CN110482836A - A kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption - Google Patents

A kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption Download PDF

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Publication number
CN110482836A
CN110482836A CN201910346676.9A CN201910346676A CN110482836A CN 110482836 A CN110482836 A CN 110482836A CN 201910346676 A CN201910346676 A CN 201910346676A CN 110482836 A CN110482836 A CN 110482836A
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China
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thermal desorption
reactor
oily sludge
anaerobism
reaction
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CN201910346676.9A
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Inventor
胡家富
肖航
张会文
杨帆
孙淑雲
李敏
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Nanjing Hehai Environmental Research Institute Co Ltd
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Nanjing Hehai Environmental Research Institute Co Ltd
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Priority to CN201910346676.9A priority Critical patent/CN110482836A/en
Publication of CN110482836A publication Critical patent/CN110482836A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/006Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/18Treatment of sludge; Devices therefor by thermal conditioning
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1003Waste materials
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00Specifically adapted fuels
    • C10L2270/02Specifically adapted fuels for internal combustion engines
    • C10L2270/026Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Abstract

Oily sludge recycling and method for innocent treatment the present invention relates to a kind based on anaerobism thermal desorption, the processing method is as follows: the chemical heat washed reaction device that step 1) oily sludge successively passes through level-one, second level is connected with three-level 3, is furnished with blender in each reactor;Step 2 enters the settling tank of three alternate runs after third-stage reactor by liquid level difference, and time of repose is 0.5-6 hours;The crude oil of top of the tank is directly pumped into oil storage tank after the settle and separate of step 3) settling tank, the viscous mixture of bottom is pumped into three phase separation centrifuge, oil after centrifuge separation is mutually collected to oil storage tank, liquid phase is discharged into sewage disposal system, solid phase enters greasy filth anaerobism thermal desorption device, the recycling of the program realization energy, solid residue being capable of stabilizing heavy metal after handling simultaneously, it is stable in the presence of in nature as oxide, convenient for security landfill disposition, perfectly solve the problems, such as oily sludge resource utilization and subsequent disposition.

