CN105174669A - Harmless treatment technology for waste oil base mud - Google Patents
Harmless treatment technology for waste oil base mud Download PDFInfo
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- CN105174669A CN105174669A CN201510636166.7A CN201510636166A CN105174669A CN 105174669 A CN105174669 A CN 105174669A CN 201510636166 A CN201510636166 A CN 201510636166A CN 105174669 A CN105174669 A CN 105174669A
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- harmless treatment
- oily sludge
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
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Abstract
The invention discloses a harmless treatment technology for waste oil base mud and solves the problems of higher energy consumption and overlong treatment time in the prior art. The technology comprising steps of screening, conditioning, conditioning enhancement through preheating, negative-pressure pyrolysis, condensation and fractionation is adopted to treat oily sludge and has the characteristics of high efficiency, energy saving and environment protection; compared with a conventional pyrolysis technology, the harmless treatment technology has the advantages that the work period is shortened by 15%, the energy consumption is reduced by 20%, and the economic benefit is increased remarkably.
Description
Technical field
The present invention relates to a kind of discarded oil-base mud harmless treatment process.
Background technology
Oil base drilling fluid, as a kind of excellent drilling fluid system, has high temperature resistance, anti-salt, antipollution, anti-collapse property is good, oilness is good, be beneficial to maintenance, be beneficial to stabilizing borehole, effectively can suppress the water-sensitive strata advantage such as reservoir protec-tion to greatest extent.Now be widely used as the important means of boring deep-well, ultra deep well, high-inclination directional well, horizontal well and water sensitivity bad ground, and obtain positive effect.But along with the use of oil base drilling fluid, create a large amount of discarded oil-base mud.
Oily sludge has the features such as oleaginousness is high, viscosity is large, particle is thin, dehydration is difficult.Its composition is extremely complicated, general containing heavy metal salts such as a large amount of aged crude oil, wax, bituminous matter, colloid, suspended solid, bacterium, salt, acidifying gas and a small amount of copper, zinc, chromium, mercury, simultaneously also containing toxic substances such as benzene series, anthracene, pyrene, phenols.The pollution that the accumulation for a long time of discarded oil-base mud can cause the havoc of surface vegetation to cause soil surface and underground water, directly or indirectly produces huge harm to plant animal and human health; In addition, containing more petroleum substance metal and inorganic mineral etc. in discarded oil-base mud, there is important petroleum vapor recovery and metalliferous mineral recycle value.Domesticly require to carry out harmless treatment to oily waste, therefore from the angle of environment protection and economic benefit, the discarded oil base treatment of mud technology finding a kind of economical and efficient seems particularly urgent and important.
From the phase at the beginning of the seventies in last century, domestic and international researchist sets about the research work carrying out Sludge in Oilfields process, successively have developed multiple contained Mud Treatment Technology.At present both at home and abroad oily sludge recycling technology mainly contains the treatment technology such as solvent extraction, matting, modified-mechanical separation, pyrolysis, ultrasonic, microwave, re-injection profile control, electrodynamics, freezing melting.
(1) solvent extraction technology: solvent extraction technology has different distribution capability based on solute in two kinds of immiscible solvents, utilizes " similar mix " principle, selects a kind of suitable solvent to make extraction agent, extracted by crude oil from oily sludge.This technology can realize oil, water, mud three-phase are effectively separated, and can realize the minimizing of oily sludge, resource utilization and harmless treatment to greatest extent.Its technical process is: 1. extraction agent and greasy filth fully mix in reaction tower, carries out breakdown of emulsion, extraction and dehydration under certain temperature, realizes oil, water, mud three phase separation; 2. solvent oil realizes extraction agent and former oil separating at Distallation systm; 3. dewater, solids after de-oiling realizes being separated of extraction agent and waste residue at Distallation systm.
