CN105419855A - Treatment process of high-slag-content sump oil - Google Patents
Treatment process of high-slag-content sump oil Download PDFInfo
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- CN105419855A CN105419855A CN201610016603.XA CN201610016603A CN105419855A CN 105419855 A CN105419855 A CN 105419855A CN 201610016603 A CN201610016603 A CN 201610016603A CN 105419855 A CN105419855 A CN 105419855A
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- oil
- sump oil
- slag
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- slag inclusion
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a treatment process of high-slag-content sump oil and relates to the technical field of separation of high-slag-content sump oil. KMnO4 is adopted as a pre-oxidizing agent to perform oxidizing degradation on colloidal asphaltene on the surface of slag, meanwhile, the stabilizing effect of solid particles on an interfacial film is damaged, in other words, the slag washing effect of an oxidizing agent is achieved, the macromolecular structure of polymers is degraded into small molecules, a regular-layer-shaped structure formed by a surface active agent on an oil and water interface is damaged, steric hindrance is reduced, oil droplet aggregation is promoted, and a good pretreatment effect is achieved for the situation that a subsequent demulsifying agent enters the sump oil to play a role. Then, a demulsifying agent of a compound type and a flocculating agent are sequentially added, due to the fact that demulsifying dross is electrically negative, the inorganic cationic flocculating agent is added to neutralize charges of the solid particles, affinity between the solid particles and water molecules is reduced, the coagulation force between the particles is increased so that the particle size of alum floc can be increased, and therefore further flocculating setting separation happens to part of dross remaining in an oil layer, water and slag are removed, and crude oil is recycled.
Description
Technical field
The present invention relates to the separation technology field of high slag inclusion sump oil.
Background technology
Content and the salinity of the salt in the high slag inclusion sump oil produced when cutting dispose of sewage between water, electrofining, equipment washing and water treatment vehicle from certain refinery production plant Central Plains oil tank, oils, colloid, bituminous matter, solid particulate are all higher.Sump oil source is more assorted, and nature difference is large, the multiple emulsification system having water-in-oil, oil-in-water and formed by water-in-oil and oil-in-water.The naturally occurring emulsifying agents such as the colloid itself contained, bituminous matter, solid particulate, be enriched in water-oil interface, form firmly interfacial film, have extremely strong interfacial tension, intractability is very big.In the actual production of refinery, the sump oil produced is often containing higher grain slag, and general grain slag amount is at 10-80%.Sump oil long-term storage is not only the waste of petroleum resources, and can bring great pollution to environment, therefore must carry out harmless treatment to it.
At present the method that slag adopts is taken off for sump oil breaking emulsion and dewatering varied, and each tool pros and cons.The sump oil that the chemical demulsification method of hot settling process and routine is serious to emulsification, particularly high slag inclusion sump oil demulsification is unsatisfactory, processes more difficult; Electrochemical process process sump oil is higher to electrochemical equipment requirements, is not suitable for promoting; Though burning method can reduce the pollution of breakdown of emulsion mud to environment, complicated operation, processing cost is high, and the SO generated
2deng larger to the harm of environment; Though centrifuging is better to the treatment effect of sump oil three phase separation, expense is too high, has larger limitation; Biological treatment pollutes little but long processing period.Along with becoming increasingly conspicuous of environmental issue, find that a kind of processing costs is low, breakdown of emulsion efficiency is high and eco-friendly technique has become the inexorable trend of sump oil process.
Along with the development of technology of reservoir sweep, the various medicaments added in exploitation make the emulsifying stability of follow-up sump oil high, and add single emulsion splitter and often have significant limitation, and this makes sump oil breakdown of emulsion more difficult.Therefore, be necessary to add preoxidation agent in chemical demulsification technique, play the Effect of Pretreatment of preoxidation agent, give security for follow-up emulsion splitter and flocculation agent play a role, thus realize the efficient breakdown of emulsion to high slag inclusion sump oil.
Summary of the invention
The present invention seeks to for the deficiencies in the prior art and defect, propose a kind for the treatment of process of high slag inclusion sump oil.
Technical solution of the present invention is: high slag inclusion sump oil is heated to 50 ~ 90 DEG C, is mixed into KMnO successively
4the aqueous solution, emulsion splitter, flocculant aqueous solution, make oil, water, slag three phase separation through sedimentation.
