CN102503056B - Biological oil recovery method for oil-containing sludge in refinery - Google Patents
Biological oil recovery method for oil-containing sludge in refinery Download PDFInfo
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Abstract
The invention relates to a biological oil recovery method for an oil-containing sludge in a refinery. The method comprises the following steps of: mixing oil-containing sludge, a biological surfactant and water to obtain a first mixture, heating the first mixture, and stirring to fully contact the oil-containing sludge with the surfactant; preserving heat of the stirred first mixture, and standing to partition the first mixture into an oil layer, an emulsifying layer and a sludge layer; separating the oil layer, the emulsifying layer and the sludge layer, recovering the oil layer to obtain oil, adding acid into the emulsifying layer to obtain a second mixture, and heating and oscillating the second mixture to fully contact the acid with the emulsifying layer; and after oscillation is completed, preserving heat of the oscillated second mixture, standing into an oil layer and a water layer, and recovering the oil layer to obtain oil. Due to the adoption of the method provided by the invention, the difficulty in subsequent sludge treatment/disposal can be lowered, the problem of environment pollution of the oil-containing sludge is solved, and the originally-wasted oil resource can be recovered on a large scale.
Description
Technical field
The present invention relates to the recovery and treatment method of a kind of refinery oily sludge, relate in particular to the oil product biological recovery method of a kind of refinery oily sludge, belong to the petroleum refining field for the treatment of of solid waste.
Background technology
The Sewage treatment systems of petroleum refinery and oil movement and storage system can produce a large amount of oily sludges.This oily sludge mainly contains oil trap bed mud, flotation cell scum silica frost, oil tank bed mud etc., usually oil length is between 10%-50%, the resource utilization recovery value is high, be discharged into such as half-hearted the processing and go in the environment, not only can cause larger pollution to surrounding soil, water body, vegetation, also can waste a large amount of petroleum resources simultaneously.The sewage load of the refinery of present large-scale oil refining enterprise is generally all larger, sewage treatment process is all more sound, and the greasy filth generation is also larger simultaneously, the greasy filth kind, greasy filth character has typicalness in Petrochemical Enterprises, and the pressure that greasy filth recycling and minimizing are processed is large.
Researching and developing a kind of method that can recycle efficiently petroleum refinery's oily sludge is one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide the recovery method of a kind of refinery oily sludge, by adopting bio-surfactant oily sludge is processed, realize the efficient recovery to oil product.
For achieving the above object, the present invention at first provides the oil product biological recovery method of a kind of refinery oily sludge, and it may further comprise the steps:
(1), oily sludge, bio-surfactant and water are mixed to get the first mixture, the first mixture is heated, stirs, oily sludge is fully contacted with tensio-active agent;
(2), the first mixture after stirring is incubated and leaves standstill, make the first mixture be divided into oil reservoir, emulsion layer and mud layer;
(3), oil reservoir, emulsion layer and mud layer are separated, oil reservoir reclaimed obtain oil product, add acid in the emulsion layer to obtain the second mixture, the second mixture is heated, vibrate, make sourly fully to contact with emulsion layer;
(4), after vibration finishes, the second mixture through vibration is incubated, and leaves standstill and make it be divided into oil product layer and water layer, the oil product layer is reclaimed obtain oil product.
In aforesaid method provided by the present invention, preferably, step (1) is: oily sludge, bio-surfactant and water are mixed to get the first mixture, utilize heating in water bath to 50-70 ℃ after the sealing, speed with 100-200r/min (being preferably 180r/min) stirs 30min, and oily sludge is fully contacted with tensio-active agent.
In aforesaid method provided by the present invention, preferably, in step (1), the volume ratio of oily sludge, water and bio-surfactant is 1: 1: 0.15.
In aforesaid method provided by the present invention, preferably, in step (1), bio-surfactant at first is mixed to get bio-surfactant solution with water, and then is mixed to get mutually the first mixture with oily sludge.
In aforesaid method provided by the present invention, preferably, step (2) is: the first mixture after will stirring places 50-70 ℃ water-bath insulation and leaves standstill 20min, makes the first mixture be divided into oil reservoir, emulsion layer and mud layer.
In aforesaid method provided by the present invention, preferably, step (3) is: oil reservoir, emulsion layer and mud layer are separated, the oil reservoir recovery is obtained oil product, add acid in the emulsion layer and obtain the second mixture, after the sealing, be heated to 60-70 ℃ and carry out the vibration of 10min with the speed of 150-200r/min, acid is fully contacted with emulsion layer.The acid that adds in the naphtenic acid process in this step can be as adding medicament in follow-up sewage treatment process, and the potential of hydrogen of buffering sewage can not cause secondary pollution, also can reduce the medicament input cost.
