CN111204941A - Treatment process of bagged high-viscosity oily sludge - Google Patents
Treatment process of bagged high-viscosity oily sludge Download PDFInfo
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Abstract
The application provides a treatment process of bagged high-viscosity oily sludge, which comprises a bag breaking pretreatment stage, a primary cleaning stage, a centrifugal treatment stage, a secondary cleaning stage and an emulsified oil demulsification and solidification stage, and the treatment process is used for realizing efficient treatment of the high-viscosity oily sludge. After treatment, the oil-water interface can be detected in real time by the solid content on-line monitor, oil meeting the requirements is obtained, the oil not meeting the requirements is remixed with the next batch of oil samples for demulsification and purification, and the oil recovery rate of the process can reach more than 90%.
Description
Technical Field
The invention relates to the field of hazardous waste treatment, in particular to a treatment process of bagged high-viscosity oily sludge.
Background
The oily sludge belongs to HW08 specified hazardous waste, the hazardous waste has large production amount and high storage amount, and the oily sludge has the potential of resource recovery due to high oil content. The dangerous waste has large shape difference which is closely related to the quality of crude oil due to colloidThe density of the asphaltene is generally higher than that of normal crude oil, so that the heavy component content of the low-sludge in the tank is higher, and meanwhile, the heavy component in the sludge is increased due to volatilization of the light component in the sludge stacking process. A large part of crude oil purchased outside China is heavy crude oil, a large amount of heavy oil is produced in oil fields of Xinjiang and Liaohe at home, and a container for storing the oil products can generate a large amount of heavy oil sludge in a warehouse and a tank. Therefore, the proportion of the high-viscosity and high-viscosity oil sludge in the oily sludge generated in China is high. The oil sludge is in a semi-solid state, has the oil content of more than 30 percent, has higher oil condensation point, even contains asphaltene with ultrahigh molecular weight, and the asphalt is in CCL4In addition, the surface of particles in the oil sludge adsorbs a large amount of colloid asphaltene, the viscous resistance is large, the density of oil, water and solid phases is close, and the particle size range of a solid phase is large, so that the extraction method and the mechanical centrifugal separation have large limitations. Another characteristic of this kind of fatlute is exactly that the bonding ability is strong, often causes equipment sieve mesh, discharge gate, agitating unit to bond and stops up, if contain cotton yarn, this kind of problem is more serious during the braided bag, often becomes the biggest factor that restricts equipment normal operating.
In the oil-water separation process, free oil is easy to separate, adsorbed oil can be partially separated under the action of a medicament and an external force, but bound oil is extremely difficult to separate, most of the oil is asphaltene, the polar head of the asphaltene is bound on the surface of solid-phase particles, and the part of oil often causes unqualified treatment or the solid-phase oil content is high. Meanwhile, a large amount of solid phase components still exist in the oil phase of the oil sludge after oil-water-solid three-phase separation, and the components have small particle size, adsorb the asphaltene on the surface, adsorb the asphaltene on the oil-water interface position and play a role of an emulsification reinforcing agent. Because of the existence of a large amount of solid phases, a large amount of black impurities are suspended in a water phase in the purification process, so that an oil-water interface is fuzzy and is not beneficial to separation control.
Disclosure of Invention
The invention aims to provide a treatment process of bagged high-viscosity oily sludge, which aims to solve the problems in the background art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a treatment process of bagged high-viscosity oily sludge comprises the following steps:
s1, pressing oil-containing sludge to be treated to a preset thickness based on an extrusion device;
s2, puncturing based on a hollow spray head to puncture an oil sludge bag, detecting whether a hard object is met or not based on a pressure sensor configured on the hollow spray head in the puncturing process, stopping puncturing if the hard object is met, moving the hollow spray head to a cleaning position, spraying a hot cleaning solution added with a cleaning agent through the hollow spray head for a first preset time T1, and repeating S1 until oil sludge is dispersed in the cleaning solution;
s3, feeding the punctured silk bags and the large hard materials into a vibrating screen to separate the large hard materials from the silk materials, feeding the separated silk materials into a cleaning machine, and cleaning and removing adhered oil sludge on the surfaces of the silk materials under the action of high temperature and a cleaning agent;
s4, washing water for washing the oil sludge bag and oil sludge under washing by using a washing device;
s5, centrifuging water cleaned by the cleaning device based on a three-phase centrifugal device, sending the centrifuged oil sludge phase into an ultrasonic cleaner for secondary ultrasonic cleaning for a third preset time T3, wherein the frequency of the ultrasonic cleaner is 28 KHZ;
and S6, collecting the oil phase collected after centrifugation and ultrasonic treatment based on a de-solidification purification tank, and performing de-solidification and demulsification treatment.
