CN103058471A - Method for treatment of oil sludge by thermal treatment-supercritical extraction - Google Patents

Method for treatment of oil sludge by thermal treatment-supercritical extraction Download PDF

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Publication number
CN103058471A
CN103058471A CN2011103213519A CN201110321351A CN103058471A CN 103058471 A CN103058471 A CN 103058471A CN 2011103213519 A CN2011103213519 A CN 2011103213519A CN 201110321351 A CN201110321351 A CN 201110321351A CN 103058471 A CN103058471 A CN 103058471A
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China
Prior art keywords
extraction
supercritical extraction
supercritical
greasy filth
oil
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CN2011103213519A
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Chinese (zh)
Inventor
赵昕
回军
赵景霞
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to CN2011103213519A priority Critical patent/CN103058471A/en
Publication of CN103058471A publication Critical patent/CN103058471A/en
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Abstract

The invention discloses a method for treatment of oil sludge by thermal treatment-supercritical extraction. The method comprises: heating oil sludge subjected to mechanical dewatering to 100-300DEG C under an anaerobic condition, then making the oil sludge enter a separation tower to perform hot flash, recovering the light oil and water generated in the flash through condensation, taking heavy oil and solids out in the form of slurry, and subjecting the slurry and an extracting agent to supercritical fluid extraction; carrying out settling separation on the extract, thus obtaining oil and solids. On the basis of proper supercritical extraction, the method provided in the invention adds thermal treatment flash to remove the water and light oil from the oil sludge, and performs selective supercritical extraction on heavy oil, thus shortening the extraction time and improving the supercritical extraction effect.

