CN112661384B - Method for reconstructing high-water-content oil sludge - Google Patents
Method for reconstructing high-water-content oil sludge Download PDFInfo
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Abstract
The invention is applicable to the field of high-water-content oil sludge treatment, and provides a method for reconstructing high-water-content oil sludge, which comprises the following steps: step S1: adding the high water-containing oil sludge and a phase transfer agent into a mixer for uniform mixing to obtain an unstable high water-containing oil sludge Pickering emulsion system; step S2: the unstable high water-bearing oil-mud Pickering emulsion system is subjected to water and oil phase transfer through pipeline type shearing equipment, the water and the oil are transferred into a phase transfer agent to be dissolved together, and suspended matters in the unstable high water-bearing oil-mud Pickering emulsion system are also converted into small particles with uniform sizes from different particle sizes under the action of the pipeline type shearing equipment, so that the unstable high water-bearing oil-mud Pickering emulsion system is converted into an oil system suspended matter, namely the high water-bearing oil mud is reconstructed. After the high-water-content oil sludge is reconstructed by the system, the subsequent separation and drying treatment is more facilitated, and the reduction effect is more obvious.
Description
Technical Field
The invention belongs to the field of high-water-content oil sludge treatment, and particularly relates to a method for reconstructing high-water-content oil sludge.
Background
In the process of treating wastewater in an oil refinery, a large amount of bottom sludge of an oil separation tank, floating slag of an air flotation tank, residual activated sludge of a biochemical tank and the like can be generated, wherein the floating slag of the air flotation tank occupies the largest proportion and comprises suspended solid, emulsified oil and micro-bubbles, the sludge is suspended in the wastewater, and the sludge is usually treated by a method of carrying out concentration in a sludge concentration tank, carrying out centrifugal dehydration treatment and then carrying out landfill treatment or recycling, burning and the like. The oil sludge after the preliminary centrifugal dehydration by the centrifugal machine has complex organic matter components, high water content, good stability and large processing difficulty, still belongs to high-water-content oil sludge, the oil content of the oil sludge is generally 5-10 percent, the water content of the oil sludge is 60-85 percent, and the oil sludge additionally contains about 10-15 percent of solid matters (mud, sand and the like). The interfacial film existing between the water and oil interfaces prevents coalescence between water drops/oil drops, and is very stable due to the surface active substances (including colloid and asphaltene) existing between the interfaces. There are two different types of emulsions in sludge: an O/W type emulsion is an oil-in-water type emulsion with water as a continuous phase and water-insoluble organic liquid as a dispersed phase; the other is water-in-oil emulsion with water as dispersed phase and water insoluble organic liquid as continuous phase, i.e. W/O type emulsion. In addition, the solid materials may be coated with multiple emulsions such as water-in-oil (W/O/W) or oil-in-water (O/W/O) because of their different shapes and sizes. It is because of its high oil and water content, high emulsification degree, high viscosity, and difficult solid-liquid separation, which makes the high water content oil mud more difficult to handle.
Various oil sludge treatment technologies have been developed at present at home and abroad, and mainly include a landfill method, an incineration method, a solvent extraction method, a drying and reducing method and the like. The landfill method is most adopted at present, a large amount of land resources are occupied, and the high-water-content oil sludge cannot be treated, so that the resources are wasted, and the environment is polluted. The incineration method consumes much energy because the water content in the high-water-content oil sludge is higher than 80%, and simultaneously generates a large amount of waste gas, so that the equipment investment and the operating cost are also higher. The solvent extraction method uses a large amount of extracting agents in the solvent extraction process, so that the cost is high, and the equipment maintenance cost, depreciation cost and treatment cost are high in the process; the drying decrement method is a pure decrement method, and because water in the oil sludge is mainly in an emulsified state, the dehydration is difficult, and the problems of flammability, explosiveness, easy coking and blockage of equipment also exist. Whichever method is adopted for the treatment, the lower the water content of the sludge, the better. The water content is low, the sludge reprocessing amount is small, and the energy consumption loss is small if the subsequent resource treatment is carried out; if the subsequent landfill is carried out, the cost is lower; and vice versa. With the stricter environmental protection laws and regulations of countries in the world, the requirements of reduction, stabilization and resource treatment of oil sludge are higher and higher.
Disclosure of Invention
The invention aims to provide a method for reconstructing high-water-content oil sludge, which is more beneficial to subsequent separation and drying treatment after the high-water-content oil sludge is reconstructed by a system, has more remarkable reduction effect, and can reduce the pollution influence of the high-water-content oil sludge on the environment; and secondly, recovering oil and water in the high-water-content oil sludge to achieve the recycling value of resources.