(2) chemical cleaning method: chemical cleaning method adds a certain proportion of hot water and chemical agent as tensio-active agent etc. in oily sludge, the character of oil/liquid phase and oil/mud phase interface in oily sludge is changed by effects such as the rolling of chemical agent, emulsification, dissolving, solubilisings, crude oil is stripped down from silt particle surface washing, and then through the technique such as sedimentation, eddy flow, oily sludge is separated into oil, water, silt particle three-phase.Its technical process is: the 1. preparation of chemical; 2. oily sludge is joined in chemical, carry out chemical removal; 3. the profit silt particle mixture after cleaning enters in liquid-solid separator and carries out three phase separation.
(3) pyrolytic technique: pyrolytic technique is based on thermolability organic in oily sludge, under anaerobic, utilize heat energy that the heavy constituent in crude oil is converted into light constituent by thermolysis effect, then be evaporated from mud in a gaseous form, thus realize being separated of crude oil and silt particle.The gas that this process produces forms three kinds of phase materials after cooling: gas phase is based on methane and carbon dioxide; Liquid phase is based on normal temperature fuel oil and water; Solid phase is inorganic mineral and carbon residue.Its technical process is: 1. oily sludge is through screening pre-treatment, removes large granular impurity, transfers to pyrolysis reactor; 2. in pyrolysis oven, oily sludge carries out pyrolysis; 3. the oil gas volatilized is reclaimed by circulating water condensing.
Pyrolytic technique is the Main Means being widely used in oily sludge harmless treatment at present abroad, is a kind of oily sludge high-temperature processing technology of remodeling.Affect the size etc. because have pyrolysis temperature, pyrolysis rate, the gas-solid phase residence time and material of pyrolytic process and products collection efficiency thereof, wherein pyrolysis temperature is topmost influence factor, and it all has a great impact pyrolysis product distribution, productive rate and pyrolysis gas calorific value.At a lower temperature, hydro carbons macromolecular cleavage becomes more small molecular, and oil content is relatively many; Along with temperature raises, except macromolecular cleavage, also there is second pyrolysis in many intermediate products, and below C5 molecule and gaseous constituent increase, and gas yield is directly proportional growth, and various acid, tar, carbon slag reduce relatively.Although but above-mentioned technology has its advantage, be also faced with a corresponding difficult problem.
1, solvent extraction technology: the advantage of this technology is: process is relatively more thorough, can extract most of petroleum substance and reclaim, and effectively can remove microscale harmful substance; Technological process is simple, quick, selectivity is high.But face two hang-ups: one is lack a kind of efficient, nuisanceless, extraction agent that potential safety hazard is little; Two is that the problem of loss of extractant is solved not yet very well, and cost is higher.At present, abstraction technique is not also widely used in disposal of oily sludge.
2, chemical cleaning method: this technique major advantage is: simple and convenient operation flow, reliability is strong, and oil recovery rate is higher.Chemical has adverse influence to environment, and specificity is strong, may not have desired result or complete failure after effective object changes.The development in connecting to composite and expansion of current oily sludge chemical cleaning technique, compared with original single dose, significantly improves through composite and its crude oil recovery rate even that expands.
3, pyrolytic technique: this technology major advantage is: the rate of recovery of oil content (hydrocarbon compound) is higher, more thorough to disposal of oily sludge, after process, solid residue oil length is lower than 0.01%, in residue, putrefactive organism content is little, and ash melting can prevent the stripping of metal species material, reduces the secondary pollution to environment; Shortcoming is: energy consumption is comparatively large, and complex technical process, invests higher.Along with the strict control of oily sludge discharge index, because having, process is thorough, speed is fast for this technique, resource recycling high, will become the important way of disposal of oily sludge.
Summary of the invention
The object of the present invention is to provide a kind of discarded oil-base mud harmless treatment process, solve prior art energy consumption excessive, the problem that the treatment time is long.