Description

Thermal treatment-supercritical extraction is processed the method for greasy filth
Technical field
The present invention relates to a kind for the treatment of process of oily sludge.
Background technology
Greasy filth mainly refers to because the oily sludge that the crude oil that causes of a variety of causes or other oil product and earth etc. form, and the oily sediment that system takes out of in the normal production in oil field etc., be a kind of solid waste that is rich in mineral oil, main component is crude oil, Ni Heshui.The solid particulate size can be from not enough micron to several inches, and great majority are between l to 100 micron, and crude oil kind, refinery structure and operational condition are depended in oil composition, and the composition of mud may temporal evolution and change.Usually contain certain crude oil (concentration quality 5%~80%), heavy metal ion (such as iron, copper, nickel etc.) and inorganic salts (concentration quality 5%~20%) compound etc. in the mud.Generally contain the materials such as benzene homologues, phenols in these greasy filth, and follow stench and toxicity, if directly contact with physical environment, can make that the soil poisons, acidifying or alkalization, cause the change of soil and soil structure, hinder plant root growth and can cause larger pollution to water body and vegetation, also mean the waste of petroleum resources simultaneously.
By national Hazardous Waste List, greasy filth is listed in Hazardous wastes, and it just attracts great attention to chronicity and the potentiality of environmental hazard.Carrying out greasy filth management and Study of Prevention Technology is a vital task of present national environmental protection work.Therefore, how these oily sludges being carried out innoxious and recycling, also is the important environmental issue that pendulum needs to be resolved hurrily in face of oil refining industry.
The technology of processing at present oily sludge mainly contains resource recovery, harmless treatment and comprehensive utilization technique etc.Resource recycling technology comprises solvent extration, WATER-WASHING METHOD, micro emulsion washing, breakdown of emulsion method etc.Greasy filth harmless treatment treatment technology comprises immobilization processing, the technology such as biological treatment, burning.Comprehensive utilization technique comprises that thermolysis, brickmaking are paved the way and other purposes.The treatment technology of greasy filth is varied, and every kind of method has relative merits and the scope of application separately.Along with the increasingly stringent of environmental regulation and perfect, the Oilfield Oil-Contained Silt treatment technology will attract great attention, the inexorable trend that oily sandy sludge is innoxious, resource utilization, comprehensive utilization treatment technology will become the development of oil sludge and sand treatment technology.
Solvent extration is commonly use in the greasy filth treatment technology a kind of, its utilization " similar mixing " principle, select suitable organic solvent to make extraction agent, with organism from greasy filth by solvent extraction out after, by distillation solvent separated from mixture and to recycle, the crude oil of recovery then is used for freshening.US484271 adopts extraction oxidation oxidation style that oily sludge is processed, and adds first a kind of light hydrocarbon and make extraction agent in mud, and after extraction, oily and most of organism is removed, residual mud HNO 3Oxide treatment under 200 ~ 375 ℃ and condition of normal pressure.
CN02133117.0 adopts the technical finesse oily sludge of " extraction heat-dehydration-solid-liquid separation ", oily sludge is carried out mechanical dehydration, then mix and preheating with extraction solvent oil, carry out extraction heat-processed after mixing, then carry out solid-liquid separation, liquid phase enters coker, and solid phase can be used as fuel, and the vapour phase of extraction heat-dehydration is carried out oily water separation after condensation.The method process is simple, need not specific installation, investment and process cost are low, not only effectively processed oily sludge, and wherein valuable components is fully utilized, simultaneously can not bring disadvantageous effect to after-treatment device, but energy consumption is higher, and centimetre does not utilize the various valuable constituents in the greasy filth.
Avila Ch á vez M. A[Separation Science and Technology, 2007,42 (10): 2327-2345]. wait and utilize a kind of special supercritical fluid extraction equipment, adopt overcritical ethane extraction agent from the petroleum tank bed mud, to extract hydrocarbon, research thinks that maximum percentage extraction is corresponding to the pressure and temperature of high solvent density, the obvious enrichment of hydrocarbon component of extraction.But because the emulsification degree of greasy filth is high, solid impurity is many, and solid water for complexity-oil-rock steady structure adopts extraction or the supercritical extraction method of routine, and the extraction time of needs is long, and extraction efficiency is low, has limited its application.
Summary of the invention
The technical problem to be solved in the present invention provides the method that a kind of thermal treatment flash distillation-supercritical extraction is processed greasy filth, can fully reclaim the various valuable constituents in the greasy filth, the industrial application good economy performance.
Thermal treatment flash distillation of the present invention-supercritical extraction is processed the method for greasy filth, and concrete steps are as follows:
(1) greasy filth behind the mechanical dehydration is heated to 100~300 ℃ under anoxic condition, preferred 150~250 ℃, then enter knockout tower and carry out flash evaporation, the lightweight oil content that flashes off and water reclaim by the mode of condensation, and heavy oil content and solids are taken out in knockout tower with the form of mud.
(2) mud and the extraction agent after the above-mentioned thermal treatment flash distillation enters supercritical extraction unit, sets supercritical extraction pressure and supercritical extraction temperature, carries out supercritical extraction.Extraction agent is selected from carbonic acid gas, methane, ethane, propane or ethene, is preferably carbonic acid gas or ethane.Solvent quantity is that every gram greasy filth uses 20~50 milliliters of extraction agents, and supercritical extraction pressure is 3~8 MPa, and the supercritical extraction temperature is 30~100 ℃, and the supercritical extraction time is 1~2 h.
(3) material after the extraction enters primary separator and separates with second-stage separator, recycle after the solvent gasification, extract is emitted from the separator bottom, after settlement separate, obtain oil content and solids, solids acts as a fuel through the de-oiling drying or after solidifying, and the gained oil content is as coking or catalytically cracked material.
