CN103058482A - Method for treatment of oil sludge by thermal conversion - Google Patents
Method for treatment of oil sludge by thermal conversion Download PDFInfo
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- CN103058482A CN103058482A CN2011103213434A CN201110321343A CN103058482A CN 103058482 A CN103058482 A CN 103058482A CN 2011103213434 A CN2011103213434 A CN 2011103213434A CN 201110321343 A CN201110321343 A CN 201110321343A CN 103058482 A CN103058482 A CN 103058482A
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Abstract
The invention discloses a method for treatment of oil sludge by thermal conversion. The method utilizes a fluidized bed reactor as an oil sludge thermal conversion reactor, and adopts coke particles or coal particles with a size of 2-20 meshes as a coking carrier and a heat carrier. Preheated oil sludge contacts with the coke particles or coal particles to undergo a thermal cracking reaction, and the generated high temperature oil gas is subjected to separation, thus obtaining products. The coking carrier then enters a heater, and most of the coke particles enter a gasifier to undergo gasification so as to generate water gas. The high temperature water gas and coke powder return to the heater, and undergo heat exchange with the coking carrier. The coke powder subjected to heat exchange is taken as a heat carrier and is recycled to the reactor. In the invention, fluid thermal conversion is employed to treat the oil sludge, and the obtained products mainly comprise water gas and liquid generated oil. The method provided in the invention has the characteristics of continuous operation, good flexibility, low coke yield, high oil sludge utilization rate and high recovery efficiency.
Description
Technical field
The present invention relates to a kind for the treatment of process to oily sludge, specifically a kind of method that adopts the fluidisation thermal transition to process greasy filth.
Background technology
Oily sludge mainly refers to because the oily sludge that the crude oil that causes of a variety of causes and earth form, and the oily sediment that system takes out of in the normal production in oil field, is a kind of solid waste that is rich in mineral oil, and 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 density crude oil (5%～80%), heavy metal ion (such as iron, copper, nickel etc.) and inorganic salts (5%～20%) compound etc. in the mud.Generally contain the materials such as benzene homologues, phenols, kind class 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 present oil refining industry.
The technology of processing at present oily sludge mainly contains resource recovery, harmless treatment and comprehensive utilization technique.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 oil-containing mud sand is varied, and every kind of method has relative merits and the scope of application separately.
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.
US Patent No. 484271 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.
Chinese patent ZL02133117.0 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, and investment and process cost are low, not only effectively processed oily sludge, and wherein valuable components are fully utilized, and can not bring disadvantageous effect to after-treatment device simultaneously.
Summary of the invention
For the deficiencies in the prior art, the technical problem to be solved in the present invention provides the method that greasy filth is processed in a kind of fluidisation thermal transition.
The method of greasy filth is processed in thermal transition provided by the invention, specifically may further comprise the steps:
(1) removes mechanical impurity after the greasy filth process dehydration pre-treatment, after preheating, send into fluidized-bed reactor;
(2) greasy filth that enters fluidized-bed reactor contacts with high temperature green coke carrier, thermal conversion reaction occurs, obtain high-temperature oil gas, be attached to the coke on the green coke carrier, wherein temperature of reaction is controlled to be 450～550 ℃, burnt grain is 1: 8～9 with the mass ratio of greasy filth, and the reaction times is 5～30 min;
(3) the green coke carrier that adheres to coke enters well heater and heats through behind the stripping, provides coking required heat, and the bed temperature of well heater is 600～700 ℃, and carrier pump around circuit fluidized bed reactor reacts after the heat exchange;
(4) high-temperature oil gas through the washing and separate, isolate the green coke carrier after, enter separation column and separate, obtain gas and liquid.
Process the method for greasy filth according to thermal transition of the present invention, wherein also comprise step (5): remaining green coke carrier enters in the gasifier in the described well heater, under 800～1000 ℃ high temperature, generate water-gas (thick product) with air, steam reaction, water-gas is got back to heat is provided in the well heater with removing carrier behind the coke, discharges well heater after the green coke carrier heat exchange that transports with fluidized-bed reactor.
