CN103058483A - Method for treatment of oil sludge - Google Patents

Method for treatment of oil sludge Download PDF

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Publication number
CN103058483A
CN103058483A CN2011103213877A CN201110321387A CN103058483A CN 103058483 A CN103058483 A CN 103058483A CN 2011103213877 A CN2011103213877 A CN 2011103213877A CN 201110321387 A CN201110321387 A CN 201110321387A CN 103058483 A CN103058483 A CN 103058483A
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China
Prior art keywords
oil
carrier
accordance
greasy filth
green coke
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Pending
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CN2011103213877A
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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 CN2011103213877A priority Critical patent/CN103058483A/en
Publication of CN103058483A publication Critical patent/CN103058483A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a method for treatment of oil sludge. The method disclosed in the invention utilizes a fluidized bed reactor as an oil sludge thermal conversion reactor, and takes coke particles or coal particles with a particle size of 2-20 meshes as a coking carrier and a heat carrier, contacting preheated oil sludge with a fluidization carrier to perform a thermal cracking reaction, separating the obtained high temperature oil gas so as to obtain a product, leaving the coking carrier to enter a regenerator to undergo charring regeneration, and cycling the regenerated coke particles back to the fluidized bed reactor for reaction. The invention adopts fluid thermal conversion to treat the oil sludge, and the obtained products mainly include gas and liquid generated oil. The method has the characteristics of continuous operation, good flexibility, low coke yield, high oil sludge utilization rate and high recovery efficiency.

Description

A kind of method of processing greasy filth
Technical field
The present invention relates to a kind for the treatment of process to oily sludge, specifically a kind of method that adopts fluidisation thermal transition technical finesse 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 present invention proposes the method that greasy filth is processed in a kind of fluidisation thermal transition.
The method of processing greasy filth provided by the invention 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 ℃, the mass ratio of green coke carrier and greasy filth is 1: 8~9, and the reaction times is 5~30 min;
(3) after high-temperature oil gas is passed through washing and separated, enter separation column and separate, obtain gas and liquid.
The method for the treatment of in accordance with the present invention greasy filth, wherein also comprise step (4): step (2) gained adheres to the green coke carrier of coke through behind the stripping, enter revivifier and carry out coke burning regeneration, the bed temperature of revivifier is 600~700 ℃, green coke carrier pump around circuit fluidized bed reactor after the regeneration reacts, and unnecessary green coke carrier is discharged from revivifier.
Green coke carrier described in the present invention is burnt grain or coal grain, and the granularity of green coke carrier is 2~20 orders.
The method for the treatment of in accordance with the present invention greasy filth, wherein the preheating temperature of the described greasy filth of step (1) is 300~350 ℃.
The described washing of step (3) can be by washing realization with washing oil to high-temperature oil gas, and wherein washing oil is generally wax oil or diesel oil, as being the generation fluid body that the invention separation column obtains.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 separation can adopt cyclonic separator to carry out separating of high-temperature oil gas and green coke carrier.
In the step (4), described green coke carrier behind the stripped vapor stripping, can be first go out ash content through screening and separating after, enter again revivifier and burn.
Owing to containing the oil content of some amount and certain fraction distribution in the greasy filth, mainly containing 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; greasy filth thermal conversion reaction device of the present invention is fluidized-bed reactor; be full of the burnt grain of 2~20 orders or the coal grain of fluidisation in the device; with burnt grain or coal grain as the green coke carrier; send into fluid bed regenerator behind burnt grain or the coal grain green coke and carry out coke burning regeneration, recirculation is returned in the reactor as thermal barrier afterwards.
The present invention utilizes fluidized-bed reactor; with the burnt grain of 2~20 purposes or coal grain as the green coke carrier; make that the greasy filth through preheating contacts with the green coke carrier of fluidisation after the pre-treatment; heat scission reaction occurs; described green coke carrier is namely supplied with the required heat of greasy filth reaction at this moment; the green coke carrier that has served 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; the carrier of coking then carries out coke burning regeneration; loop back in the reactor after the regeneration; the heat that utilizes the high temperature coke burning regeneration to produce participates in heat scission reaction.
But adopt fluidisation thermal conversion process of the present invention that greasy filth is processed to have operate continuously, but handiness is good, coke yield is low, reliability is high and the advantage such as cleaner production.
Description of drawings
Fig. 1 is the process flow diagram of processing greasy filth method of the present invention.
Embodiment
Below in conjunction with accompanying drawing method of the present invention is described further.
Embodiment 1
Adopt technical process shown in Figure 1, explanation the inventive method as an example of certain refinery's oil tank bottom greasy filth example.This 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 ℃, a little higher than normal pressure of pressure, and burnt grain is 1: 9 with the mass ratio of greasy filth, the reaction times is 30min; Fluidizing medium is 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) 10%, green coke are deposited on the burnt grain of fluidized.The oil gas that reaction generates is told the burnt grain that carries through cyclonic separator, enter the washing section of reactor head.Reaction product in washing section, remove solid particulate and 500 ℃ muddy liquid separation out, muddy liquid is back in the reactor.Washing section top material is sent into separation column, is separated into coking liquid product and coking gas.Burnt grain constantly becomes large in the reaction process, and the stripping stage of the burnt grain of part through the bottom enters fluid bed regenerator with the oil gas that the water vapour stripping goes out wherein.Send into air by regenerator bottoms and make burnt grain carry out partial combustion, burn 15% burnt grain, make bed temperature maintain 700 ℃.The effect that reactor plays thermal barrier is returned in the burnt grain recirculation of high temperature, base feed oil preheating and the required heat of reaction.Flue gas after burning goes waste heat boiler to reclaim heat after telling the burnt grain that carries through cyclonic separator.Unnecessary coke takes out from reactor or revivifier, delivers to coke storage bunker.Greasy filth is behind the fluidisation thermal conversion reaction, and its transformation efficiency is 97.8%, and liquid yield is 82.5%, and coke yield is 9.8%.In the liquid-phase product<200 ℃ of cuts account for 25.2%, 200~350 ℃ of cuts and account for 33.4%, and 350 ℃ of cuts account for 41.1%.
Embodiment 2
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 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 no longer loops back reactor, but directly extract out, namely reaction raw materials is disposable passes through.Temperature of reaction is chosen as 530 ℃, and burnt grain is 1: 8 with the mass ratio of greasy filth, and greasy filth is 20min with the contact reacts time of burnt grain.Greasy filth is behind the fluidisation thermal conversion reaction, and its transformation efficiency is 98.2%, and liquid yield is 84.7%, and coke yield is 8.9%.In the liquid-phase product<200 ℃ of cuts account for 19.7%, 200~350 ℃ of cuts and account for 34%, and 350 ℃ of cuts account for 46.3%.