In aforesaid method provided by the present invention, preferably, in step (3), the acid of adopting is hydrochloric acid and/or phosphoric acid, and preferably, the concentration of described acid is 1mol/L.
In aforesaid method provided by the present invention, preferably, in step (3), oily sludge is 100 with the volume ratio of acid: 1.67-6.67, more preferably 100: 3.33.
In aforesaid method provided by the present invention, preferably, step (4) is: after vibration is finished, the second mixture through vibration is carried out the insulation of 20min 50-70 ℃ water-bath, and leave standstill and make it be divided into oil product layer and water layer, the oil product layer is reclaimed obtain oil product.
In aforesaid method provided by the present invention, preferably, the bio-surfactant that adopts is Glycolipids Biosurfactants via.
The flow process of the oil product biological recovery method of refinery provided by the present invention oily sludge as shown in Figure 1, it can carry out according to following concrete steps:
At first (for example: Glycolipids Biosurfactants via) mix with water, then add oily sludge, obtain the first mixture, wherein, the volume ratio of oily sludge, water and bio-surfactant is 1: 1: 0.15 with bio-surfactant;
At constant temperature (heating in water bath, 50-70 ℃) it is lower that (rotating speed is 150-200r/min with agitator, time is 30min) the first mixture is stirred, oily sludge is fully smashed, tensio-active agent is fully spread and fully contact with the interface of oily sludge body, make the surface of oily sludge progressively change water-wet into by original glossy wetting, thereby make the oil content in the oily sludge emulsified, enter into mutually water from mud;
Subsequently the first mixture after the emulsification is incubated and leaves standstill that (heating in water bath, 20min), is layered as it by 50-70 ℃: oil reservoir, emulsion layer, water and mud layer (mud phase);
After layering interfaces appears clearly in emulsion layer and mud layer, shift emulsion layer, and acid adding (preferred concentration is hydrochloric acid and/or the phosphoric acid of 1mol/L) is regulated pH, and (oily sludge is preferably 100 with the volume ratio of acid: 1.67-6.67), obtain the second mixture, then (temperature is 60-70 ℃ the second mixture to be placed shaking table insulation vibration, rotating speed is 150-200r/min, time is 10min), make acid fully destroy the stability of bio-surfactant, the bio-surfactant loss of activity, thus oil product is separated from destroyed emulsion layer;
After vibration is finished, leave standstill (heating in water bath to being incubated through the second mixture that vibrates, 60-70 ℃, 20min), make emulsion layer be layered as water layer (water) and oil product layer (oil product mutually), the oil product layer is reclaimed, then mix the highly purified oil product of acquisition with the oil product that preceding step reclaims.
In the oil product biological recovery method of refinery provided by the present invention oily sludge, the bio-surfactant of destroyed, the loss of activity of stability again can activity recovery after acid base equilibrium, continues on for the recovery of oil product.
The oil product biological recovery method of refinery provided by the present invention oily sludge meets environmental requirement, not only can reclaim a part of crude oil, and discarded raffinate can also further be degraded by microorganisms, turn harm into good, effectively solved refinery's oily sludge recycling and the large difficult problem of minimizing processing pressure.
Method provided by the present invention can reduce the difficulty of follow-up sludge treatment/disposal on the one hand, solve the problem of environmental pollution of oily sludge, and can also significantly reclaim the oil product resource of waste, the double goal of pursuing energy-saving and emission-reduction and productivity effect for enterprise provides favourable guarantee, and important using value is arranged.
Description of drawings
Fig. 1 is the schematic flow sheet of the oil product biological recovery method of refinery provided by the present invention oily sludge.
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, existing technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as restriction to practical range of the present invention.