The invention is realized by a method for reconstructing high-water-content oil sludge, which comprises the following steps:
step S1: adding the high water-containing oil sludge and a phase transfer agent into a mixer for uniform mixing to obtain an unstable high water-containing oil sludge Pickering emulsion system;
step S2: and (2) transferring water and an oil phase of the unstable high-water-content oil-sludge Pickering emulsion system prepared in the step (S1) through pipeline type shearing equipment, transferring the water and the oil into a phase transfer agent to be mutually dissolved, and converting suspended matters in the unstable high-water-content oil-sludge Pickering emulsion system from different particle sizes into small particles with uniform sizes under the action of pipeline type shearing equipment so as to convert the unstable high-water-content oil-sludge Pickering emulsion system into an oil system suspended matter, namely reconstructing the high-water-content oil-sludge system.
The invention further adopts the technical scheme that: the specific step of the step S1 is to add the high water-containing oil sludge and 35-85% of phase transfer agent by weight or volume ratio of the high water-containing oil sludge into a mixer, and uniformly mix the uneven high water-containing oil sludge and the phase transfer agent at room temperature to 80 ℃ and at the stirring speed of 80-150 rpm to obtain an unstable high water-containing oil sludge Pickering emulsion system.
The further technical scheme of the invention is as follows: the more specific step of the step S1 is to add the high water-containing oil sludge and the phase transfer agent with the weight ratio or the volume ratio of 45 percent of the high water-containing oil sludge into a mixer, and uniformly mix the uneven high water-containing oil sludge and the phase transfer agent at 50 ℃ and the stirring speed of 100rpm to obtain the unstable high water-containing oil sludge Pickering emulsion system.
The further technical scheme of the invention is as follows: the concrete steps of the step S2 are that the unstable high water-bearing cement Pickering emulsion system prepared in the step S1 is subjected to phase transfer of water and oil in the unstable high water-bearing cement Pickering emulsion system through an in-line high shear dispersion emulsifying machine or high pressure homogenizer or homogenizing emulsifying machine under the conditions that the working temperature is between room temperature and 65 ℃, the working time is between 1 and 10min, the shearing rate is between 2500 and 12000rpm, the standard speed of a rotor is between 20 and 70m/S, and the working pressure is between normal pressure and 15.0MPa, the water and the oil are transferred into a phase transfer agent to be mutually dissolved together, and suspended matters in the unstable high water-bearing cement Pickering emulsion system are also converted into small particles with uniform sizes from the particles under the action of the high shear dispersion emulsifying machine or high pressure homogenizer or homogenizing emulsifying machine, so that the unstable high water-bearing cement Pickering emulsion system is converted into the oil suspension, namely the high water-bearing cement Pickering emulsion system is reconstructed.
The invention further adopts the technical scheme that: the phase transfer agent comprises 10-80 wt% of alcohol Rm- (OH) n or low-carbon alcohol ether solvent, wherein m =1-4, n =1-3, and 20-90 wt% of aromatic hydrocarbon solvent or mineral oil.
The further technical scheme of the invention is as follows: the phase transfer agent also comprises a surfactant which promotes the mutual solubility of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or mineral oil and plays roles of demulsification, oil displacement and auxiliary phase transfer in high water-containing oil sludge, and the weight percentage of the surfactant is 0.2-2% of the total weight of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or mineral oil.
The invention further adopts the technical scheme that: the phase transfer agent also comprises organic phenol, amine antioxidant and polymerization inhibitor for preventing high water-containing oil sludge from coking and scaling in the process of drying and recovering oil and water, and the weight percentage of the organic phenol, the amine antioxidant and the polymerization inhibitor is 0.2 to 1 percent of the total weight of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mineral oil.
The further technical scheme of the invention is as follows: the weight percentage of the alcohol Rm- (OH) n or the low-carbon alcohol ether solvent is 40-65%; the weight percentage of the aromatic hydrocarbon solvent or the mineral oil is 35 to 60 percent.
The further technical scheme of the invention is as follows: the alcohol Rm- (OH) n is one or more of ethanol, isopropanol, ethylene glycol or diethylene glycol, and the low-carbon alcohol ether solvent is one or more of ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclohexanediol monomethyl ether or ethylene glycol butyl ether; the aromatic hydrocarbon solvent is one or more of benzene, toluene, mixed xylene, mixed trimethylbenzene, tetramethylbenzene or ethylbenzene, and the mineral oil is one or more of gasoline, diesel oil, raffinate oil or aromatic hydrocarbon solvent oil.