Claims (10)

1. method of processing greasy filth 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 ℃, the mass ratio of green coke carrier and greasy filth is 1: 8~9, and the reaction times is 5~30 min;
(3) after high-temperature oil gas is passed through washing and separated, 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 (4): adhere to the green coke carrier of coke through behind the stripping, enter revivifier and burn, the green coke carrier pump around circuit fluidized bed reactor after the regeneration reacts.
3. in accordance with the method for claim 2, it is characterized in that, the bed temperature of described revivifier is 600~700 ℃.
4. in accordance with the method for claim 1, it is characterized in that, the green coke carrier described in the step (2) is burnt grain or coal grain, and the granularity of green coke carrier is 2~20 orders.
5. in accordance with the method for claim 1, it is characterized in that, wherein the preheating temperature of the described greasy filth of step (1) is 300~350 ℃.
6. in accordance with the method for claim 2, it is characterized in that, the green coke carrier described in the step (4) after the process screening and separating goes out ash content first, enters revivifier again and burns behind the stripped vapor stripping.
7. in accordance with the method for claim 1, it is characterized in that, the described washing of step (3) is by washing realization with washing oil to high-temperature oil gas, and wherein washing oil is wax oil or diesel oil.
8. in accordance with the method for claim 7, it is characterized in that, described washing oil is that the liquid that separation column obtains generates oil.
9. in accordance with the method for claim 1, it is characterized in that, obtain muddy liquid by washing, described muddy liquid returns fluidized-bed reactor and carries out the cycling hot decomposition, perhaps direct extraction device.
10. in accordance with the method for claim 1, it is characterized in that, the described high-temperature oil gas of step (3) adopts cyclonic separator to carry out with separating of green coke carrier.
CN2011103213877A 2011-10-21 2011-10-21 Method for treatment of oil sludge Pending CN103058483A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739175A (en) * 2013-12-17 2014-04-23 辽宁石油化工大学 Method for processing oil sludge
CN105174669A (en) * 2015-09-30 2015-12-23 达州军华环保科技有限公司 Harmless treatment technology for waste oil base mud
CN108423960A (en) * 2018-03-06 2018-08-21 华东理工大学 Sludge Hydrocracking utilizes method and device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307244A (en) * 2008-06-27 2008-11-19 东南大学 Oil-making method of double-bed interactive and circling type for pyrolyzing sludge
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307244A (en) * 2008-06-27 2008-11-19 东南大学 Oil-making method of double-bed interactive and circling type for pyrolyzing sludge
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
徐振刚等: "《型煤技术》", 30 November 2001, 煤炭工业出版社 *
赵东风等: "焦化法处理含油污泥工艺流程研究", 《环境科学研究》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103739175A (en) * 2013-12-17 2014-04-23 辽宁石油化工大学 Method for processing oil sludge
CN105174669A (en) * 2015-09-30 2015-12-23 达州军华环保科技有限公司 Harmless treatment technology for waste oil base mud
CN105174669B (en) * 2015-09-30 2018-07-06 四川光隆环保科技有限公司 Discarded oil-base mud harmless treatment process
CN108423960A (en) * 2018-03-06 2018-08-21 华东理工大学 Sludge Hydrocracking utilizes method and device
CN108423960B (en) * 2018-03-06 2022-01-18 华东理工大学 Sludge cracking and hydrogenation utilization method and device

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Application publication date: 20130424