(content of embodiment all is to make amendment as foundation take the embodiment that you provide, and whether would you please consider suitable)
Embodiment 1
Present embodiment provides the oil product biological recovery method of a kind of refinery oily sludge, and it may further comprise the steps:
Water is mixed by 1: 0.15 volume ratio with Glycolipids Biosurfactants via, obtain bio-surfactant solution;
With water ratio be 10.7%, oil-contg is that 30.34% oily sludge and bio-surfactant solution are mixed to get the first mixture, wherein, the volume ratio of oily sludge and water, bio-surfactant is 1: 1: 0.15, the first mixture is placed 60 ℃ of heating in water bath, after the first mixture temperature is elevated to 60 ℃, adopt agitator to stir 30min with 180r/min, make bio-surfactant carry out emulsification to oily sludge;
The first mixture after the emulsification is incubated in 60 ℃ of water-baths leaves standstill 20min, make it be layered as three-phase: oil reservoir, emulsion layer, mud layer;
Oil reservoir is separated with emulsion layer, oil reservoir reclaimed obtain oil product, the phosphoric acid (volume ratio that is oily sludge and phosphoric acid is 100: 3.33) that adds the 1mol/L that accounts for oily sludge volume 3.33% in emulsion layer obtains the second mixture, the second mixture is placed the vibrator of 60 ℃ of constant temperature, with the velocity fluctuation 10min of 180r/min;
Place 60 ℃ of water-baths to leave standstill 20min in the second mixture after the vibration, it is layered as: oil product layer and water layer, the recovery of oil product layer obtained oil product, reclaim the oil product that obtains with above-mentioned steps and merge;
Outward transport processing after the dehydration of the mud layer of sedimentation after the emulsification, the waste water that sewage produces together with breakdown of emulsion enters Sewage treatment systems and processes; Through above-mentioned emulsification, breakdown of emulsion, separation, so that originally be difficult for easier the sloughing of moisture of being removed by mechanical force in the oily sludge, and 91 ± 2% oil content is recovered in the oily sludge.
Embodiment 2
Present embodiment provides the oil product biological recovery method of a kind of refinery oily sludge, and it may further comprise the steps:
Water is mixed by 1: 0.15 volume ratio with Glycolipids Biosurfactants via, obtain bio-surfactant solution;
With water ratio be 79.94%, oil-contg is that 10% oily sludge and bio-surfactant solution are mixed to get the first mixture, wherein, the volume ratio of oily sludge and water, bio-surfactant is 1: 1: 0.15, the first mixture is placed 60 ℃ of heating in water bath, after the first mixture temperature is elevated to 60 ℃, adopt agitator to stir 30min with 150r/min, make bio-surfactant carry out emulsification to oily sludge;
The first mixture after the emulsification is incubated in 60 ℃ of water-baths leaves standstill 20min, make it be layered as three-phase: oil reservoir, emulsion layer, mud layer;
Oil reservoir is separated with emulsion layer, oil reservoir reclaimed obtain oil product, the phosphoric acid (volume ratio that is oily sludge and phosphoric acid is 100: 1.67) that adds the 1mol/L that accounts for oily sludge volume 1.67% in emulsion layer obtains the second mixture, the second mixture is placed the vibrator of 60 ℃ of constant temperature, with the velocity fluctuation 10min of 150r/min;
Place 60 ℃ of water-baths to leave standstill 20min in the second mixture after the vibration, it is layered as: oil product layer and water layer, the recovery of oil product layer obtained oil product, reclaim the oil product that obtains with above-mentioned steps and merge;
Outward transport processing after the dehydration of the mud layer of sedimentation after the emulsification, the waste water that sewage produces together with breakdown of emulsion enters Sewage treatment systems and processes; Through above-mentioned emulsification, breakdown of emulsion, separation, so that originally be difficult for easier the sloughing of moisture of being removed by mechanical force in the oily sludge, and 85 ± 3% oil content is recovered in the oily sludge.
Embodiment 3
Present embodiment provides the oil product biological recovery method of a kind of refinery oily sludge, and it may further comprise the steps:
Water is mixed by 1: 0.15 volume ratio with Glycolipids Biosurfactants via, obtain bio-surfactant solution;
With water ratio be 14.46%, oil-contg is that 51.78% oily sludge and bio-surfactant solution are mixed to get the first mixture, wherein, the volume ratio of oily sludge and water, bio-surfactant is 1: 1: 0.15, the first mixture is placed 70 ℃ of heating in water bath, after the first mixture temperature is elevated to 70 ℃, adopt agitator to stir 30min with 200r/min, make bio-surfactant carry out emulsification to oily sludge;
The first mixture after the emulsification is incubated in 60 ℃ of water-baths leaves standstill 20min, make it be layered as three-phase: oil reservoir, emulsion layer, mud layer;
Oil reservoir is separated with emulsion layer, oil reservoir reclaimed obtain oil product, the phosphoric acid (volume ratio that is oily sludge and phosphoric acid is 100: 6.67) that adds the 1mol/L that accounts for oily sludge volume 6.67% in emulsion layer obtains the second mixture, the second mixture is placed the vibrator of 70 ℃ of constant temperature, with the velocity fluctuation 10min of 200r/min;
Place 70 ℃ of water-baths to leave standstill 20min in the second mixture after the vibration, it is layered as: oil product layer and water layer, the recovery of oil product layer obtained oil product, reclaim the oil product that obtains with above-mentioned steps and merge;
Outward transport processing after the dehydration of the mud layer of sedimentation after the emulsification, the waste water that sewage produces together with breakdown of emulsion enters Sewage treatment systems and processes; Through above-mentioned emulsification, breakdown of emulsion, separation, so that originally be difficult for easier the sloughing of moisture of being removed by mechanical force in the oily sludge, and 95 ± 2% oil content is recovered in the oily sludge.