Description

A kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption
Technical field
The present invention relates to a kind of processing methods, and in particular to a kind of oily sludge recycling and nothing based on anaerobism thermal desorption Evilization processing method belongs to disposal of oily sludge and application technology as the second resource field.
Background technique
It can be generated in petrochemical industry, in crude oil production, production, transport, storage and refining process a large amount of Oily sludge, the oily sludge amount that China's oil chemical plant generates every year according to statistics are about 3,000,000 tons (with 80% moisture content meters). It is toxic containing a large amount of benzene, phenol, polycyclic aromatic hydrocarbon, heavy metal, various chemical addition agents and pathogen microorganism etc. in oily sludge Harmful substance is defined as HW08 waste mineral oil and danger wastes containing mineral oil by ecological environment portion, while containing in greasy filth There is a petroleum hydrocarbon hydrocarbon of 30%-70%, energy value with higher, based on environment, economic coordinated development, how Resource utilization is carried out to oily sludge and has become worldwide a difficult problem using with innoxious appropriate disposition, is obtained The extensive concern of people in the industry.
For a long time, China's oily sludge mostly uses incineration method and landfill method to dispose, and amount of landfill is very big, short several In ten years, the crude oil of waste is similar to the production capacity in a medium-scale oil field, not only causes the serious wasting of resources, but also The pollution risk of soil, underground water is increased, or even has had resulted in huge environmental pollution.Oily sludge complicated component is A kind of extremely intractable danger wastes, the oil-sludge treatment technology based on burning, fill can not synchronize realization to containing greasy dirt The recycling and harmlessness disposing of mud.Therefore, disposal of oily sludge new technology is explored, recycles energy object therein to greatest extent Matter, reducing oily sludge risk of environmental pollution seems increasingly important, and therefore, a kind of new scheme of urgent need solves above-mentioned skill Art problem.
Summary of the invention
The present invention exactly aiming at the problems existing in the prior art, provides a kind of oily sludge money based on anaerobism thermal desorption Source and method for innocent treatment, the technical solution can by greasy filth crude oil and the high Extra-value ingredient such as Hydrocarbon Organic from Extracted in solid matter, realize the recycling of the energy, at the same after handling solid residue can stabilizing heavy metal, become oxygen Compound is stable in the presence of in nature, is disposed convenient for security landfill, perfectly solves oily sludge resource utilization and subsequent The problem of disposition.
To achieve the goals above, technical scheme is as follows, a kind of oily sludge money based on anaerobism thermal desorption Source and method for innocent treatment, which is characterized in that the processing method is as follows:
The chemical heat washed reaction device that step 1) oily sludge successively passes through level-one, second level is connected with three-level 3, each reactor In be furnished with blender, wherein first-stage reactor is high speed reactor, second reactor is intermediate reactor, third-stage reactor is high Fast reactor;
Step 2 enters the settling tank of three alternate runs, time of repose 0.5-6 after third-stage reactor by liquid level difference Hour;
The crude oil of top of the tank is directly pumped into oil storage tank after the settle and separate of step 3) settling tank, and the viscous mixture of bottom is pumped into Three phase separation centrifuge, centrifugal rotational speed 5000-8000r/min, reaction time 20-30min.Oil after centrifuge separation is mutually received Collection is to oil storage tank, and liquid phase is discharged into sewage disposal system, and solid phase enters greasy filth anaerobism thermal desorption device.
As an improvement of the present invention, the stirring rate of level-one high speed reactor is 1200- in the step 1) 1500r/min, the demulsifier added are Nacl and Cacl2 mixed liquor, and molal weight ratio is (2-3): 1, dosage is that greasy filth is exhausted The 2.5-5.5% of amount of dry matter, hot water wash temperature are 65-85 DEG C, and the reaction time is about 6-12 minutes, passes through liquid after reaction Potential difference enters second reactor.
As an improvement of the present invention, the stirring rate of second level intermediate reactor is 600-1000 in the step 1) R/min, the demulsifier added are isopropanol, and dosage is the 1.0-3.0% of greasy filth over dry amount of substance, and hot water wash temperature is 60-80 DEG C, the reaction time is about 10-15 minutes, enters third-stage reactor by liquid level difference after reaction;
As an improvement of the present invention, the stirring rate of three-level high speed reactor is 1000-1200r/ in the step 1) Min, mixing time are 1-3 minutes, and ionization analysis reaction unit is directly added into simultaneous reactions device, adjust pH value to 6-9, using straight Galvanic electricity carries out ionization analysis, current strength 4.0-8.0A, and the reaction time is 10-15 minute, pass through after reaction liquid level difference into Enter the settling tank of 3 alternate runs, time of repose is 0.5-6 hours.
As an improvement of the present invention, the ionization analysis reaction unit anode in the step 1) is copper, mercury, titanium inertia gold Category is combined according to the ratio of 1:2:2, and the cathode used is multiple according to the ratio of 1:1:2 for zinc, aluminium, iron low-hydrogen over-potential metal It closes, parallel is used between electrode, the spacing between electrode is 6.0~12.0cm, electrode effective area and anti- Answer device volume ratio 1:17-1:33.