Process the method for greasy filth according to thermal transition of the present invention, wherein can also comprise step (6), the gases such as water-gas of discharging from the well heater top again through dedusting, carry out desulfurization after reclaiming residual coke powder, just obtain product water coal gas behind interchanger heat exchange, high pressure steam generator heat-obtaining.
Green coke carrier described in the inventive method is burnt grain or coal grain, and the granularity of green coke carrier is 2～20 orders.
The present invention processes in the method for greasy filth, and wherein the preheating temperature of the described preheating of step (1) is 300～350 ℃.
In the step (3), described green coke carrier behind the stripped vapor stripping, can go out ash content by screening and separating first after, enter again well heater and heat.
The described washing of step (4) can be by washing realization with washing oil to high-temperature oil gas, and wherein washing oil is selected from wax oil or diesel oil, and the liquid that separation column obtains among preferred the present invention generates oil.Can remove solid particulate and the muddy condenses of high temperature is got off by washing, the muddy liquid of the condensation that obtains can return fluidized-bed reactor to carry out cycling hot and decomposes, perhaps direct extraction device.Described high-temperature oil gas can adopt cyclonic separator to carry out with separating of green coke carrier.
Owing to contain the oil content of some amount and certain fraction distribution in the greasy filth, mainly contain alkane, alkene, naphthenic hydrocarbon, aromatic hydrocarbon, colloid and bituminous matter etc.Thermal conversion reaction can occur in oil content in the greasy filth at a certain temperature.The thermal conversion reaction of hydro carbons is a kind of parallel consecutive reaction of complexity, basically can be divided into cracking and condensation both direction.Cracking generates less molecule (such as carburet hydrogen), and the condensation direction generates larger molecule (such as colloid, bituminous matter, coke etc.).It has been generally acknowledged that the hydro carbons thermal response is free radical reaction, in thermal conversion processes, oil content generally is heated to and namely begins cracking about 370 ℃, and simultaneously condensation reaction is accelerated with the increase of cracking level.Under low cracking severity, the aromatic hydrocarbons in raw material and the oil content is main coking parent; Under high cracking severity, the polycondensate that secondary reaction generates is main coking parent.
For avoiding generating too much coke; blocking pipeline; the present invention utilizes fluidized-bed reactor as greasy filth thermal conversion reaction device; with the burnt grain of 2～20 purposes or coal grain as the fluidisation carrier; make that the greasy filth through preheating contacts with the carrier of fluidisation after the pre-treatment; heat scission reaction occurs; described fluidisation carrier had both been supplied with the required heat of greasy filth reaction at this moment; the green coke carrier that serves as again simultaneously restructuring minute condensation reaction in the greasy filth; the high-temperature oil gas that obtains after the reaction is left fluidized-bed reactor after treatment; and the carrier of coking enters well heater; afterwards the burnt grain of part as thermal barrier recirculation return in the reactor, most of burnt grain then enters into gasifier and gasifies to produce water-gas.
But have operate continuously, handiness is good, coke yield low and can produces the advantages such as water-gas, the high cleaner production of reliability but adopt the fluidisation thermal transition that greasy filth is processed.And the present invention processes the product that greasy filth obtains and comprises that mainly water-gas and liquid generate oil, have the advantages that the greasy filth utilization ratio is high, organic efficiency is high.
Description of drawings
Fig. 1 is the block diagram that the greasy filth method is processed in thermal transition of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments method of the present invention is elaborated.
Embodiment 1
Adopt technical process shown in Figure 1, the explanation specific embodiment of the invention as an example of certain refinery's oil tank bottom greasy filth example.Greasy filth oil-containing 75%(quality), moisture 14%, all the other are solid matter.
