot, filters out solid chloride and remaining solid antichlor, the mixture that molten state polyethylene, molten state polypropylene and molten state hydrocarbon compound are formed is squeezed into next reactor carries out catalytic cracking reaction.Advantage is：The present invention effectively can remove the chlorine element in waste plastics, also, caused hydrogen chloride gas is reacted with antichlor immediately, and any equipment in whole technological process will not be caused to corrode, hydrogen chloride zero-emission is also realized, do not pollute the environment；Using the method for the present invention, high quality oils can be prepared, also, cost is low, can promote the use of on a large scale.
Description
Technical field
The invention belongs to Waste plastic recycling technology field, and in particular to a kind of waste plastic oil-refining method.
Background technology
At present, the processing of waste plastics mainly has three kinds of landfill, burning electricity generation, recycling modes in solid waste, wherein, fill out
Bury and easily produce secondary pollution with burning electricity generation both of which, be progressively eliminated.Recycling mode turns into useless modeling
Expect the main flow of processing, recycling mode mainly includes two kinds：The first, after waste plastics recovery and being granulated, then is made each
Kind utensil, articles for use etc.；Second, after reclaiming waste plastics, catalytic cracking waste-plastic and the fuel oil products that high added value is made, this
Kind mode is applied in research and production extensively because economic benefit is higher.
At present, in Catalytic Cracking of Waste Plastics for Producing Fuel Oil production, waste plastics removes Main Ingredients and Appearance polythene PE and polypropylene
It is total in cracking waste plastics system feeding both just by screening also containing 10%~20% or so polyvinylchloride outside PP
A certain amount of polyvinyl chloride can be contained.Therefore, in waste plastics catalytic pyrolysis process, polyvinyl chloride occurs de- at 200~350 DEG C
Chlorine reacts, and produces hydrogen chloride gas, is mixed with waste plastics containing a small amount of moisture, hydrochloric acid is generated, to reactor, pipeline and valve
Deng seriously corroded.To solve the problems, such as hcl corrosion relevant device, some semiworks react in cracking waste plastics handling process
Container uses batch (-type) rotary furnace, and production efficiency is low, and safety and environmental protection does not reach requirement in addition, lacks hydrogen chloride gas processing and arranges
Apply, caused partial oxidation hydrogen is discharged into air, and environment is caused seriously to pollute.And some larger waste plastics
Producer is handled, some has used the waste plastics Deep Catalytic Cracking process of continous way, and sets hydrochlorination device, splits
Gas caused by solution passes through graininess antichlor absorbing hydrogen chloride.Although such technique avoids subsequent pipeline, valve and equipment
Hydrogen chloride gas even hydrochloric acid is contacted, but for the reactor before hydrochlorination device, pipeline and valve, still can not
What is avoided contacts with hydrogen chloride even hydrochloric acid, still causes equipment corrosion.Although it can be made using anti-chlorine ion corrosion material
Relevant device, but equipment cost greatly increases.
The content of the invention
The defects of existing for prior art, the present invention provide a kind of waste plastic oil-refining method, can effectively solve above-mentioned ask
Topic.
The technical solution adopted by the present invention is as follows：
The present invention provides a kind of waste plastic oil-refining method, comprises the following steps：
Step 1, antichlor is mixed with waste plastics, is added in 350 DEG C of reactors and is mixed and stirred for solvent naphtha jointly；
Wherein, the mol ratio of chlorine element of the antichlor with containing in waste plastics is more than 1：1；Waste plastics includes：Polyethylene, polypropylene and poly-
Vinyl chloride；In 350 DEG C of reactors, polyethylene and polypropylene turn into molten state；Dechlorination reaction occurs for polyvinyl chloride, produces chlorination
Hydrogen and hydrocarbon compound, hydrocarbon compound are molten state in 350 DEG C of reactors；Also, caused hydrogen chloride gas is stood
Reacted with antichlor, generate solid chloride and water vapour；Water vapour is directly discharged from the exhaust outlet of reactor；
Step 2, reactor bottom discharge mixed material；Wherein, the mixed material includes molten state polyethylene, molten state
Polypropylene, molten state hydrocarbon compound, remaining solid antichlor and solid chloride；Described in being filtered immediately by filter while hot
Mixed material, solid chloride and remaining solid antichlor are filtered out, by molten state polyethylene, molten state polypropylene and molten state hydrocarbon
The mixture that class compound is formed squeezes into next reactor and carries out catalytic cracking reaction, so circulation, realizes continuous feed, even
Continuous discharging, removes de-chlorine hydride and solid chloride in time；Hydrogen chloride zero-emission is achieved in, any equipment will not be corroded.