The present invention is in view of KMnO
4the strong oxidizing property of self and the demulsification in laboratory, propose and adopt KMnO
4, emulsion splitter and flocculation agent process refinery height slag inclusion sump oil breaking emulsion and dewatering take off slag technique.The present invention adopts KMnO
4as preoxidation agent, oxidative degradation is carried out to (general emulsion splitter are difficult to play a role to this) such as the gum asphalts on slag surface, destroy solid particulate to the firm effect of interfacial film simultaneously, namely " washery slag " effect of oxygenant is played, the macromolecular structure of polymkeric substance is degraded to small molecules, destroy the regular laminate structure that surfactant is formed on water-oil interface, reduce sterically hindered, promote oil droplet coalescence, play good Effect of Pretreatment for emulsion splitter subsequently enters to play a role.Then composite emulsion breaker, flocculation agent is added successively, because breakdown of emulsion scum silica frost is electronegativity, therefore the electric charge added with solid particles band in inorganic cation flocculation agent, reduce the avidity of solid particulate and water molecules, cohesive force between increase particle is to increase the particle diameter of flco, thus make part remain in the further flocculation deposition seperation of scum silica frost of oil reservoir, realize dehydration, de-slag and reclaim crude oil.
Cost of the present invention is lower, simple to operate, reaction temperature and, the water quality of deviating from water is good, dehydration rate is high and crude oil recovery rate is high.High slag inclusion sump oil after process of the present invention, makes oil-contg be 32.6%, water-content 32.4%, slag content is that the dehydration rate of the slag inclusion sump oil of 35.0% reaches 97.2%, crude oil recovery rate reaches 95.6%, compared with reclaiming crude oil, improves 47.6% and 31.0% respectively with simple emulsion splitter breaking emulsion and dewatering.
The present invention is applicable to the dirty oil handling of each refinery height slag inclusion, can ensure oil recovery freshening, realizes the resource utilization recycling of sump oil, to the economic benefit too increasing enterprise while the process of sump oil environmental recovery bonds, has larger commercial introduction and is worth.
Further, KMnO of the present invention
4kMnO in the aqueous solution
4be 2000 ~ 10000mg: 1L with the ratio of mixture of high slag inclusion sump oil.In this concentration range, KMnO
4not only oxidative degradation is carried out to the gum asphalt etc. on slag surface, the macromolecular structures such as gum asphalt are degraded to small molecules, reduce solid particulate to the firm effect of interfacial film, and the regular laminate structure that the tensio-active agent that can destroy in sump oil is formed on water-oil interface, reduce sterically hindered, promote oil droplet coalescence, play good Effect of Pretreatment for the follow-up emulsion splitter added plays a role.This concentration range KMnO
4sump oil breaking emulsion and dewatering rate can be made to improve 20% ~ 30%.
The ratio of mixture of described emulsion splitter and high slag inclusion sump oil is 750 ~ 1750mg: 1L.In this concentration range, naturally occurring emulsifying agent generation physics, chemical reaction in emulsion splitter and sump oil, cause water-oil interface character to change, and destroys the rock steady structure of interfacial film, realize the reduction of oil water interfacial tension, expands the field of activity of water-oil interface.This concentration range emulsion splitter can make sump oil breaking emulsion and dewatering rate improve 6% ~ 17%.
In described flocculant aqueous solution, the ratio of mixture of flocculation agent and high slag inclusion sump oil is 400 ~ 2000mg: 1L.In this concentration range, flocculation agent can in and the electric charge of solid particles band, remain in the further flocculating settling of scum silica frost in oil reservoir after being completed by breakdown of emulsion, improve the breaking emulsion and dewatering rate of sump oil.This concentration range flocculation agent can make the breaking emulsion and dewatering rate of sump oil improve 5% ~ 11%.
Embodiment
High slag inclusion sump oil carries out breaking emulsion and dewatering and takes off Slag treatment step:
1, it is 2.0h that the high slag inclusion sump oil getting 1000L heats 1.5 ~ 2.0h(optimum in 50 ~ 90 DEG C of water-baths), preferably 80 DEG C.
2, after 40min, in sump oil, the KMnO that 5L concentration is 400-2000g/L is added
4the aqueous solution, stirs and makes it mix.
3, after 30min, in sump oil, add the emulsion splitter of 750-1750g, stir and make it mix.
Emulsion splitter by mass ratio 1: 1 oil-soluble demulsifier SP-2 and water-soluble demulsifier DF-4 is composite makes.
4, after 30min, in sump oil, add the flocculant aqueous solution that 5L concentration is 80-400g/L, stir and make it mix.
Flocculation agent is inorganic cation flocculant poly aluminum chloride.
5, the sump oil after process is carried out settlement separate, realize oil-water residue three phase separation, reclaim crude oil.