The present invention is achieved through the following technical solutions:
Discarded oil-base mud harmless treatment process, comprises the following steps:
(1) sieve: by oily sludge through vibratory screening apparatus, isolate the solid impurity of larger particles, and deslagging;
(2) modified: in the oily sludge after step (1) process, to add medicament carry out modified modification, change Sludge Surface particle physics chemical property and component;
(3) preheating strengthening is modified: under the oily sludge after step (2) being processed is placed in the condition of 80 ~ 180 DEG C, heating 10 ~ 20min;
(4) negative pressure cracking: carry out thermo-cracking to the oily sludge after step (3) process under condition of negative pressure, obtain volatiles, cracking temperature is: 300 ~ 500;
(5) condensation: in the oily sludge after step (4) being processed, volatiles obtains mixing oil through condensation liquefaction;
(6) fractionation: passed into by mixing oil in separation column and carry out fractionation, by water and separating of oil, obtains lightweight oil and diesel oil.
Further, the medicament in described step (2) comprises adjusting material, tensio-active agent, auxiliary, catalyst for cracking.
Again further, described adjusting material is CH
3oH, described tensio-active agent is sulfated castor oil, and described thick auxiliary agent is sodium carbonate, and described catalyst for cracking is Al
2o
3.
Further, by mass, CH
3the add-on of OH is: 2.5 ~ 3%; The add-on of sulfated castor oil is 0.3 ~ 0.4%; The add-on of sodium carbonate is: 2 ~ 3%; Al
2o
3add-on be: 0.01 ~ 0.03%.
In addition, the addition sequence of described step (2) Chinese medicine is: first add adjusting material, then adds tensio-active agent and auxiliary, finally adds catalyst for cracking.
The present invention has the following advantages and beneficial effect:
(1) the present invention adopts screening, and---modified---preheating strengthening is modified, and---the art breading oily sludge of negative pressure cracking---condensation---fractionation, has feature that is efficient, energy-saving and environmental protection; With current cracking technology ratio, the work period shortens 15%, and energy consumption reduces by 20%, and economic benefit significantly improves.
(2) the present invention is by carrying out preheating strengthening modifier treatment to oily sludge, can strengthen brokenly glue effect, improve crude oil and silt particle separating effect, increase the contact area of raw material and medicament, improve speed of reaction; Preheating greasy filth can be avoided unevenly causing the incomplete phenomenon of cracking, preliminary catalytic cracking because being heated; In addition, the activity of medicament can be increased, improve the activity of particle, the scission reaction speed of latter stage is improved.
(3) the present invention is by negative pressure cracking process, reduces the boiling point of oil, makes it rapid oil removing, because temperature is low, can shorten deslagging cooling time.Because cracking temperature under normal pressure is 440 ~ 750 DEG C, but adopt negative pressure cracking process, temperature-controllable is built in 300 ~ 500 DEG C, and optimum temps controls at 300 ~ 400 DEG C.
(4) the present invention adds medicament and carries out modified, can change Sludge Surface particle physics chemical property and component, reduce the difficulty of cracking, shorten cracking required time about 15%.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Embodiment
Discarded oil-base mud harmless treatment process, comprises the following steps:
(1) sieve: by oily sludge through vibratory screening apparatus, promptly isolate the solid impurity of larger particles, and continuous deslagging rapidly.
(2) modified: before oily sludge enters pyrolyzer, to add medicament carry out modified modification, change Sludge Surface particle physics chemical property and component, the difficulty of cracking can be reduced, shorten cracking required time about 15%.
But the present embodiment the medicament that adds comprise adjusting material, tensio-active agent, auxiliary, catalyst for cracking; Wherein adjusting material can change the physico-chemical property of ion surface, makes it to a certain extent crude oil is separated with silt, increases reaction contact area; Tensio-active agent and auxiliary, can increase specific surface area and the mobility of greasy filth particle, in the preheating strengthening modified stage, greasy filth viscosity reduced greatly, is heated more rapidly, evenly and prevented from caking, can reduces cracking energy consumption widely; Catalyst for cracking, can the cracking such as catalysis aged crude oil, bituminous matter, generates various lightweight oil.