Preferably, the antichlor is metal oxide, metal salt of weak acid or basic metal complexes.
Preferably, the metal oxide is calcium type oxide, zinc type oxide, magnesium type oxide or copper type oxide；
The metal salt of weak acid is calcium class salt of weak acid, zinc class salt of weak acid, magnesium class salt of weak acid or copper class salt of weak acid；The alkalinous metal complexing
Thing is zinc hydroxide.
Preferably, the calcium type oxide is CaO；The zinc type oxide is ZnO；The calcium class salt of weak acid is CaCO3；
The zinc hydroxide is Zn (OH)2；The zinc class salt of weak acid is ZnCO3。
A kind of waste plastic oil-refining method provided by the invention has advantages below：
The present invention can effectively by waste plastics chlorine element remove, also, caused hydrogen chloride gas immediately with dechlorination
Agent is reacted, and any equipment in whole technological process will not be caused to corrode, hydrogen chloride zero-emission is also realized, will not pollute ring
Border；Using the method for the present invention, high quality oils can be prepared, also, cost is low, can promote the use of on a large scale.
Brief description of the drawings
Fig. 1 is a kind of schematic flow sheet of waste plastic oil-refining method provided by the invention.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein only to
The present invention is explained, is not intended to limit the present invention.
Hydrogen chloride gas can be produced for waste plastics catalytic pyrolysis process in the prior art, the hydrochloric acid of generation is mixed with steam
The problem of serious to equipment corrosion, the method that dechlorination is absorbed from current gas is different, and the present invention is provided at a kind of continuous waste plastics
The dechlorination process of reason, hydrogen chloride can be eliminated at once while hydrogen chloride produces, with installing dechlorination apparatus phase after reactor additional
Than avoiding the danger of the corrosion and damages such as reactor.
With reference to figure 1, a kind of waste plastic oil-refining method provided by the invention, comprise the following steps：
Step 1, antichlor is mixed with waste plastics, is added in 350 DEG C of reactors and is mixed and stirred for solvent naphtha jointly；
Wherein, the mol ratio of chlorine element of the antichlor with containing in waste plastics is more than 1：1；Waste plastics includes：Polyethylene, polypropylene and poly-
Vinyl chloride；In 350 DEG C of reactors, polyethylene and polypropylene turn into molten state；Dechlorination reaction occurs for polyvinyl chloride, produces chlorination
Hydrogen and hydrocarbon compound, hydrocarbon compound are molten state in 350 DEG C of reactors；Also, caused hydrogen chloride gas is stood
Reacted with antichlor, generate solid chloride and water vapour；Water vapour is directly discharged from the exhaust outlet of reactor；Its
In, antichlor is metal oxide, metal salt of weak acid or basic metal complexes.Metal oxide be the calcium type oxide such as CaO,
The zinc such as ZnO type oxide, magnesium type oxide or copper type oxide；Metal salt of weak acid is CaCO3Deng calcium class salt of weak acid, ZnCO3Deng zinc
Class salt of weak acid, magnesium class salt of weak acid or copper class salt of weak acid；Basic metal complexes are Zn (OH)2Deng zinc hydroxide.
Step 2, reactor bottom discharge mixed material；Wherein, mixed material includes molten state polyethylene, molten state poly- third
Alkene, molten state hydrocarbon compound, remaining solid antichlor and solid chloride；Mixture is filtered by filter immediately while hot
Material, filters out solid chloride and remaining solid antichlor, by molten state polyethylene, molten state polypropylene and molten state hydrocarbon
The mixture that thing is formed squeezes into next reactor and carries out catalytic cracking reaction, so circulation, realizes continuous feed, continuously goes out
Material, removes de-chlorine hydride and solid chloride in time；Hydrogen chloride zero-emission is achieved in, any equipment will not be corroded.
Antichlor used in present invention process is high temperature modification antichlor, is reacted rapidly with hydrogen chloride, therefore in chlorine
Change hydrogen to can be carried out eliminating once generation.Excessive antichlor and the chloride of generation are solid powder at high temperature, because
This, it is only necessary to it can be filtered out by simple filters, make chlorine is not present in plastic raw materials used in catalytic cracking reaction
Element, it thus avoid chlorine element etc. and subsequent catalyst cracking had an impact.Antichlor used in the present invention is simple and easy to get
Inorganic matter, cost is low, and need not be granulated, suitable for large-scale production.