Preferably, the step S1 includes conveying the oily sludge to be treated from a feeding disc to a crushing and dispersing device, and extruding the oily sludge to a preset thickness of 5-10cm by using an extruding device.
Preferably, the pressing device is provided with a plurality of holes for pressing the plate, and a retractable hollow spray head is arranged in the holes.
Preferably, the temperature of the hot washing solution of S2 is 85 ℃ or higher.
Preferably, the hollow acupuncture probe is made of high-strength alloy steel and is provided with a pressure sensor, and when the pressure sensor exceeds a preset value, the hollow acupuncture probe is judged to encounter a hard object.
Preferably, the hollow acupuncture probe judges that a hard object is encountered when the pressure sensor exceeds 0.1 mpa.
Preferably, the S4 is cleaned for a second preset time T2.
Preferably, in S6, the discharge port of the solid removal purification tank is equipped with a water content meter for online monitoring of the water content and solid content in the discharged liquid, and when the water content is lower than 5% and the solid content is lower than 0.5%, the discharge port is switched to the clean oil tank for storage.
Preferably, the cleaning agent in S2 comprises, by mass, 20-30% of sodium dodecyl diphenyl oxide disulfonate, 20-40% of octylphenol polyoxyethylene ether, 5-8% of fatty alcohol polyoxyethylene ether, 3.5-6.8% of alcohol ether carboxylate, 0.5-2.5% of propylene glycol block polyether, 0-0.5% of DTPA chelating agent and water.
Advantageous effects
Compared with the prior art, the treatment process of the bagged high-viscosity oily sludge provided by the embodiment of the application comprises bag breaking pretreatment, primary cleaning, centrifugal treatment, secondary cleaning treatment and emulsified oil demulsification and solidification removal treatment. Wherein the secondary cleaning adopts ultrasonic cleaning. The demulsification and solidification removal treatment of the emulsified oil can automatically transfer the obtained solid in the emulsified oil to a water phase after wetting and reversing, and the solidification removal purification tank provided with the online monitor for water content and solid content in the oil can detect an oil-water interface in real time, thereby being beneficial to separation control.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate exemplary embodiments, features, and aspects of the invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 is a schematic flow diagram of a process for treating oily sludge according to an embodiment of the present invention;
FIG. 2 is a diagram showing the results of XRD analysis of a sample after cleaning and degreasing in a muffle furnace (450 ℃ C.) according to an embodiment of the present invention.
Detailed Description
Various exemplary embodiments, features and aspects of the present invention will be described in detail below with reference to the accompanying drawings. In the drawings, like reference numbers can indicate functionally identical or similar elements. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The embodiment of the application provides a treatment process of bagged high-viscosity oily sludge, which comprises a bag breaking pretreatment stage, a primary cleaning stage, a centrifugal treatment stage, a secondary cleaning stage and an emulsified oil demulsification and solidification stage, wherein the bag breaking pretreatment stage is used for separating large hard impurities and filamentous impurities with the particle size larger than 20mm, and the treatment process can realize high-efficiency treatment of the high-viscosity oily sludge.