The invention further adopts the technical scheme that: the surfactant comprises one or more of propylene glycol block polyether, alkylphenol polyoxyethylene ether, castor oil/hydrogenated castor oil polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, phenol-amine-aldehyde resin polyoxypropylene polyoxyethylene ether or acrylamide modified copolymer; the organic phenol, the amine antioxidant and the polymerization inhibitor are one or more of p-phenylenediamine, hydroquinone, p-tert-butyl catechol or p-benzylaminophenol.
The invention has the beneficial effects that: the effect of oil sludge reduction is achieved by reconstructing a high water-bearing oil sludge Pickering emulsion liquid system into an oil suspension system, the problem of recontamination of acidification tempering discharged hydrogen sulfide gas and the defects of poor effect and high energy consumption of other tempering methods are effectively eliminated, the phase transfer agent can be recycled, the drying effect is good, and the method has the characteristics of simplicity in operation, low safety risk, low energy consumption and low investment, and the effects of reduction and recycling are remarkable.
Drawings
FIG. 1 is a diagram of the stabilization mechanism of a Pickering emulsion provided by an embodiment of the invention;
FIG. 2 is a simulation diagram of the reconstruction effect of the architecture provided by the embodiment of the present invention;
FIG. 3 is a comparison graph of microscopic observation results before and after reconstitution of a high water content oil sludge provided by an embodiment of the invention;
fig. 4 is a block flow diagram of a method for reconstructing high-water content oil sludge according to an embodiment of the present invention.
Detailed Description
The high-water-content oil sludge is a complex system formed by mixing water, solid particles and oil, wherein organic matter components are complex, the water content is high, the stability is good, the treatment difficulty is high, the water content is 60-80%, the oil content is generally 8-10%, and about 10-15% of solid matters (mud, sand, biomass and the like) are contained.
The Pickering emulsion is an emulsion obtained by using ultrafine solid particles as an emulsifier, and the solid powder used as the emulsifier includes clay, silica, metal hydroxide, graphite, carbon black, and the like. The type of emulsion obtained depends on which phase preferentially wets the solid particles, usually one phase that preferentially wets the solid particles is the external phase. If the solid particles are wetted by the oil phase, the emulsion is W/O; conversely, if the solid particles are wetted by the aqueous phase, the emulsion is of the O/W type.
The solid components in the high water content oil sludge mainly comprise silicon dioxide, aluminum oxide, metal oxides, carbon powder and the like in a catalyst used in an oil refining process, the properties of the solid particles used as an emulsifier in the Pickering emulsion are similar, the solid particles are more similar to the Pickering emulsion due to surface active substances (including colloid and asphaltene) existing between solid interfaces of the oil sludge, and the emulsion in the oil sludge has two different types: an O/W type emulsion is an oil-in-water type emulsion with water as a continuous phase and water-insoluble organic liquid as a dispersed phase; the other is water-in-oil emulsion with water as dispersed phase and water insoluble organic liquid as continuous phase, i.e. W/O type emulsion. Therefore, the present patent is different from the present patent in that the oil refinery high water content oil sludge is studied as a Pickering emulsion system, but the solid content in the oil sludge is different in shape and size, the solid content is higher, and multiple emulsions such as water-in-oil-in-water (W/O/W) or oil-in-water-in-oil (O/W/O) may be adsorbed therein, so the system is more complicated than the pure Pickering emulsion system, so we refer to the high water content oil sludge as: pickering like emulsion system.
Numerous researches indicate that two main viewpoints mainly exist in the stabilization mechanism of Pickering emulsion, one viewpoint is that the stability of the Pickering emulsion is related to a protective film formed by particles adsorbed on an oil-water interface, namely the theory of a solid particle interface film is also called as a mechanical barrier theory and is shown in figure 1 (a), the theory is that solid particle emulsifying agents are closely distributed on the surface of emulsion liquid drops, a layer of compact film is formed between oil/water interfaces, and collision coalescence among the emulsion liquid drops is spatially blocked; meanwhile, the particle emulsifier is adsorbed on the surface of the liquid drop, the mutual repulsion between the liquid drops of the emulsion is increased, the stability of the emulsion is improved under the combined action of the particle emulsifier and the liquid drops of the emulsion, and otherwise, the stability of the emulsion can be reduced; another view is that the formation of a three-dimensional grid structure in the system of the particles increases the viscosity of the emulsion continuous phase, namely a three-dimensional viscoelastic particle network mechanism: the interactions between colloidal particles adsorbed at the oil/water interface are mainly electrostatic, dipole, van der waals, hydrophobic and DLVO forces. When the particles are adsorbed at the oil/water interface, the electrostatic, hydrophobic and DLVO repulsion forces between the particles act through the aqueous phase, the dipolar forces act through the oil phase, and the van der waals forces act through both the aqueous and oil phases. Researches find that a stable Pickering emulsion system has a three-dimensional network structure, so that the layering phenomenon of the emulsion can be effectively slowed or inhibited, liquid drops can be prevented from approaching and colliding, and the coalescence phenomenon among emulsion liquid drops is reduced, as shown in figure 1 (b).