Two embodiments are described below：
Embodiment one：
Step 1, antichlor CaO is mixed with waste plastics, is added to oil miscible solvent to merge in 350 DEG C of reactors jointly and stirs
Mix；Wherein, the mol ratio of chlorine elements of the antichlor CaO with containing in waste plastics is 1.5：1；Waste plastics includes：Polyethylene, poly- third
Alkene and polyvinyl chloride；In 350 DEG C of reactors, polyethylene and polypropylene turn into molten state；Dechlorination reaction, production occur for polyvinyl chloride
Raw hydrogen chloride gas and hydrocarbon compound, hydrocarbon compound are molten state in 350 DEG C of reactors；Also, caused hydrogen chloride
Gas reacts with antichlor CaO immediately, generates solid calcium chloride and water vapour；Water vapour is directly from the exhaust outlet of reactor
Discharge；
Step 2, reactor bottom discharge mixed material；Wherein, mixed material includes molten state polyethylene, molten state poly- third
Alkene, molten state hydrocarbon compound, remaining solid CaO and solid calcium chloride；Mixed material, filter are filtered by filter immediately while hot
Except remaining solid CaO and solid calcium chloride, molten state polyethylene, molten state polypropylene and molten state hydrocarbon compound are formed
Mixture squeezes into next reactor and carries out catalytic cracking reaction, so circulation, realizes continuous feed, continuous discharge, removes in time
De-chlorine hydride and solid calcium chloride；Hydrogen chloride zero-emission is achieved in, any equipment will not be corroded.
After testing, the oil being prepared after catalytic cracking reaction, the molar concentration of its chlorine element contained are less than 0.1%.
Embodiment two：
Step 1, by antichlor Zn (OH)2Mixed with waste plastics, be added in 350 DEG C of reactors and mixed with solvent naphtha jointly
And stir；Wherein, antichlor Zn (OH)2The mol ratio of chlorine element with containing in waste plastics is 1.7：1；Waste plastics includes：It is poly-
Ethene, polypropylene and polyvinyl chloride；In 350 DEG C of reactors, polyethylene and polypropylene turn into molten state；Polyvinyl chloride occurs de-
Chlorine reacts, and it is molten state in 350 DEG C of reactors to produce hydrogen chloride gas and hydrocarbon compound, hydrocarbon compound；Also, produce
Hydrogen chloride gas immediately with antichlor Zn (OH)2React, generate Zinc chloride solid and water vapour；Water vapour is directly from anti-
The exhaust outlet of kettle is answered to discharge；
Step 2, reactor bottom discharge mixed material；Wherein, mixed material includes molten state polyethylene, molten state poly- third
Alkene, molten state hydrocarbon compound, remaining solid Zn (OH)2And Zinc chloride solid；Mixture is filtered by filter immediately while hot
Material, filters out remaining solid Zn (OH)2And Zinc chloride solid, by molten state polyethylene, molten state polypropylene and molten state hydro carbons
The mixture that compound is formed squeezes into next reactor and carries out catalytic cracking reaction, so circulation, realizes continuous feed, continuously goes out
Material, removes de-chlorine hydride and solid calcium chloride in time；Hydrogen chloride zero-emission is achieved in, any equipment will not be corroded.
After testing, the oil being prepared after catalytic cracking reaction, the molar concentration of its chlorine element contained are less than 0.1%.
The present invention can effectively by waste plastics chlorine element remove, also, caused hydrogen chloride gas immediately with dechlorination
Agent is reacted, and any equipment in whole technological process will not be caused to corrode, hydrogen chloride zero-emission is also realized, will not pollute ring
Border；Using the method for the present invention, high quality oils can be prepared, also, cost is low, can promote the use of on a large scale.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
Depending on protection scope of the present invention.