Remove mechanical impurity after the greasy filth process dehydration pre-treatment, in process furnace, be heated to 350 ℃, enter fluidized-bed reactor through pipeline again.Be full of the burnt grain of 10～20 orders of fluidisation in the reactor.The greasy filth that enters fluidized-bed reactor carries out thermal transition in reactor, temperature of reaction is 500 ℃, and a little higher than normal pressure of pressure, fluidizing medium are oil gas and the water vapor that entered by the bottom.Thermal conversion reaction generates liquid product, gas and coke.The total coking yield of control process (in toluene insolubles) is 10%, and green coke is deposited on the burnt grain of fluidized.The oil gas that reaction generates is told the burnt grain that carries through cyclonic separator, enters the washing section of reactor head.Reaction product in washing section, remove solid particulate and under 500 ℃ the muddy condenses, and be back in the reactor.Washing section top material is sent into separation column, is separated into coking liquid product and coking gas.The stripping stage of burnt grain through the bottom enters well heater with the oil gas that the water vapour stripping goes out wherein after the reaction process.Water-gas and the coke powder sent into from gasifier in the well heater, the focusing grain heats, and the effect that reactor plays thermal barrier is returned in the burnt grain part recirculation of high temperature, base feed oil preheating and the required heat of reaction.Most of burnt grain enters into gasifier, at 800 ℃ of lower and air, steam reaction production water-gas.Contain H in the water-gas
2, H
2S, CO, CO
2, N
2, H
2The gases such as O.Water-gas and coke powder are got back to heat are provided in the well heater.From well heater top expellant gas through interchanger heat exchange, high pressure steam generator heat-obtaining, again through dedusting, reclaim residual coke powder after desulfurization, just be water-gas gas.Greasy filth is behind the fluidisation thermal conversion reaction, and liquid yield is 82.2%, in the liquid-phase product＜200 ℃ of cuts account for 15.8%, 200～350 ℃ of cuts and account for 24.3%, 350 ℃ of cuts account for 42.1%, gas recovery ratio 7.6%.
Embodiment 2
The explanation specific embodiment of the invention as an example of certain refinery's oil tank bottom greasy filth example.Greasy filth oil-containing 67%, moisture 23%, all the other are solid matter.Technical process is identical with embodiment 1, and difference is in the washing section of reactor〉500 ℃ muddy liquid do not loop back reactor, but directly extract out, namely reaction raw materials is disposable passes through.Temperature of reaction is chosen as 530 ℃.Temperature is 900 ℃ in the gasifier.Greasy filth is behind the fluidisation thermal conversion reaction, and its transformation efficiency is 98.2%, and liquid yield is 87.0%, in the liquid-phase product＜200 ℃ of cuts account for 17.7%, 200～350 ℃ of cuts and account for 25.8%, 350 ℃ of cuts account for 43.5%, gas recovery ratio 6.8%.
Claims (11)
1. the method for greasy filth is processed in a thermal transition, may further comprise the steps:
(1) removes mechanical impurity after the greasy filth process dehydration pre-treatment, after preheating, send into fluidized-bed reactor;
(2) greasy filth that enters fluidized-bed reactor contacts with high temperature green coke carrier, and thermal conversion reaction occurs, and obtains high-temperature oil gas, is attached to the coke on the green coke carrier;
(3) the green coke carrier that adheres to coke enters well heater and heats, and provides coking required heat, and the bed temperature of well heater is 600～700 ℃, and heat exchange rear portion green coke carrier pump around circuit fluidized bed reactor reacts;
(4) high-temperature oil gas through the washing and separate, isolate the green coke carrier after, enter separation column and separate, obtain gas and liquid.
2. in accordance with the method for claim 1, it is characterized in that, also comprise step (5): the green coke carrier of remainder enters in the gasifier in the described well heater, under 800～1000 ℃ of temperature, generate water-gas with air, steam reaction, water-gas is got back in the well heater with the green coke carrier of removing behind the coke, discharges well heater after the green coke carrier heat exchange of the coking of carrying with fluidized-bed reactor.
3. in accordance with the method for claim 2, it is characterized in that, also comprise step (6): the water-gas gas of discharging from the well heater top again through dedusting, carry out desulfurization after reclaiming residual coke powder, obtains product water coal gas behind interchanger heat exchange, high pressure steam generator heat-obtaining.