Claims (13)
1. the oil product biological recovery method of refinery's oily sludge, it may further comprise the steps:
(1), oily sludge, bio-surfactant and water are mixed to get the first mixture, the first mixture is heated, stirs, oily sludge is fully contacted with bio-surfactant, and the volume ratio of described oily sludge, water and bio-surfactant is 1: 1: 0.15;
(2), the first mixture after stirring is incubated and leaves standstill, make the first mixture be divided into oil reservoir, emulsion layer and mud layer;
(3), oil reservoir, emulsion layer and mud layer are separated, oil reservoir reclaimed obtain oil product, add acid in the emulsion layer to obtain the second mixture, the second mixture is heated, vibrate, make sourly fully to contact with emulsion layer;
(4), after vibration finishes, the second mixture through vibration is incubated, and leaves standstill and make it be divided into oil product layer and water layer, the oil product layer is reclaimed obtain oil product.
2. method according to claim 1, wherein, in the described step (1), oily sludge, bio-surfactant and water are mixed to get the first mixture, be heated to 50-70 ℃, speed with 100-200r/min stirs 10-400min, and oily sludge is fully contacted with bio-surfactant.
3. method according to claim 2, wherein, described bio-surfactant at first is mixed to get bio-surfactant solution with water, and then is mixed to get described the first mixture with described oily sludge.
4. method according to claim 1, wherein, described step (2) is: the first mixture insulation after will stirring is left standstill 20min at 60-70 ℃, makes the first mixture be divided into oil reservoir, emulsion layer and mud layer.
5. method according to claim 1, wherein, described step (3) is: oil reservoir, emulsion layer and mud layer are separated, the oil reservoir recovery is obtained oil product, add acid in the emulsion layer and obtain the second mixture, be heated to 50-70 ℃ and carry out the vibration of 10min with the speed of 100-200r/min, acid is fully contacted with emulsion layer.
6. method according to claim 1 or 5, wherein, in described step (3), described acid is hydrochloric acid and/or phosphoric acid.
7. method according to claim 6, wherein, the concentration of described acid is 1mol/L.
8. method according to claim 1 or 5, wherein, in described step (3), the volume ratio of described oily sludge and described acid is 100: 1.67-6.67.
9. method according to claim 6, wherein, in described step (3), the volume ratio of described oily sludge and described acid is 100: 1.67-6.67.
10. method according to claim 8, wherein, the volume ratio of described oily sludge and described acid is 100: 3.33.
11. method according to claim 9, wherein, the volume ratio of described oily sludge and described acid is 100: 3.33.
12. method according to claim 1, wherein, described step (4) is: after vibration is finished, to through the second mixture of vibration at 50-70 ℃ of insulation 20min, and leave standstill and make it be divided into oil product layer and water layer, the oil product layer is reclaimed obtains oil product.
13. method according to claim 1, wherein, described bio-surfactant is Glycolipids Biosurfactants via.
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| CN105481215B (en) * | 2015-10-15 | 2018-05-18 | 北京理工大学 | A kind of method using microorganism recycling oil-containing hazardous waste Crude Oil |
| CN112830650A (en) * | 2021-03-04 | 2021-05-25 | 榕知(杭州)信息技术有限公司 | Process for treating oily sludge generated in crude oil exploitation process by microorganisms |
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| CN1281736C (en) * | 2003-12-09 | 2006-10-25 | 中国科学院成都生物研究所 | Biology method for treating oily sludge |
| CN101088942B (en) * | 2006-06-14 | 2010-10-06 | 中国科学院生态环境研究中心 | Process of treating oil-containing sludge |
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