Claims (4)
- A kind of 1. waste plastic oil-refining method, it is characterised in that comprise the following steps：Step 1, antichlor is mixed with waste plastics, is added in 350 DEG C of reactors and is mixed and stirred for solvent naphtha jointly；Its In, the mol ratio of chlorine element of the antichlor with containing in waste plastics is more than 1：1；Waste plastics includes：Polyethylene, polypropylene and polychlorostyrene Ethene；In 350 DEG C of reactors, polyethylene and polypropylene turn into molten state；Dechlorination reaction occurs for polyvinyl chloride, produces hydrogen chloride Gas and hydrocarbon compound, hydrocarbon compound are molten state in 350 DEG C of reactors；Also, caused hydrogen chloride gas is immediately Reacted with antichlor, generate solid chloride and water vapour；Water vapour is directly discharged from the exhaust outlet of reactor；Step 2, reactor bottom discharge mixed material；Wherein, the mixed material includes molten state polyethylene, molten state poly- third Alkene, molten state hydrocarbon compound, remaining solid antichlor and solid chloride；The mixing is filtered by filter immediately while hot Material, solid chloride and remaining solid antichlor are filtered out, by molten state polyethylene, molten state polypropylene and molten state hydro carbons The mixture that compound is formed squeezes into next reactor and carries out catalytic cracking reaction, so circulation, realizes continuous feed, continuously goes out Material, removes de-chlorine hydride and solid chloride in time；Hydrogen chloride zero-emission is achieved in, any equipment will not be corroded.
- 2. a kind of waste plastic oil-refining method according to claim 1, it is characterised in that the antichlor aoxidizes for metal Thing, metal salt of weak acid or basic metal complexes.
- 3. a kind of waste plastic oil-refining method according to claim 2, it is characterised in that the metal oxide is calcium class oxygen Compound, zinc type oxide, magnesium type oxide or copper type oxide；The metal salt of weak acid be calcium class salt of weak acid, zinc class salt of weak acid, Magnesium class salt of weak acid or copper class salt of weak acid；The basic metal complexes are zinc hydroxide.
- 4. a kind of waste plastic oil-refining method according to claim 3, it is characterised in that the calcium type oxide is CaO；Institute It is ZnO to state zinc type oxide；The calcium class salt of weak acid is CaCO3；The zinc hydroxide is Zn (OH)2；The zinc class weak acid Salt is ZnCO3。
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| CN201710675497.0A CN107434979A (en) | 2017-08-09 | 2017-08-09 | A kind of waste plastic oil-refining method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762588A (en) * | 2019-01-31 | 2019-05-17 | 河南银洲新型建材有限公司 | A kind of waste disposal method and its pyrolysis furnace and cracker |
| CN112534030A (en) * | 2018-07-20 | 2021-03-19 | 耐思特公司 | Purification of recovered and renewable organic materials |
| CN112646597A (en) * | 2020-12-14 | 2021-04-13 | 蓝德环保科技集团股份有限公司 | Automatic continuous operation reaction device and method for preparing fuel oil by cracking waste plastics |
| CN112646619A (en) * | 2020-02-25 | 2021-04-13 | 四川华益聚能石油化工有限公司 | Gasoline product oil |
| CN114507113A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| CN116925812A (en) * | 2022-03-31 | 2023-10-24 | 中国石油化工股份有限公司 | Method and system for dechlorination of waste plastic oil |
| WO2023218220A1 (en) * | 2022-05-10 | 2023-11-16 | Azuola Andrei Gaggion | High temperature repolymerization recycling and plastics |
| WO2024129223A1 (en) * | 2022-12-12 | 2024-06-20 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
| WO2024129222A1 (en) * | 2022-12-12 | 2024-06-20 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112534030A (en) * | 2018-07-20 | 2021-03-19 | 耐思特公司 | Purification of recovered and renewable organic materials |
| CN109762588A (en) * | 2019-01-31 | 2019-05-17 | 河南银洲新型建材有限公司 | A kind of waste disposal method and its pyrolysis furnace and cracker |
| CN112646619A (en) * | 2020-02-25 | 2021-04-13 | 四川华益聚能石油化工有限公司 | Gasoline product oil |
| CN114507113A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| CN114507113B (en) * | 2020-10-28 | 2024-03-12 | 中国石油化工股份有限公司 | Method and system for preparing ethylene and propylene from waste plastics |
| CN112646597A (en) * | 2020-12-14 | 2021-04-13 | 蓝德环保科技集团股份有限公司 | Automatic continuous operation reaction device and method for preparing fuel oil by cracking waste plastics |
| CN116925812A (en) * | 2022-03-31 | 2023-10-24 | 中国石油化工股份有限公司 | Method and system for dechlorination of waste plastic oil |
| WO2023218220A1 (en) * | 2022-05-10 | 2023-11-16 | Azuola Andrei Gaggion | High temperature repolymerization recycling and plastics |
| WO2024129223A1 (en) * | 2022-12-12 | 2024-06-20 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
| WO2024129222A1 (en) * | 2022-12-12 | 2024-06-20 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
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