4. in accordance with the method for claim 1, it is characterized in that the described temperature of reaction of step (2) is controlled to be 450～550 ℃, the mass ratio of green coke carrier and greasy filth is 1: 8～9, and the reaction times is 5～30min.
5. in accordance with the method for claim 1, it is characterized in that described green coke carrier is burnt grain or coal grain, the granularity of green coke carrier is 2～20 orders.
6. in accordance with the method for claim 1, it is characterized in that wherein the preheating temperature of the described preheating of step (1) is 300～350 ℃.
7. in accordance with the method for claim 1, it is characterized in that, adhere to the green coke carrier of coke described in the step (3) behind the stripped vapor stripping, go out ash content by screening and separating first after, enter again well heater and heat.
8. in accordance with the method for claim 1, it is characterized in that the described washing of step (4) is by washing realization with washing oil to high-temperature oil gas, washing oil is selected from wax oil or diesel oil.
9. according to claim 1 or 8 described methods, it is characterized in that described washing oil is that the liquid that separation column obtains generates oil.
10. in accordance with the method for claim 9, it is characterized in that, obtain the muddy liquid of condensation by washing, described muddy liquid returns fluidized-bed reactor to carry out cycling hot and decomposes, perhaps direct extraction device.
11. in accordance with the method for claim 1, it is characterized in that described high-temperature oil gas adopts cyclonic separator to carry out with separating of green coke carrier.
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| CN2011103213434A CN103058482A (en) | 2011-10-21 | 2011-10-21 | Method for treatment of oil sludge by thermal conversion |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603645B (en) * | 2017-10-30 | 2019-10-11 | 西北化工研究院 | A kind of method that coupling processing oil field tank bottom oil sludge preparation gasification is burnt |
| CN112538369A (en) * | 2019-09-23 | 2021-03-23 | 中国石油大学(北京) | Method and device for coupling heavy oil hydrogen pressurized catalytic cracking with coke gasification |
| CN112664955A (en) * | 2020-12-21 | 2021-04-16 | 湖南长科诚享石化科技有限公司 | System for be used for handling solid sediment of oiliness |
| CN113307468A (en) * | 2021-05-10 | 2021-08-27 | 国网山东省电力公司电力科学研究院 | Treatment method and treatment system for oily sludge |
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| US4804459A (en) * | 1985-04-04 | 1989-02-14 | Engelhard Corporation | Process for upgrading tar sand bitumen |
| CN101358136A (en) * | 2008-10-07 | 2009-02-04 | 中国石油大学(北京) | Method for directly fluid coking oil sand and apparatus |
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Patent Citations (3)
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| US4804459A (en) * | 1985-04-04 | 1989-02-14 | Engelhard Corporation | Process for upgrading tar sand bitumen |
| CN101358136A (en) * | 2008-10-07 | 2009-02-04 | 中国石油大学(北京) | Method for directly fluid coking oil sand and apparatus |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603645B (en) * | 2017-10-30 | 2019-10-11 | 西北化工研究院 | A kind of method that coupling processing oil field tank bottom oil sludge preparation gasification is burnt |
| CN112538369A (en) * | 2019-09-23 | 2021-03-23 | 中国石油大学(北京) | Method and device for coupling heavy oil hydrogen pressurized catalytic cracking with coke gasification |
| CN112538369B (en) * | 2019-09-23 | 2022-02-25 | 中国石油大学(北京) | Method and device for coupling heavy oil hydrogen pressurized catalytic cracking with coke gasification |
| CN112664955A (en) * | 2020-12-21 | 2021-04-16 | 湖南长科诚享石化科技有限公司 | System for be used for handling solid sediment of oiliness |
| CN113307468A (en) * | 2021-05-10 | 2021-08-27 | 国网山东省电力公司电力科学研究院 | Treatment method and treatment system for oily sludge |
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Application publication date: 20130424 |