The treatment process of the oily sludge proposed in the present application is described below with reference to fig. 1, which comprises:
the bag-breaking pretreatment stage comprises the following steps,
s1, pressing oily sludge (hereinafter referred to as oil sludge) to be treated to a preset thickness (for example, 5-10 cm) based on an extrusion device, namely conveying the oily sludge to be treated to a crushing and dispersing device from a feeding disc, extruding a sludge bag or sludge (for example, up/down extrusion and left/right extrusion) by utilizing the plasticity of semisolid oil sludge to press the oily sludge to the preset thickness (for example, 5-10 cm),
s2, puncturing the oil sludge bag based on a hollow spray head (also called a needle head), detecting whether a hard object is met based on a pressure sensor of the hollow spray head in the puncturing process,
if the hard object is met, the puncture is stopped, the hollow spray head moves to the cleaning position (for example, the hollow spray head body is buried in the oil sludge, the oil sludge needle is dispersed through the high-temperature high-pressure solution), the hot cleaning solution added with the cleaning agent is sprayed through the hollow spray head for a first preset time T1 (after the operation is finished, the hollow spray head retracts into the steel plate hole), and S1 is repeated until the oil sludge is dispersed in the cleaning solution.
Wherein the temperature of the hot washing solution is above 85 ℃ (such as 90 ℃) and the pressure is 5-10 mpa, the hot washing solution is sprayed for 5s, and then the side face of the oil sludge bag is extruded to the thickness of 5-10cm by utilizing the hollow spray head to needle the oil sludge. The hollow acupuncture probe adopts high-strength alloy steel and has the characteristics of wear resistance and corrosion resistance. The device is provided with a pressure sensor, when the pressure sensor exceeds a preset value (such as 0.1mpa), a hard object is judged to be met, the sprayed oil-sludge-containing washing liquid can be recycled, and the proportion of the washing liquid to the oil sludge is 4: 1 to 6: 1, fine adjustment is carried out according to the oil sludge solid content. Preferably, the steel plate of the extrusion device is used for extrusion, the telescopic needle head is arranged in the hole of the steel plate, after the steel plate is extruded to a certain thickness, the needle head protrudes out, and the oil sludge bag is punctured through the needle head. The pressure sensor is located on the upper part of the needle.
And S3, feeding the needled silk bag and the large hard materials into a vibrating screen to separate the large hard materials from the silk materials, feeding the separated silk materials into a cleaning machine, and cleaning to remove oil sludge adhered to the surfaces of the silk materials under the action of a cleaning agent at high temperature. The cleaning machine (such as a roller cleaning machine) is added with 120kg of silk bag weight at a time, the volume of a rotating drum is 1.2 cubic, the washing rotating speed is 32r/min, the motor power is 11kw, and the dehydration rotating speed is 670 r/min. The equipment has the double effects of cleaning, dewatering and drying. In one embodiment, after the silk bags enter the cleaning machine, 5 times of clear water and 1.5% of cleaning agent are added, the silk bags are cleaned twice, 10 minutes are carried out each time, then the silk bags are dehydrated and dried, the time of one batch is 30 minutes, 2000 woven bags can be cleaned by one machine every day, and 2.8kg of oil sludge is remained in each oil sludge bag.
And S4, washing the water for washing the sludge bag and the sludge under washing by using a washing device. Preferably, the washing is performed by stirring (e.g. at a rotation speed of 100r/min), the washing is performed for a second predetermined time T2 (e.g. 30min depending on the application),
and S5, centrifuging water cleaned by the cleaning device based on the three-phase centrifugal device and sending the centrifuged oil sludge phase into an ultrasonic cleaner for secondary ultrasonic cleaning. The ultrasonic cleaner utilizes the cavitation, thermal and mechanical action of ultrasonic waves. And (3) further cleaning the oil sludge phase, wherein most of free oil and attached oil are separated, but a large amount of bound oil still remains, the oil products are mainly asphaltenes, the molecular weight of the oil products is chemically bonded with the particle surface, and the oil content is 8-15%. Cavitation, namely, the ultrasonic wave can rapidly break the original bubbles or the new bubbles under the action of certain frequency, the internal temperature of the bubbles can reach thousands of degrees centigrade at the moment of breaking, the pressure reaches thousands of atmospheric pressures or even tens of thousands of atmospheric pressures, the acceleration generated in the breaking process is dozens of times of the acceleration of gravity, local high temperature and high pressure are generated, the oxidation-reduction reaction is promoted, and the high molecular substance is depolymerized, so that the glued asphaltene molecular bonds are broken, and the oil removal rate is improved. The ultrasonic cleaner is characterized in that the frequency is 28KHZ, the power is 50kw, the temperature is 90 ℃, the temperature is kept for a third preset time T3 (for example, 20min), at the moment, the chemical bonding bonds are broken through the cavitation action, meanwhile, a part of asphaltene is broken, the molecular weight is reduced, the oil and the solid are separated, then, based on the emulsification action of the cleaning agent, the oil phase is quickly emulsified into an oil-in-water emulsion after being separated from the surface of the solid phase, so that the oil and the solid are separated, and through the design, the oil content is reduced to be below 2%.