The main factors influencing the stability of the Pickering emulsion liquid system include 3 parameters of interfacial tension, three-phase contact angle and particle size of the emulsion system:
water-wetting particles can stabilize oil-in-water (o/w) emulsion systems, while oil-wetting particles can be used to stabilize water-in-oil (w/o) systems. Excessively hydrophilic or lipophilic solid particles tend to remain more in the aqueous or oil phase and are not effective in stabilizing the emulsion. The three-phase contact angle of a solid particle is closely related to the interfacial desorption energy of the solid particle. The desorption energy of solid particles refers to the energy consumed for transferring a solid particle adsorbed on an oil-water interface into a solvent phase, and the higher the desorption energy is, the more stable the emulsion is. The desorption energy is an important parameter for representing the stability of an emulsion system, and the desorption energy of solid particles is related to the size of the particles, the position of the solid particles on an interface and the interfacial tension, as shown in formula (1):
ΔG remove =πR 2 σ(1±cosθ)2 (1)
in the formula,. DELTA.G remove Desorption energy for solid particles, J; r is the radius of solid particles, nm; sigma is interfacial tension N/m; theta is the solid particle three-phase contact angle, DEG; theta<At 90 degrees, the symbol in brackets is "-", and the particles are hydrophilic and are easy to form o/w emulsion; theta>At 90 deg.C, the symbol in parentheses is "+", and the particles are lipophilic and easily form w/o emulsion.
As can be seen from the formula (1), when theta is approximately equal to 90 degrees, the desorption energy value is the largest, the formed emulsion has the strongest stability, theoretically, the particles can form w/o emulsion and o/w emulsion, and the type of the emulsion can be determined by the volume ratio of oil phase to water phase.
From the above formula, 3 parameters of interfacial tension, three-phase contact angle and particle size of the emulsion system can change the stability of the Pickering emulsion.
Taking oil refinery high water content oil sludge as a Pickering emulsion system, knowing from formula (1) that the stability of the high water content oil sludge emulsion can be reduced by reducing the desorption energy of solid particles in the high water content oil sludge, according to the Pickering emulsion stabilization mechanism, a special phase transfer agent is developed, and by utilizing the extremely strong charge reduction performance and the amphiphilic performance of the special phase transfer agent, the radius R of the solid particles in the high water content oil sludge, the three-phase contact angle theta of the solid particles, the interfacial tension sigma and the oil-water phase volume ratio are changed through the coupling effect of machinery and the phase transfer agent; meanwhile, the interaction force among solid particles such as electrostatic force, dipole force, van der Waals force, hydrophobic force and DLVO force is eliminated, the original stable three-dimensional network structure of the oil sludge is broken, so that the solid particles such as silt, carbon powder, biomass and the like are gathered and settled, and the high-water-content oil sludge is reconstructed into an unstable oil system suspension system from a stable Pickering-like emulsion liquid system.
In a reconstructed oil system suspension system, due to sufficient contact, double electric layers and interface films of various colloidal particles are broken, water and oil in an original system can be coalesced, the water and oil phases are transferred into a phase transfer agent by taking the phase transfer agent as a medium, oil/water and water/oil emulsion wrapped in solid matters are released at the same time, a continuous phase-oil/water emulsion (O/W) in the original oil sludge system is converted into oil/agent/water mixed liquid, the original stability of a high-water-content oil-sludge Pickering emulsion system is broken, and the effect of separating oil and water from oil sludge is achieved; on the other hand, the particle size of the suspension in the reconstructed system is changed from different sizes to the basically uniform particle size, the steric hindrance between particles is reduced, the charges on the surface of the suspension can be neutralized due to the multifunctional effect of the phase transfer agent, the aggregation and sedimentation of the suspension such as silt, carbon powder, biomass and the like are facilitated, and the effect of subsequent treatment is improved. The effect of the system reconstruction simulation is shown in fig. 2.