Through preferred, the adjusting material of the present embodiment selects CH
3oH, sulfated castor oil selected by tensio-active agent, and sodium carbonate selected by auxiliary, and catalyst for cracking selects Al
2o
3.Its concrete add-on is as follows: by mass, CH
3the add-on of OH is: 2.5 ~ 3%; The add-on of sulfated castor oil is 0.3 ~ 0.4%; The add-on of sodium carbonate is: 2 ~ 3%; Al
2o
3add-on be: 0.01 ~ 0.03%.
(3) preheating strengthening is modified: under the oily sludge after step (2) being processed is placed in the condition of 80 ~ 180 DEG C, heating 10 ~ 20min.Its role is to: the 1. broken glue effect of strengthening, improve crude oil and silt separating effect, increase the contact area of raw material and tensio-active agent+auxiliary, catalyst for cracking, raising speed of reaction; 2. preheating greasy filth, avoids unevenly causing the incomplete phenomenon of cracking, preliminary catalytic cracking because being heated; 3. increase the activity of tensio-active agent+auxiliary, improve the activity of particle, the scission reaction speed of latter stage is improved.
(4) negative pressure cracking: carry out thermo-cracking under condition of negative pressure, chemical bond rupture when macromolecular complex proton is heated under anoxic conditions, the reactions such as isomerization and small molecules polymerization, finally generate small-molecule substance; Adopt the major cause of negative pressure cracking to be reduce the boiling point of oil, make it fuel-displaced rapidly, because temperature is low, deslagging cooling time can be shortened.Under normal pressure, cracking temperature is 440 ~ 750 DEG C, but (negative pressure, catalyzer) temperature can realize cracking at 300 ~ 400 DEG C at the process conditions.
(5) condensation: obtain mixing oil through subcooling condensate after negative pressure cracking, be collected in hold-up vessel.
(6) fractionation: because the boiling point of different components in mixing oil is different, in separation column, by control temperature, comes water with separating of oil, obtains lightweight oil and the diesel oil of separation simultaneously.
The present invention analyzes the residual body refuse of cracking oil refining, and concrete outcome is as follows:
The residual body refuse leach liquor result of laboratory test (unit: mg/L) of table 1 cracking oil refining
| Sample | COD | pH | Ammonia nitrogen | Petroleum-type | Colourity |
| Refining slag | 87 | 8.9 | 3 | 4.59 | 0 |
| Emission standard | 100 | 6.0-9.0 | 15 | 5 | 50 |
Can be found out by above-mentioned result of laboratory test, the body refuse after adopting process of the present invention to contain mud reaches the standard of directly discharge.
What deserves to be explained is method of the present invention very environmental protection, be described as follows:
1, waste gas: whole treating processes is be in hermetically sealed operation substantially, does not directly discharge the phenomenon of " three wastes ".By oiled waste gas burning device, oiliness waste gas can be made to be fully burned in boiler heat release, and boiler exhaust gas is through environmental protection three-stage filtration, and alkali lye spray equipment reaches tasteless, colourless discharge environmental protection standard.Passing through security device---water-sealed filter, burner Thorough combustion, namely eliminates exhaust emission, again saves mass energy.
2, useless solids: through chemical examination, solid waste reaches discharging standards after this art breading, can be directly used in well site backfill or cement auxiliary material etc.
3, waste water: the waste water that oily water separation produces is used for cooling system make up water, realizes non-wastewater discharge.Greasy filth is in treating processes, and can produce some has weakly acidic waste water (measure little, easily process).By to add in weak lye and after, neutral waste water through three-stage filtration, reach innoxious after, be discharged to cooling water recirculation system.
In addition, present invention reduces temperature during cracking, thus saved the energy, pyrolysis time also shortens 0.5h relative to conventional art simultaneously, and energy consumption reduces widely; In addition, because temperature is low, slag dumping also just shortens cooling time, and the work period shortens relatively.
According to above-described embodiment, just the present invention can be realized well.What deserves to be explained is; under prerequisite based on above-mentioned design, for solving same technical problem, even if some making on the invention are without substantial change or polishing; the essence of the technical scheme adopted is still the same with the present invention, therefore it also should in protection scope of the present invention.