The oil phase collected after centrifugation and ultrasonic treatment is subjected to de-solidification demulsification treatment, the water content of the oil phase is 30-70%, the solid content is 2-6%, the particle size of the solid phase is less than 20 microns, if solid-liquid separation cannot be realized by means of centrifugation, oil sludge particles with the particle size of less than 10 microns and natural surfactants such as asphaltene and the like are adsorbed on the surface, the particles are adsorbed between oil-water interfaces and act like an emulsification enhancer, and meanwhile, the cleaned oil phase has heavy components higher than 30%, the viscosity of an oil product is high, the condensation point exceeds 90 ℃, and the density is 0.92-0.98 g/ml, so that the de-solidification separation of the oil phase is extremely difficult.
The following processing steps, after S5,
and S6, based on the combined treatment stage of chemical demulsification, solidification and high-temperature sedimentation and purification, treating the oil phase collected after centrifugation and ultrasonic treatment based on the combined process of chemical demulsification, solidification and high-temperature sedimentation and purification. The method comprises the steps of collecting an oil phase collected after centrifugation and ultrasonic treatment by using a de-solidification purification tank, performing de-solidification demulsification treatment, and adding a de-solidification demulsifier into the de-solidification purification tank, wherein the de-solidification demulsifier adopts the principle of strong wetting reversal, demulsification dehydration and high-temperature sedimentation assistance. And a water content tester is arranged at the discharge port of the purification tank and used for monitoring the water content and the solid content in the discharged liquid on line, and when the water content is lower than 5 percent and the solid content is lower than 0.5 percent, the discharge port is switched to the oil purification tank for storage. The mechanism is that after the oil phase particles are wetted and reversed, the surfaces of the oil phase particles are changed from lipophilicity to hydrophilicity, the macromolecules in the medicament play a role of adsorption bridging, the particles are adsorbed around the macromolecules and automatically migrate from the oil phase to the water phase under the action of gravity, and the small water droplets are agglomerated into large water droplets under the action of the demulsifier of the water-in-oil emulsion and are separated by sedimentation under the action of gravity. The wetting reversal speed of the particle surface and the dehydration speed are matched and cooperated with each other, and the dehydration speed is faster than the particle migration speed, so that the phenomena of low water content and high solid content are caused.
The above treatment process is described below with reference to specific examples:
example 1 the sludge was a bunker-clean sludge and the crude oil was from heavy crude oil from venezuela, south america.
⑴ the indexes of oil-water-solid three phases in the oil sludge are as follows:
table 1 ⑵ oil phase four component test data are:
TABLE 2 separation results of four components of crude oil
The oil phase was further tested for density 0.978g/ml, viscosity 30000cp (20 ℃).
⑶ solid phase composition testing
The cleaned and degreased sample was calcined in a muffle furnace (450 ℃) for 4 hours and then subjected to XRD analysis and XRF analysis, and the results are shown in FIG. 2 and Table 3, respectively. Combining the results of the two results, it was confirmed again that the solid phase in the sample was iron oxide and quartz, wherein the content of iron oxide was 93.86%.
Substance(s) | Na2O | MgO | Al2O3 | SiO2 | Cl | K2O | CaO |
Content (%) | --- | 0.042 | 0.077 | 1.171 | 0.064 | 0.041 | 0.407 |
Substance(s) | MnO | Fe2O3 | |||||
Content (%) | 0.443 | 93.86 |
Table 3 XRF results for sample No. 22 after oil removal calcination
⑷ solid phase particle size test
The residual solid phase of the oily sludge after solvent extraction is subjected to a laser particle size test, wherein the particle size of more than 20 mu m accounts for 59 percent.