The reconstruction of the high water-containing oil sludge Pickering emulsion system is generated by means of the dual action of chemical additives and mechanical coupling, the main factors influencing the reconstruction effect are the composition and the addition amount of a phase transfer agent, the phase transfer agent has extremely strong charge reduction performance and amphiphilic performance, the charges on the surfaces of oil sludge particles can be eliminated, colloid and asphaltene serving as surface active ingredients on the surfaces of solid particles are dissolved, the interfacial tension sigma on the surfaces of the oil sludge particles is reduced, the three-phase contact angle theta of the solid particles is changed, and meanwhile, the volume ratio of oil to water is changed by adding the phase transfer agent; secondly, the function of special equipment cannot be ignored, and the radius R of the solid particles can be reduced and the three-phase contact angle theta of the solid particles can be changed through the function of the special equipment. The main parameters of equipment influence are mainly shear rate, linear speed of rotor and working time.
Fig. 4 shows a method for reconstructing high water content sludge provided by the present invention, which comprises the following steps:
step S1: adding the high water-containing oil sludge and the phase transfer agent into a mixer for uniform mixing to obtain an unstable high water-containing oil sludge Pickering emulsion system.
The specific step of the step S1 is to add the high water-containing oil sludge and 35-85% of phase transfer agent by weight or volume ratio of the high water-containing oil sludge into a mixer, and uniformly mix the uneven high water-containing oil sludge and the phase transfer agent at room temperature to 80 ℃ and at the stirring speed of 80-150 rpm to obtain an unstable high water-containing oil sludge Pickering emulsion system.
The more specific step of the step S1 is to add the high water-containing oil sludge and the phase transfer agent which accounts for 45 percent of the weight ratio or the volume ratio of the high water-containing oil sludge into a mixer, and evenly mix the uneven high water-containing oil sludge and the phase transfer agent at 50 ℃ and the stirring speed of 100rpm to obtain the unstable high water-containing oil sludge Pickering emulsion system.
Step S2: and (2) transferring water and an oil phase of the unstable high-water-content oil-sludge Pickering emulsion system prepared in the step (S1) through pipeline type shearing equipment, transferring the water and the oil into a phase transfer agent to be mutually dissolved, and converting suspended matters in the unstable high-water-content oil-sludge Pickering emulsion system from different particle sizes into small particles with uniform sizes under the action of pipeline type shearing equipment so as to convert the unstable high-water-content oil-sludge Pickering emulsion system into an oil system suspended matter, namely reconstructing the high-water-content oil-sludge system.
The concrete steps of the step S2 are that the unstable high water-bearing oil sludge Pickering emulsion system prepared in the step S1 is subjected to phase transfer of water and oil in the unstable high water-bearing oil sludge Pickering emulsion system through a pipeline high shear dispersing emulsifying machine or a high pressure homogenizer or a homogenizing emulsifying machine under the conditions that the working temperature is between room temperature and 65 ℃, the working time is between 1 and 10min, the shearing rate is between 2500 and 12000rpm, the standard speed of a rotor is between 20 and 70m/S, and the working pressure is between normal pressure and 15.0MPa, the water and the oil are transferred into a phase transfer agent to be mutually dissolved together, and suspended matters in the unstable high water-bearing oil sludge Pickering emulsion system are also converted into small uniform particles from different sizes of the particles under the action of the high shear dispersing emulsifying machine or the high pressure homogenizer or the homogenizing emulsifying machine, so that the unstable high water-bearing oil sludge Pickering emulsion system is converted into the oil suspension system, namely the high water-bearing oil sludge is reconstructed.
The phase transfer agent comprises free water, capillary water and emulsified water of oil-in-water/water-in-oil type which are in high water content oil sludge are transferred into the phase transfer agent from a stable high water content oil sludge colloid system, the weight percentage of the alcohol Rm- (OH) n or low carbon alcohol ether solvent is 10-80% according to the higher weight percentage of the high water content oil sludge, wherein m =1-4, n =1-3, and the oil content in the high water content oil sludge colloid system is dissolved, the charge in the system and the colloid and the asphaltene in the oil content are eliminated, so that the original phase balance of the high water content oil sludge colloid system is destroyed, the oil sludge colloid system is reconstructed, and the weight percentage of the aromatic hydrocarbon solvent or the mineral oil is 20-90% according to the higher weight percentage of the oil content in the high water content oil sludge. In the process of reconstructing the oil sludge colloid system, double electric layers and interface films of various colloidal particles are broken, so that oil molecules are favorably transferred to a phase transfer agent on one hand, the effect that the oil molecules are transferred to a phase transfer agent liquid from the surface of a solid body to the inside of the solid body in a wrapping manner is achieved, oil recovery is favorably realized, and the aggregation and sedimentation of the solid body such as sand, dust, solid biomass and the like are favorably realized on the other hand, and preferably, the weight percentage of the alcohol Rm- (OH) n or low-carbon alcohol ether solvent is in the range of 40-65% according to the general composition of the existing oil sludge. Preferably, the weight percentage of the aromatic hydrocarbon solvent or mineral oil is in the range 35% to 60% depending on the prevailing composition of the oil sludge at present.