As an improvement of the present invention, in the step 3) greasy filth thermal desorption device include feed unit, gear unit, Thermal desorption cavity, gas-fired heater, nitrogen processed protection system, evaporation recovery unit, tail gas treating unit, discharging dreg removing system;Institute The reaction temperature for stating thermal desorption device is 400-600 DEG C, is passed through nitrogen as protection gas, maintenance inside cavity pressure is 0.3- 0.5Mpa, desorption object are discharged into evaporation recovery unit, are passed through low-pressure nitrogen in the ratio of discharge rate 2%-5% and are continuously purged;Institute Evaporation condensing gas after the recovery is stated as assisted gas, the slag-drip opening of reuse to thermal desorption cavity, discharge system accesses clear water reserviors It is directly immersed under the water surface, inhibits fugitive dust using hydration reaction, avoid generating secondary pollution.
Compared with the existing technology, the invention has the advantages that, 1) thermal desorption in the technical solution is not to burn, material Can directly be contacted with combustion flame or burning gases at no time, entire reaction process in inertia anoxybiotic environment into Row, to prevent from aoxidizing or destroying the chemical component in oily sludge;
2) crude quality after program separation and recovery is good, and moisture content is equivalent to the low of business oil plant less than 0.3% in oily phase Quality oil distillate, may be directly applied to diesel engine, bring considerable economic benefit for enterprise.
3) it is greatly lowered using greasy filth quality after program processing and volume, quality mitigates to the 4%- of raw material quality 8%, the 2%-6% of reduction in bulk to raw material volume,
4) organic pollutant removal rate is greater than 99% in program greasy filth, and crude oil recovery rate reaches 95% or more, the gas such as no dioxin State pollutant generate, solid residue can stabilizing heavy metal, become oxide and be stable in the presence of nature, meet stringent environmental protection Standard requirements are convenient for security landfill.
Detailed description of the invention
Fig. 1 processing technological flow figure of the present invention.
Specific embodiment:
In order to deepen the understanding of the present invention, the present embodiment is described in detail with reference to the accompanying drawing.
Embodiment 1: referring to Fig. 1, a kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption, institute It is as follows to state processing method:
The chemical heat washed reaction device that step 1) oily sludge successively passes through level-one, second level is connected with three-level 3, each reactor In be furnished with blender, wherein first-stage reactor is high speed reactor, second reactor is intermediate reactor, third-stage reactor is high Fast reactor;
Step 2 enters the settling tank of three alternate runs, time of repose 0.5-6 after third-stage reactor by liquid level difference Hour;
The crude oil of top of the tank is directly pumped into oil storage tank after the settle and separate of step 3) settling tank, and the viscous mixture of bottom is pumped into Three phase separation centrifuge, centrifugal rotational speed 5000-8000r/min, reaction time 20-30min.Oil after centrifuge separation is mutually received Collection is to oil storage tank, and liquid phase is discharged into sewage disposal system, and solid phase enters greasy filth anaerobism thermal desorption device.
The stirring rate of level-one high speed reactor is 1200-1500r/min in the step 1), and the demulsifier added is Nacl and Cacl2 mixed liquor, molal weight ratio are (2-3): 1, dosage is the 2.5-5.5% of greasy filth over dry amount of substance, hot water wash Temperature is 65-85 DEG C, and the reaction time is about 6-12 minutes, enters second reactor by liquid level difference after reaction.
The stirring rate of second level intermediate reactor is 600-1000 r/min in the step 1), and the demulsifier added is different Propyl alcohol, dosage are the 1.0-3.0% of greasy filth over dry amount of substance, and hot water wash temperature is 60-80 DEG C, and the reaction time is about 10-15 points Clock enters third-stage reactor by liquid level difference after reaction;
The stirring rate of three-level high speed reactor is 1000-1200r/min in the step 1), and mixing time is 1-3 minutes, together When reactor in be directly added into ionization analysis reaction unit, adjust pH value to 6-9, carry out ionization analysis, current strength using direct current For 4.0-8.0A, the reaction time is 10-15 minutes, enters the settling tank of 3 alternate runs by liquid level difference after reaction, quiet Setting the time is 0.5-6 hours.
It is compound according to the ratio of 1:2:2 for copper, mercury, titanium inert metal that reaction unit anode is analysed in ionization in the step 1) It forms, the cathode used is combined for zinc, aluminium, iron low-hydrogen over-potential metal according to the ratio of 1:1:2, using simultaneously between electrode Join connection type, the spacing between electrode is 6.0~12.0cm, electrode effective area and reaction unit volume ratio 1:17-1:33.
Greasy filth thermal desorption device includes feed unit, gear unit, thermal desorption cavity, gas heating in the step 3) Furnace, nitrogen processed protection system, evaporation recovery unit, tail gas treating unit, discharging dreg removing system;The reaction temperature of the thermal desorption device Degree is 400-600 DEG C, is passed through nitrogen as protection gas, and maintenance inside cavity pressure is 0.3-0.5Mpa, and desorption object is discharged into evaporation Recovery unit is passed through low-pressure nitrogen in the ratio of discharge rate 2%-5% and is continuously purged, and prevents from aoxidizing or destroying the original in greasy filth Oil and other organic components.For the evaporation condensing gas after the recovery as assisted gas, reuse to thermal desorption cavity improves thermal energy The slag-drip opening access clear water reserviors of utilization rate, discharge system are directly immersed under the water surface, are inhibited fugitive dust using hydration reaction, are avoided Generate secondary pollution.
It should be noted that above-described embodiment, is not intended to limit the scope of protection of the present invention, in above-mentioned technical proposal On the basis of made equivalents or substitution each fall within the range that the claims in the present invention are protected.