Claims (5)
1. discarded oil-base mud harmless treatment process, is characterized in that, comprise the following steps:
(1) sieve: by oily sludge through vibratory screening apparatus, isolate the solid impurity of larger particles, and deslagging;
(2) modified: in the oily sludge after step (1) process, to add medicament carry out modified modification, change Sludge Surface particle physics chemical property and component;
(3) preheating strengthening is modified: under the oily sludge after step (2) being processed is placed in the condition of 80 ~ 180 DEG C, heating 10 ~ 20min;
(4) negative pressure cracking: carry out thermo-cracking to the oily sludge after step (3) process under condition of negative pressure, cracking temperature is: 300 ~ 500 DEG C;
(5) condensation: in the oily sludge after step (4) being processed, volatiles obtains mixing oil through condensation liquefaction;
(6) fractionation: passed into by mixing oil in separation column and carry out fractionation, by water and separating of oil, obtains lightweight oil and diesel oil.
2. discarded oil-base mud harmless treatment process according to claim 1, is characterized in that, the medicament in described step (2) comprises adjusting material, tensio-active agent, auxiliary, catalyst for cracking.
3. discarded oil-base mud harmless treatment process according to claim 2, is characterized in that, described adjusting material is CH
3oH, described tensio-active agent is sulfated castor oil, and described thick auxiliary agent is sodium carbonate, and described catalyst for cracking is Al
2o
3.
4. discarded oil-base mud harmless treatment process according to claim 3, is characterized in that, by mass, and CH
3the add-on of OH is: 2.5 ~ 3%; The add-on of sulfated castor oil is 0.3 ~ 0.4%; The add-on of sodium carbonate is: 2 ~ 3%; Al
2o
3add-on be: 0.01 ~ 0.03%.
5. the discarded oil-base mud harmless treatment process according to any one of claim 2 ~ 4, is characterized in that, the addition sequence of described step (2) Chinese medicine is: first add adjusting material, then adds tensio-active agent and auxiliary, finally adds catalyst for cracking.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304096A (en) * | 2016-04-21 | 2017-10-31 | 李润超 | A kind of oily sludge pyrolysis processing technology |
| CN106498190B (en) * | 2016-11-02 | 2018-04-03 | 江西理工大学 | The method of neodymium iron boron greasy filth waste material in-situ carbon thermocatalytic chlorination recovering rare earth product |
| CN108017250A (en) * | 2017-11-15 | 2018-05-11 | 袁东升 | Pyrohydrolysis formula oily sediment Harmless and Comprehensive Disposal technique |
| CN108623120A (en) * | 2017-03-21 | 2018-10-09 | 上海利泽环保科技有限公司 | A kind of composition and its preparation method and application |
| CN110950513A (en) * | 2019-11-26 | 2020-04-03 | 西安交通大学 | Method for treating bottom mud by utilizing surfactant pretreatment-hydrothermal oxidation-thermal cracking coupling method |
| CN113137195A (en) * | 2021-04-02 | 2021-07-20 | 安洁行方流体管理技术有限公司 | Recycling method and system for base liquid thrown out by oil-based drilling cuttings |
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| CN110950513A (en) * | 2019-11-26 | 2020-04-03 | 西安交通大学 | Method for treating bottom mud by utilizing surfactant pretreatment-hydrothermal oxidation-thermal cracking coupling method |
| CN113137195A (en) * | 2021-04-02 | 2021-07-20 | 安洁行方流体管理技术有限公司 | Recycling method and system for base liquid thrown out by oil-based drilling cuttings |
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Effective date of registration: 20230713 Address after: 635000 China (Puguang) Microglass New Material Industrial Park, Xuanhan County, Dazhou City, Sichuan Province Patentee after: Sichuan Yilong Environmental Protection Technology Co.,Ltd. Address before: No. 712, 7th floor, unit 1, building 1, No. 1700, North Tianfu Avenue, Chengdu hi tech Zone, Sichuan 610000 Patentee before: SICHUAN GUANGLONG ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. |