The alcohol Rm- (OH) n is one or more of ethanol, isopropanol, ethylene glycol or diethylene glycol, and the low-carbon alcohol ether solvent is one or more of ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclohexanediol monomethyl ether or ethylene glycol butyl ether. The aromatic hydrocarbon solvent is one or more of benzene, toluene, mixed xylene, mixed trimethylbenzene, tetramethylbenzene or ethylbenzene, and the mineral oil is one or more of gasoline, diesel oil, raffinate oil or aromatic hydrocarbon solvent oil.
The phase transfer agent also comprises a surfactant which promotes the alcohol Rm- (OH) n or low carbon alcohol ether solvent to be mutually soluble with the aromatic hydrocarbon solvent or mineral oil and plays roles of demulsification, oil displacement and auxiliary phase transfer in high water-containing oil sludge, and the weight percentage of the surfactant is 0.2-2% of the total weight of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or mineral oil. The surfactant comprises one or more of propylene glycol block polyether, alkylphenol polyoxyethylene ether, castor oil/hydrogenated castor oil polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, phenol-amine-aldehyde resin polyoxypropylene polyoxyethylene ether or acrylamide modified copolymer.
The phase transfer agent also comprises organic phenol, amine antioxidant and polymerization inhibitor for preventing the high water-containing oil sludge from coking and scaling in the process of drying and recovering oil and water, and the weight percentage of the organic phenol, the amine antioxidant and the polymerization inhibitor is 0.2 to 1 percent of the total weight of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mineral oil. The organic phenol, the amine antioxidant and the polymerization inhibitor are one or more of p-phenylenediamine, hydroquinone, p-tert-butyl catechol, p-benzyl aminophenol and the like.
A specific example of a method for reconstituting such a high water content sludge is employed.
The first embodiment.
The treated sample in this example was high-water content sludge (water content: 88.74%, oil content: 7.79%, solid content: 3.47%) from a petrochemical plant of Lanzhou
In this embodiment S1, 300g and 135g of the special phase transfer agent for high water content oil sludge are weighed and added into a 1000ml flask with stirring, the temperature is raised to 50 ℃, and the mixture is stirred for 10min at a rotation speed of 80rpm, so as to obtain an unstable water content oil sludge Pickering emulsion system by uniform mixing;
in this example S2, 435g of an unstable high water-containing oil sludge Pickering emulsion system obtained by uniformly mixing the phase transfer agent prepared in S1 is put into a homogenizer to be homogenized for 5min at 50 ℃ and a shear rate of 5000rpm, so as to prepare an unstable homogeneous oil suspension system; 184.2g of oil sludge was obtained after centrifugal separation.
And (3) drying the oil sludge obtained by the separation of the S2 in a 500ml rotary evaporator to obtain 27.7g of dried oil sludge.
In this example, the amount of the high water content sludge was reduced to 90.34%, and the oil component in the recovered high water content sludge was more than 70%, so that the reduction and recycling effects were significant.
Example two.
The sample treated in this example was high-water content oil sludge (water content 68.58%, oil content 16.81%, solid content 14.61%) from some petrochemical plant in Jiujiang
In this embodiment S1, 300g and 135g of the special phase transfer agent for high water content oil sludge are weighed and added into 1000ml of flask with stirring, the temperature is raised to 50 ℃, and the mixture is stirred for 10min at a rotation speed of 80rpm, so as to obtain an unstable high water content oil sludge Pickering emulsion system by uniform mixing;
in this example S2, the phase transfer agent-containing mixture obtained in S1 is mixed uniformly to obtain an unstable high water-containing oil-sludge Pickering emulsion system 435g, which is put into a homogenizer to be homogenized for 3min at 50 ℃ and 8000rpm of shear rate, so as to obtain an unstable homogeneous oil suspension system; 217.8g of oil sludge is obtained after centrifugal separation.
And (3) adding the oil sludge obtained by the separation in the S2 into a 500ml rotary evaporator for drying to obtain 68.1g of dried oil sludge.
In this example, the solid content of the high water content sludge itself was high, so the amount of the high water content sludge after the treatment was reduced by only 76.98%, but the oil component in the recovered high water content sludge still exceeded 70%, and the effect of reduction and recycling was significant, and fig. 3 is a 4X effect graph observed by a microscope before and after reconstitution (left is before reconstitution, right is after reconstitution).