Claims (6)

1. a kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption, which is characterized in that the processing Method is as follows:
The chemical heat washed reaction device that step 1) oily sludge successively passes through level-one, second level is connected with three-level 3, each reactor In be furnished with blender, wherein first-stage reactor is high speed reactor, second reactor is intermediate reactor, third-stage reactor is high Fast reactor;
Step 2 enters the settling tank of three alternate runs, time of repose 0.5-6 after third-stage reactor by liquid level difference Hour;
The crude oil of top of the tank is directly pumped into oil storage tank after the settle and separate of step 3) settling tank, and the viscous mixture of bottom is pumped into Three phase separation centrifuge, centrifugal rotational speed 5000-8000r/min, reaction time 20-30min, the oil after centrifuge separation are mutually received Collection is to oil storage tank, and liquid phase is discharged into sewage disposal system, and solid phase enters greasy filth anaerobism thermal desorption device.
2. the oily sludge recycling and method for innocent treatment according to claim 1 based on anaerobism thermal desorption, special Sign is that the stirring rate of level-one high speed reactor is 1200-1500r/min in the step 1), and the demulsifier added is Nacl and Cacl2 mixed liquor, molal weight ratio are (2-3): 1, dosage is the 2.5-5.5% of greasy filth over dry amount of substance, hot water wash Temperature is 65-85 DEG C, and the reaction time is about 6-12 minutes, enters second reactor by liquid level difference after reaction.
3. the oily sludge recycling and method for innocent treatment according to claim 2 based on anaerobism thermal desorption, special Sign is that the stirring rate of second level intermediate reactor is 600-1000 r/min in the step 1), and the demulsifier added is different Propyl alcohol, dosage are the 1.0-3.0% of greasy filth over dry amount of substance, and hot water wash temperature is 60-80 DEG C, and the reaction time is about 10-15 points Clock enters third-stage reactor by liquid level difference after reaction.
4. the oily sludge recycling and method for innocent treatment according to claim 3 based on anaerobism thermal desorption, special Sign is that the stirring rate of three-level high speed reactor is 1000-1200r/min in the step 1), and mixing time is 1-3 points Clock is directly added into ionization analysis reaction unit in simultaneous reactions device, adjusts pH value to 6-9, carry out ionization analysis, electric current using direct current Intensity is 4.0-8.0A, and the reaction time is 10-15 minutes, enters the clarification of 3 alternate runs by liquid level difference after reaction Tank, time of repose are 0.5-6 hours.
5. the oily sludge recycling and method for innocent treatment according to claim 4 based on anaerobism thermal desorption, special Sign is that it is compound according to the ratio of 1:2:2 for copper, mercury, titanium inert metal that reaction unit anode is analysed in the ionization in the step 1) It forms, the cathode used is combined for zinc, aluminium, iron low-hydrogen over-potential metal according to the ratio of 1:1:2, using simultaneously between electrode Join connection type, the spacing between electrode is 6.0~12.0cm, electrode effective area and reaction unit volume ratio 1:17-1:33.
6. the oily sludge recycling and method for innocent treatment according to claim 5 based on anaerobism thermal desorption, special Sign is,
Greasy filth thermal desorption device includes feed unit, gear unit, thermal desorption cavity, gas-fired heater, system in the step 3) Nitrogen protects system, evaporation recovery unit, tail gas treating unit, discharging dreg removing system;The reaction temperature of the thermal desorption device is 400-600 DEG C, nitrogen is passed through as protection gas, and maintenance inside cavity pressure is 0.3-0.5Mpa, and desorption object is discharged into evaporation recycling Unit is passed through low-pressure nitrogen in the ratio of discharge rate 2%-5% and is continuously purged;The evaporation condensing gas after the recovery is as auxiliary The slag-drip opening access clear water reserviors of combustion-supporting gas, reuse to thermal desorption cavity, discharge system are directly immersed under the water surface, utilize hydration Response inhabitation fugitive dust avoids generating secondary pollution.
CN201910346676.9A 2019-04-27 2019-04-27 A kind of oily sludge recycling and method for innocent treatment based on anaerobism thermal desorption Pending CN110482836A (en)

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