Described supercritical extraction can adopt operate continuously, also can adopt batch operation.
When the present invention is directed to greasy filth extraction or supercritical extraction, because the extraction that the greasy filth complicated components causes difficulty, extraction time is long, the deficiency that extraction efficiency is low, on the basis of suitable supercritical extraction, increase the thermal treatment flash distillation, the moisture in the greasy filth and lightweight oil content are separated, the heavy oil content is carried out the selectivity supercritical extraction, thereby improve the supercritical extraction effect.
Description of drawings
Fig. 1 is the process flow diagram of greasy filth treatment process of the present invention.
Embodiment
The supercritical fluid extraction influence factor mainly contains extraction conditions, comprises pressure, temperature, time etc.; The kind of raw material properties and supercutical fluid.Wherein the selection of supercutical fluid is most important.In Supercritical Extraction Process, require supercutical fluid to have good solubility energy and good selectivity.For the consideration of safety, economy and environmental protection, also has following requirement for supercutical fluid simultaneously; Stable chemical nature, nontoxicity and non-corrosiveness, nonflammable and non-explosive; The service temperature of supercutical fluid should be close to normal temperature, so that save energy, and make service temperature be lower than the decomposition temperature of composition to be separated; The working pressure of supercutical fluid should be low as much as possible, to reduce the power consumption of compressor; Wide material sources, low price.In conjunction with the character of greasy filth, the present invention selects carbonic acid gas, methane, ethane, propane and other low molecule alkane, ethene and other low-molecular olefine etc. as the supercritical extraction agent, and its critical data is as shown in table 1.
The critical data of table 1 part supercritical fluid solvent
Supercutical fluid Boiling point/℃ T c/℃ P c/MPa
Carbonic acid gas -78.5 31.6 7.39
Methane -164.0 -83.0 4.60
Ethane -88.0 32.4 4.89
Propane -42.1 96.8 4.25
Ethene -103.7 9.5 5.07
The variation of supercritical flow volume density directly affects effect of extracting in the extraction process, and extracting pressure is the important parameter that affects supercritical phase density.According to the variation of extracting pressure, supercutical fluid can be divided three classes.When being high pressure, the dissolving power of supercutical fluid is strong, can dissolve to greatest extent all the components, and the low pressure critical zone only can be extracted diffluent composition or be removed objectionable constituent, the slective extraction of middle nip is asked high-low pressure, can select suitable pressure effectively to extract according to the requirement of materials abstraction.The present invention is directed to the character of greasy filth, and the extraction agent character of selecting, the extracting pressure of selection is 3~8 MPa.
At the low pressure area of Near The Critical Point, although the rising temperature can improve volatility and the diffusibility of separated portion, the density that is not enough to replenish supercutical fluid raises with temperature and the institute that sharply descends causes dissolving power to descend.In the high pressure area, the density of supercutical fluid is large, and compressibility is little, and the temperature that raises this moment can improve vapour pressure and the spread coefficient of component to be separated, thereby has improved the dissolving power of solute.For the character of greasy filth, the suitable extraction temperature of employing is 50~100 ℃.
Heat treatment technics is that greasy filth is heated to more than 100 ℃, then carries out flash distillation at knockout tower, and steam and lightweight oil content are separated out from knockout tower.Heavy oil content and solid matter remove lighter hydrocarbons as bed mud and water reclaims through after the condensation, enters supercritical extraction unit and carries out selective extraction to improve extraction efficiency and to shorten extraction time.
The inventive method processing efficiency is high, and required equipment scale is little, the industrial application good economy performance.
Embodiment 1
Explanation the inventive method as an example of certain refinery's oil tank bottom greasy filth example.Greasy filth oil-containing 65wt%, moisture 18wt%, all the other are solid matter.Select CO 2As the supercritical extraction agent.Solvent quantity is than using the 30mL extraction agent for every gram greasy filth.
Greasy filth is sent into flashing tower and is carried out flash distillation through mechanical stirring dehydration post-heating to 250 ℃.Cat head obtains water vapour and lighter hydrocarbons steam, and condensation separates by water-and-oil separator, obtains the lightweight oil content, and sewage enters Sewage treatment systems.Be the mud that heavy oil content and solids are mixed at the bottom of the flashing tower tower.
Mud is sent into supercritical extraction reactor.From storage tank (CO 2) out liquid CO 2System purifies after filtration, then is transported to preheating in the preheater by high-pressure pump, be preheated to design temperature after, enter to reach in the extraction kettle and set extracting pressure and extraction temperature, extraction temperature is 70 ℃, extracting pressure is 5MPa, extraction time 1.5h.CO in extraction kettle 2Contact with raw material, be extracted composition and be dissolved in CO 2In extract.Extract remainder carry out settlement separate after, obtain a little oil content and solids, act as a fuel after solids solidifies.Extract is with CO 2Fluid successively enters primary separator and second-stage separator, extract and CO 2Separate, receive by receiving system; CO 2Then isolate and reuse from second-stage separator.Extract is emitted from the separator bottom, directly enters catalytic cracking or coker.The percentage extraction of greasy filth is the 97.8%(quality).
Embodiment 2
Explanation the inventive method as an example of certain refinery's oil tank bottom greasy filth example.Greasy filth oil-containing 65%, moisture 18%, all the other are solid matter.It is 200 ℃ that Heating temperature is processed in flash distillation.Select ethane as the supercritical extraction agent.Extraction temperature is 70 ℃, and extracting pressure is 6MPa, and Solvent quantity is than being every gram greasy filth use 30mL extraction agent, and extraction time is 2h.Technical process is with embodiment 1, and the percentage extraction of greasy filth is the 98.6%(quality).