Example three: the sample treated in this example was high-water content oil sludge (water content 68.58%, oil content 16.81%, solid content 14.61%) from some petrochemical plant in Jiujiang
In this embodiment S1, 300g and 135g of the special phase transfer agent for high water content oil sludge are weighed and added into 1000ml of flask with stirring, the temperature is raised to 50 ℃, and the mixture is stirred for 10min at a rotation speed of 80rpm, so as to obtain an unstable high water content oil sludge Pickering emulsion system by uniform mixing;
in this example S2, 435g of an unstable high water-containing oil sludge Pickering emulsion system obtained by uniformly mixing the phase transfer agent prepared in S1 is put into a homogenizer to be homogenized for 5min at 50 ℃ and a shear rate of 5000rpm, so as to prepare an unstable homogeneous oil suspension system; and obtaining 221g of oil sludge after centrifugal separation.
And (3) drying the oil sludge obtained by the separation of the S2 in a 500ml rotary evaporator to obtain 69.4g of dried oil sludge.
In this example, the solid content of the high water content sludge itself is high, so the weight reduction of the high water content sludge after the treatment is only 76.17%, but the oil component in the recovered high water content sludge also reaches 70%, and the reduction and recycling effects are significant. The particle size distribution of the system before and after reconstruction is shown in figure 4, the particle size range is wide and uneven before reconstruction, the range is narrow after reconstruction, and the particle size distribution is even.
Comparative example one.
The sample treated in this example was high water content sludge (water content: 88.74%, oil content: 7.79%, solid content: 3.47%) from a petrochemical plant of Lanzhou
And weighing 300g of the high water content oil sludge, adding the high water content oil sludge into a 1000ml rotary evaporator, and drying the high water content oil sludge under the drying conditions of the first embodiment to obtain 57.9g of dried oil sludge.
TABLE 1 Lanzhou sludge treatment method vs. drying effect
Compared with the treatment effect of the method for reconstructing the high-water-content oil sludge in the example (dried oil sludge 27.7g, weight loss greater than 90%), the treatment effect of the method without reconstructing the high-water-content oil sludge (dried oil sludge 57.9g, weight loss only 80%) is obviously poorer, and the dried oil sludge effect is also obviously poorer, which is shown in table 1.
Comparative example two.
The sample treated in this example was high-water content oil sludge (water content 68.58%, oil content 16.81%, solid content 14.61%) from some petrochemical plant in Jiujiang
And weighing 300g of the high water content oil sludge, adding the high water content oil sludge into a 1000ml rotary evaporator, and drying the high water content oil sludge under the drying conditions of the third embodiment to obtain 95.2g of dried oil sludge.
TABLE 2 contrast drying effect of oil sludge treatment method of Jiujiang river
Compared with the treatment effect of the method for reconstructing the high water content oil sludge in the example (the dried oil sludge is 69.4g, the weight loss is more than 76%), the treatment effect of the method without reconstructing the high water content oil sludge (the dried oil sludge is 95.2g, the weight loss is only 68%) is poorer, and the drying oil sludge effect is obviously inferior, as shown in table 2.
The effect of oil sludge reduction is achieved by reconstructing a high-water-content oil sludge Pickering emulsion liquid system into an oil system suspended matter system, the problem of recontamination of acidized tempering discharged hydrogen sulfide gas and the defects of poor effect and high energy consumption of other tempering methods are effectively eliminated, the phase transfer agent can be recycled, the drying effect is good, and the method has the characteristics of simplicity in operation, low safety risk, low energy consumption and low investment, and the effects of reduction and recycling are remarkable.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A method of high water sludge reconstitution, the method comprising the steps of:
step S1: adding the high water-containing oil sludge and a phase transfer agent into a mixer for uniform mixing to obtain an unstable high water-containing oil sludge Pickering emulsion system; the phase transfer agent comprises 10-80 wt% of low-carbon alcohol ether solvent and 20-90 wt% of aromatic hydrocarbon solvent or mineral oil; the phase transfer agent also comprises a surfactant which plays roles in demulsification, oil displacement and auxiliary phase transfer in the high-water-content oil sludge and promotes the mutual solubility of the low-carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mutual solubility of the low-carbon alcohol ether solvent and the mineral oil, and the weight percentage of the surfactant is 0.2-2% of the total amount of the low-carbon alcohol ether solvent and the aromatic hydrocarbon solvent or 0.2-2% of the total amount of the low-carbon alcohol ether solvent and the mineral oil; the low-carbon alcohol ether solvent is one or more of ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclohexanediol monomethyl ether or ethylene glycol butyl ether; the surfactant comprises one or more of propylene glycol block polyether, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, hydrogenated castor oil polyoxyethylene ether and polyoxyethylene polyoxypropylene ether;
step S2: and (2) carrying out phase transfer on water and oil in the unstable high-water-content oil-sludge Pickering emulsion system under the conditions that the working temperature is between room temperature and 65 ℃, the working time is between 1 and 10min, the shearing rate is between 2500 and 12000rpm, the standard speed of a rotor is between 20 and 70m/S, and the working pressure is between normal pressure and 15.0MPa through an emulsifying machine or a high-pressure homogenizer, transferring the water and the oil into a phase transfer agent to be mutually dissolved together, and converting suspended matters in the unstable high-water-content oil-sludge Pickering emulsion system from particles with different sizes into small particles with uniform sizes under the action of the emulsifying machine or the high-pressure homogenizer so that the unstable high-water-content oil-sludge Pickering emulsion system is converted into an oil system suspended matter, namely the high-water-content oil sludge is reconstructed.