In conclusion, the oil sludge is high-solid, high-viscosity and high-consistency oil sludge, the particle size of the oil sludge is less than 20 microns and accounts for 41%, and if the partial particle size is directly subjected to centrifugal separation, large particles with viscous resistance have small particle size, so that oil-water-solid three phases are difficult to separate. The oil sludge contains 36% of oil and 39% of solids, has a large resource regeneration potential, has a small reduction space, and has an oil content reduced to within 2% after being treated by the treatment process, so that the harmfulness is reduced, and a foundation is laid for further harmless treatment. In the treatment mode, the oil sludge treatment point is designed according to the daily treatment of 200t, and the oil sludge is packaged by woven bags, wherein each bag is about 25kg, and the oil sludge test data is combined. The treatment process flow is as follows: bag breaking pretreatment, oil bag cleaning, primary cleaning of oil sludge, oil-water-solid three-phase centrifugal separation, secondary cleaning (ultrasonic cleaning) of a water-containing slag phase, three-phase centrifugal separation of the water-containing slag phase, and emulsified oil solid removal purification treatment.
The method comprises the steps of bag breaking pretreatment, primary cleaning, centrifugal separation, secondary ultrasonic cleaning and the like. (treatment of 6 samples, Nos. 1 to 6.)
Table 4 is a statistical table of the treatment of 6 samples
The equipped equipment comprises 1 needle bag breaking machine, 4 silk bag cleaning agents, 1 primary cleaning pry (50m3), 1 three-phase centrifuge (100t/h), 1 secondary ultrasonic cleaning machine (50m3), and a solid removal purification tank 4 (70m3)
The one-time cleaning process parameters are selected, wherein the temperature is 95 ℃, and the solid-liquid ratio is 1: 5, stirring speed is 100r/min, and cleaning time is 45 min.
In the centrifugal treatment, a horizontal screw centrifuge is adopted, the rotating speed is 2800r/min, and the treatment capacity is 10 tons/h.
In the treatment of the ultrasonic cleaning machine, the centrifuged water-containing slag phase enters the ultrasonic cleaning machine, the adopted frequency is 28KHZ, the power is 50kw, the temperature is 90 ℃, the duration is 20 minutes, and the water-containing slag phase enters the horizontal screw centrifuge again at the rotating speed of 3000 r/min.
The field daily treatment capacity is 200 tons, and through tests, the data after three-phase separation of oil sludge and water are obtained as follows:
the oil phase is cleaned and separated for one time for 180t, the oil content is 32.2 percent, the pure oil is 58t, the solid content is 2.5 percent (the solid content is 4.375t), and the water content is 100.6 tons; 320t of water-containing slag phase, 20 percent of solid and 64 tons of solid phase;
and (3) carrying out secondary cleaning, adding 960t of clean water, and separating 55 tons of emulsified oil (10 tons of pure oil), 160 tons of water-containing solid phase, 60 percent of water and 65 tons of absolutely dry solid phase (the oil content is 2 percent, and the oil content is 1.3 t).
The primary cleaning and the secondary cleaning jointly generate emulsified oil 235t, the total water content is 70.4%, and the solid content is 2.5%; adding 0.1% of de-solidification demulsifier, settling for 5h at the temperature of 97 ℃, discharging and separating water and oil through a discharge port, and judging an oil-water interface through an aqueous solid content online tester. Tested as shown in the following table 5
TABLE 5
According to the data, the upper oil phase meets the heavy fuel oil standard (the solid content is less than 0.5 percent), the middle oil phase is slightly poor, and the oil phase is remixed with the next batch of oil samples for demulsification and purification, so that the oil recovery rate can reach 94 percent.