Claims (8)

1. a thermal treatment-supercritical extraction is processed the method for greasy filth, may further comprise the steps:
(1) greasy filth behind the mechanical dehydration is heated to 100~300 ℃ under anoxic condition, then enters knockout tower and carry out flash evaporation, obtain heavy oil content and solids and take out in knockout tower with the form of mud;
(2) mud and the extraction agent after the above-mentioned thermal treatment flash distillation enters supercritical extraction unit, sets supercritical extraction pressure and supercritical extraction temperature, carries out supercritical extraction;
(3) material after the extraction enters primary separator and separates with second-stage separator, recycles after the solvent gasification, and extract is emitted from the separator bottom, settlement separate after, obtain oil content and solids.
2. in accordance with the method for claim 1, it is characterized in that, the lightweight oil content that step (1) flashes off and water reclaim by the mode of condensation.
3. in accordance with the method for claim 1, it is characterized in that, the condition of described supercritical extraction is, Solvent quantity is that every gram greasy filth uses 20~50 mL extraction agents, supercritical extraction pressure is 3~8MPa, and the supercritical extraction temperature is 30~100 ℃, and the supercritical extraction time is 1~2 h.
4. in accordance with the method for claim 1, it is characterized in that, described extraction agent is selected from carbonic acid gas, methane, ethane, propane or ethene.
5. according to claim 1 or 3 described methods, it is characterized in that, described extraction agent is carbonic acid gas or ethane.
6. in accordance with the method for claim 1, it is characterized in that, the described solids of step (3) acts as a fuel through the de-oiling drying or after solidifying, and the gained oil content is as coking or catalytically cracked material.
7. in accordance with the method for claim 1, it is characterized in that, enter flashing tower the greasy filth in the step (1) behind the mechanical dehydration is heated to 150~250 ℃ under anoxic condition after.
8. in accordance with the method for claim 1, it is characterized in that, described supercritical extraction adopts operate continuously or batch operation.
CN2011103213519A 2011-10-21 2011-10-21 Method for treatment of oil sludge by thermal treatment-supercritical extraction Pending CN103058471A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103395953A (en) * 2013-08-12 2013-11-20 江苏君鑫谊石油机械有限公司 Oil-sludge separation method based on CO2 supercritical extraction method
CN103979756A (en) * 2014-05-27 2014-08-13 陕西延长石油(集团)有限责任公司 Method for tempering oily sludge by using supercritical fluid through rapid swelling
CN103979757A (en) * 2014-05-27 2014-08-13 陕西延长石油(集团)有限责任公司 Method for treating oily sludge through multistage extraction-splitting coupling of supercritical fluid
CN104724894A (en) * 2015-03-24 2015-06-24 南通睿智超临界科技发展有限公司 Method for processing oily sludge through supercutical fluid
CN108395067A (en) * 2018-04-25 2018-08-14 中国石油大学(北京) A kind of technique of WATER-WASHING METHOD processing oily sludge
CN110451745A (en) * 2019-07-10 2019-11-15 合肥通用机械研究院有限公司 A kind of oil base drilling wastes supercritical processing system
CN110484346A (en) * 2019-09-18 2019-11-22 中国人民解放军陆军勤务学院 Based on supercritical CO2Regenerate the method for waste lubricating oil

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CN101041541A (en) * 2007-04-23 2007-09-26 辽河石油勘探局 Oil soil treatment technique for tank cleaning
CN101734834A (en) * 2009-12-29 2010-06-16 新疆油田勘察设计研究院 Method for recovering sandy oil-containing sludge
CN101823824A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Process for treating oily sludge

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US5059332A (en) * 1990-04-09 1991-10-22 Yukimasa Satoh Method and device for treating oil sludge and oil-containing waste water
US20020134704A1 (en) * 2001-03-22 2002-09-26 Mitchell Allen R. Process and system for continuously extracting oil from solid or liquid oil bearing material
CN1373096A (en) * 2002-04-09 2002-10-09 水志良 Process for treating oily mud by phase transfer method
CN101041541A (en) * 2007-04-23 2007-09-26 辽河石油勘探局 Oil soil treatment technique for tank cleaning
CN101823824A (en) * 2009-03-04 2010-09-08 中国石油天然气股份有限公司 Process for treating oily sludge
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103395953A (en) * 2013-08-12 2013-11-20 江苏君鑫谊石油机械有限公司 Oil-sludge separation method based on CO2 supercritical extraction method
CN103979756A (en) * 2014-05-27 2014-08-13 陕西延长石油(集团)有限责任公司 Method for tempering oily sludge by using supercritical fluid through rapid swelling
CN103979757A (en) * 2014-05-27 2014-08-13 陕西延长石油(集团)有限责任公司 Method for treating oily sludge through multistage extraction-splitting coupling of supercritical fluid
CN103979757B (en) * 2014-05-27 2015-04-08 陕西延长石油(集团)有限责任公司 Method for treating oily sludge through multistage extraction-splitting coupling of supercritical fluid
CN103979756B (en) * 2014-05-27 2015-05-20 陕西延长石油(集团)有限责任公司 Method for tempering oily sludge by using supercritical fluid through rapid swelling
CN104724894A (en) * 2015-03-24 2015-06-24 南通睿智超临界科技发展有限公司 Method for processing oily sludge through supercutical fluid
CN108395067A (en) * 2018-04-25 2018-08-14 中国石油大学(北京) A kind of technique of WATER-WASHING METHOD processing oily sludge
CN108395067B (en) * 2018-04-25 2020-06-12 中国石油大学(北京) Process for treating oily sludge by water washing method
CN110451745A (en) * 2019-07-10 2019-11-15 合肥通用机械研究院有限公司 A kind of oil base drilling wastes supercritical processing system
CN110451745B (en) * 2019-07-10 2021-11-23 合肥通用机械研究院有限公司 Oil-based drilling waste supercritical treatment system
CN110484346A (en) * 2019-09-18 2019-11-22 中国人民解放军陆军勤务学院 Based on supercritical CO2Regenerate the method for waste lubricating oil

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Application publication date: 20130424