2. The method as claimed in claim 1, wherein the step S1 is specifically performed by adding the high water content oil sludge and 35% -85% of phase transfer agent by weight or volume ratio of the high water content oil sludge into a mixer, and uniformly mixing the inhomogeneous high water content oil sludge and the phase transfer agent at room temperature to 80 ℃ and a stirring speed of 80-150 rpm to obtain an unstable high water content oil sludge Pickering emulsion system.
3. The method as claimed in claim 2, wherein the more specific step of step S1 is to add the high water content oil sludge and 45% phase transfer agent by weight or volume of the high water content oil sludge into a mixer, and mix the heterogeneous high water content oil sludge and phase transfer agent uniformly at 50 ℃ and stirring speed of 100rpm to obtain the unstable high water content oil sludge Pickering emulsion system.
4. A method according to any one of claims 1-3, wherein the emulsifier in step S2 is a homoemulsifier.
5. The method of claim 4, wherein the emulsifier in step S2 is an in-line high shear dispersing emulsifier.
6. The method according to claim 5, wherein the phase transfer agent further comprises one or more of p-phenylenediamine, hydroquinone, p-tert-butylcatechol, or p-benzylaminophenol, and the weight percentage of the one or more of p-phenylenediamine, hydroquinone, p-tert-butylcatechol, or p-benzylaminophenol is 0.2% -1% of the total amount of the lower alcohol ether solvent and the aromatic hydrocarbon solvent, or 0.2% -1% of the total amount of the lower alcohol ether solvent and the mineral oil, and is used for preventing coking or scaling of high water content oil sludge in the process of drying and recovering oil and water.
7. The method according to claim 6, wherein the lower alcohol ether solvent is 40 to 65 wt%; the weight percentage of the aromatic hydrocarbon solvent or the mineral oil is 35 to 60 percent.
8. The method of claim 7, wherein the aromatic solvent is one or more of benzene, toluene, mixed xylenes, mixed trimethylbenzenes, tetramethylbenzenes, or ethylbenzene, and the mineral oil is one or more of gasoline, diesel, raffinate, or aromatic solvent.
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| CN1069340C (en) * | 1996-12-20 | 2001-08-08 | 中国科学院广州能源研究所 | Heavy-oil emulsifying agent and application thereof |
| US8101086B2 (en) * | 2006-08-16 | 2012-01-24 | Exxonmobil Upstream Research Company | Oil/water separation of full well stream by flocculation-demulsification process |
| CN102181072B (en) * | 2011-02-24 | 2013-01-16 | 常州大学 | Preparation method of emulsion antioxidant |
| CN102268839B (en) * | 2011-07-25 | 2013-04-10 | 华南理工大学 | Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent |
| CN103449690A (en) * | 2012-05-30 | 2013-12-18 | 青海大地环境工程技术有限公司 | Purifying treatment method for oil-containing sludge |
| CN104291541B (en) * | 2014-09-10 | 2016-01-06 | 浙江大学 | A kind of method reclaiming crude oil from accumulating greasy filth |
| CN108641697A (en) * | 2018-04-20 | 2018-10-12 | 黄智慧 | A kind of preparation method of demulsifier |
| CN110054393A (en) * | 2019-04-12 | 2019-07-26 | 天津大学 | A kind of processing method of oily sludge |
| CN110760328B (en) * | 2019-10-30 | 2022-01-25 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
| CN111394118A (en) * | 2020-05-18 | 2020-07-10 | 宫传奇 | Ageing oil and fatlute minimizing crude oil recovery processing integration sled dress device |
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