Wherein step 2,3,4 all plays an important role to the breakdown of emulsion of high slag inclusion sump oil, sump oil oil water interfacial tension can be effectively reduced, reduce viscosity, destroy the emulsification system of sump oil, thus sump oil is reached effect that breaking emulsion and dewatering takes off slag, improve crude oil recovery rate.If the breaking emulsion and dewatering ability of interpolation emulsion splitter simple in step 3 to sump oil is very limited, therefore adopt the KMnO in step 2
4first carry out pre-treatment to high slag inclusion sump oil, i.e. oxidation to harness emulsion, then add composite emulsion breaker and flocculation agent, promote the three phase separation of oil-water residue, the breaking emulsion and dewatering finally realizing sump oil takes off slag.
Specific embodiment: pump into reactor from slop oil tank by 1000L sump oil, after being heated to 50 ~ 90 DEG C, according to step 2,3,4 successively by KMnO
4the aqueous solution, emulsion splitter and flocculant aqueous solution add in reactor and mix with sump oil and react, wherein KMnO
4: 6000g, emulsion splitter: 1000g, flocculation agent PAC:1600g, after reaction 2.0h, sump oil to enter in settlement separation tank after settlement separate 3.0h, upper strata oil enters crude oil recovery pond, middle level sewage enters sewage lagoon, and lower floor's grain slag then enters sludge sump, then after grain slag being entered centrifuge dehydration, discharge slag of the centrifugal end, aqueous phase enters sewage lagoon.Foul water fraction reuse in sewage lagoon, part then enters between water treatment vehicle carries out purifying treatment.
Claims (6)
1. a treatment process for high slag inclusion sump oil, is characterized in that: high slag inclusion sump oil is heated to 50 ~ 90 DEG C, is mixed into KMnO successively
4the aqueous solution, emulsion splitter, flocculant aqueous solution, make oil, water, slag three phase separation through sedimentation.
2. the treatment process of high slag inclusion sump oil according to claim 1, is characterized in that described KMnO
4kMnO in the aqueous solution
4be 2000 ~ 10000mg: 1L with the ratio of mixture of high slag inclusion sump oil.
3. the treatment process of high slag inclusion sump oil according to claim 1, is characterized in that the ratio of mixture of described emulsion splitter and high slag inclusion sump oil is 750 ~ 1750mg: 1L.
4. the treatment process of high slag inclusion sump oil according to claim 1, is characterized in that the ratio of mixture of flocculation agent and high slag inclusion sump oil in described flocculant aqueous solution is 400 ~ 2000mg: 1L.
5. the treatment process of high slag inclusion sump oil according to claim 1, is characterized in that: described emulsion splitter by mass ratio 1: 1 oil-soluble demulsifier SP-2 and water-soluble demulsifier DF-4 is composite makes.
6. the treatment process of high slag inclusion sump oil according to claim 1, is characterized in that: described flocculation agent is inorganic cation flocculant poly aluminum chloride.
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| CN201610016603.XA CN105419855B (en) | 2016-01-12 | 2016-01-12 | A kind of handling process of high slag inclusion sump oil |
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| CN201610016603.XA CN105419855B (en) | 2016-01-12 | 2016-01-12 | A kind of handling process of high slag inclusion sump oil |
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| CN105419855A true CN105419855A (en) | 2016-03-23 |
| CN105419855B CN105419855B (en) | 2017-09-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU814392A1 (en) * | 1979-01-16 | 1981-03-23 | Московский Автомобильный Завод Им.И.A.Лихачева | Method of processing waste emulsion cutting fluids |
| CN101565251A (en) * | 2009-05-26 | 2009-10-28 | 北京清大国华环保科技有限公司 | Technique for using composite demulsification-membrane method to treat high-concentration emulsified liquid waste water and device |
| CN102452760A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Treatment method for recycle of oil field produced water |
| CN103073119A (en) * | 2012-09-14 | 2013-05-01 | 大连格兰清水环境工程有限公司 | Oil-containing emulsion wastewater treatment method and apparatus thereof |
-
2016
- 2016-01-12 CN CN201610016603.XA patent/CN105419855B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU814392A1 (en) * | 1979-01-16 | 1981-03-23 | Московский Автомобильный Завод Им.И.A.Лихачева | Method of processing waste emulsion cutting fluids |
| CN101565251A (en) * | 2009-05-26 | 2009-10-28 | 北京清大国华环保科技有限公司 | Technique for using composite demulsification-membrane method to treat high-concentration emulsified liquid waste water and device |
| CN102452760A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Treatment method for recycle of oil field produced water |
| CN103073119A (en) * | 2012-09-14 | 2013-05-01 | 大连格兰清水环境工程有限公司 | Oil-containing emulsion wastewater treatment method and apparatus thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李亚峰等，: "破乳絮凝法处理稠油污水", 《沈阳建筑大学学报（自然科学版）》 * |
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