The treatment process of the bagged high-viscosity oily sludge is characterized in that during cleaning, a cleaning agent (such as the cleaning agent disclosed in the application No. 2019110499837) based on oil-water-solid three-phase separation is adopted, and the cleaning agent comprises, by mass, 20-30% of sodium dodecyl diphenyl ether disulfonate, 20-40% of octylphenol polyoxyethylene ether, 5-8% of fatty alcohol polyoxyethylene ether, 3.5-6.8% of alcohol ether carboxylate, 0.5-2.5% of propylene glycol block polyether, 0-0.5% of DTPA chelating agent and water.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.
Claims (9)
1. The treatment process of the bagged high-viscosity oily sludge is characterized by comprising the following steps of:
s1, pressing oil-containing sludge to be treated to a preset thickness based on an extrusion device;
s2, puncturing based on a hollow spray head to puncture an oil sludge bag, detecting whether a hard object is met or not based on a pressure sensor configured on the hollow spray head in the puncturing process, stopping puncturing if the hard object is met, moving the hollow spray head to a cleaning position, spraying a hot cleaning solution added with a cleaning agent through the hollow spray head for a first preset time T1, and repeating S1 until oil sludge is dispersed in the cleaning solution;
s3, feeding the punctured silk bags and the large hard materials into a vibrating screen to separate the large hard materials from the silk materials, feeding the separated silk materials into a cleaning machine, and cleaning and removing adhered oil sludge on the surfaces of the silk materials under the action of high temperature and a cleaning agent;
s4, washing water for washing the oil sludge bag and oil sludge under washing by using a washing device;
s5, centrifuging water cleaned by the cleaning device based on a three-phase centrifugal device, sending the centrifuged oil sludge phase into an ultrasonic cleaner for secondary ultrasonic cleaning for a third preset time T3, wherein the frequency of the ultrasonic cleaner is 28 KHZ;
and S6, collecting the oil phase collected after centrifugation and ultrasonic treatment based on a de-solidification purification tank, and performing de-solidification and demulsification treatment.
2. The process for treating bagged high-viscosity and high-viscosity oily sludge according to claim 1, wherein the step S1 comprises conveying the oily sludge to be treated from a feeding tray to a crushing and dispersing device, and extruding the oily sludge to a preset thickness of 5-10cm by using an extruding device.
3. The process for treating bagged high-viscosity and high-viscosity oily sludge according to claim 1, wherein the extrusion plate of the extrusion device is provided with a plurality of holes, and a telescopic hollow spray head is arranged in the holes.
4. The process for treating bagged high-viscosity and high-viscosity oily sludge according to claim 1, wherein the temperature of the hot washing solution in the S2 is more than 85 ℃.
5. The treatment process of the bagged high-viscosity oily sludge, according to claim 1, wherein the hollow needling probe is made of high-strength alloy steel and is provided with a pressure sensor, and when the pressure sensor exceeds a preset value, the bagged high-viscosity oily sludge is judged to encounter a hard object.
6. The process for treating bagged high-viscosity and high-viscosity oily sludge according to claim 5, wherein the hollow acupuncture probe judges that a hard object is encountered when the pressure sensor exceeds 0.1 mpa.
7. The process for treating bagged high-viscosity and high-viscosity oily sludge according to claim 1, wherein the washing in S4 is performed for a second preset time T2.
8. The process for treating bagged high-viscosity and high-viscosity oily sludge as claimed in claim 1, wherein in S6, a water content tester is installed at the discharge port of the de-solidification purification tank for on-line monitoring of the water content and the solid content in the discharged liquid, and when the water content is lower than 5% and the solid content is lower than 0.5%, the discharge port is switched to the oil purification tank for storage.
9. The process for treating bagged high-viscosity and high-viscosity oily sludge as claimed in claim 1, wherein the cleaning agent in S2 comprises, by mass, 20-30% of sodium dodecyl diphenyl ether disulfonate, 20-40% of octylphenol polyoxyethylene ether, 5-8% of fatty alcohol polyoxyethylene ether, 3.5-6.8% of alcohol ether carboxylate, 0.5-2.5% of propylene glycol block polyether, 0-0.5% of DTPA chelating agent and water.
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CN115007623A (en) * | 2022-05-13 | 2022-09-06 | 大连理工大学盘锦产业技术研究院 | Method and system for treating oil-containing sludge and petroleum-polluted soil |
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