CN113955919A - Phase transfer agent for high-water-content oil sludge - Google Patents
Phase transfer agent for high-water-content oil sludge Download PDFInfo
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- CN113955919A CN113955919A CN202011394525.XA CN202011394525A CN113955919A CN 113955919 A CN113955919 A CN 113955919A CN 202011394525 A CN202011394525 A CN 202011394525A CN 113955919 A CN113955919 A CN 113955919A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
Abstract
The invention is applicable to the field of high-water-content oil sludge treatment, and provides a phase transfer agent for high-water-content oil sludge, which comprises 10-80 wt% of alcohol Rm- (OH) n or low-carbon alcohol ether solvent with higher water content according to higher water content, wherein m =1-4, n =1-3, and 20-90 wt% of aromatic hydrocarbon solvent or mineral oil with higher oil content according to higher oil content in the high-water-content oil sludge. The defects in the prior art are overcome, and the pollution influence of the oil sludge on the environment can be reduced; and secondly, the oil and water in the oil sludge can be recovered, so that the aim of recycling value of resources is fulfilled.
Description
Technical Field
The invention belongs to the field of high-water-content oil sludge treatment, and particularly relates to a phase transfer agent for high-water-content oil sludge.
Background
Oil sludge is generally classified into three categories: oil field oil sludge, refined oil sludge and storage and transportation oil sludge. The oil field oil sludge refers to oil sludge generated in the oil drilling and production process, and mainly comprises ground oil sludge, drilling waste slurry and oil extraction water injection system settlement oil sludge. The oil sludge on the ground is a mixture formed by crude oil overflowing and leaking during oil drilling and permeating into the ground, soil, sand, water and the like. The drilling waste mud is a complex multi-phase system formed by mud, sewage, rock debris and the like discharged in a drilling well. In addition, the oil extraction water injection system can generate a large amount of oily sewage in the processes of secondary oil extraction and tertiary oil extraction, and the oily sewage is separated and settled to generate settled oil sludge of the oil extraction water injection system. The refined oil sludge is mainly oil refining wastewater 'three sludge', and comprises oil separation tank bottom sludge, floating slag in an air flotation tank, residual activated sludge in a biochemical tank, a small amount of dirty oil tank bottom sludge and the like generated in the oil refining wastewater treatment process. The storage and transportation oil sludge refers to oil sludge generated by depositing a small amount of heavy components such as mechanical impurities, sand grains, sludge, heavy metal salts, paraffin, chocolate green matters and the like at the bottom of a container in the storage and transportation processes of crude oil and petroleum products and oil sludge generated in the transportation process are treated by adopting a method of primary sedimentation dehydration and then outward transportation limiting stacking in many enterprises at present. With stricter environmental laws and regulations of various countries in the world, the requirements of oil sludge reduction, stabilization and resource treatment are higher and higher.
The three kinds of oil sludge have complicated organic matter components, high water content, high stability and great treatment difficulty, and belong to high water content oil sludge. The oil content is generally 8-10%, the water content is 60-80%, and the oil-water mixture further contains about 10-15% of solid matters (mud, sand and the like), because the high-water-content oil mud is a complex system formed by mixing water, the solid matters and oil, an interface film exists between the water interface and the oil interface to prevent coalescence between water drops and oil drops, and the oil-water mixture is very stable because of 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 different in shape and size, and may be wrapped in multiple emulsions such as water-in-oil-in-water (W/O/W) or oil-in-water-in-oil (O/W/O). Therefore, the treatment of the high water content oil sludge becomes a great problem for the treatment of dangerous waste.
Various treatment technologies for high-water-content oil sludge are developed at home and abroad, and mainly include a landfill method, an incineration method, a solvent extraction method, a centrifugal dehydration method, a thermal desorption method, a thermochemical demulsification method, a microwave treatment method, a microbial treatment 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 centrifugal dehydration method is a pure decrement method, and because the water in the high-water-content oil sludge is mainly in an emulsified state, the dehydration is difficult, and the aim of treating the high-water-content oil sludge cannot be really achieved. The thermal desorption method also has the problems of high energy consumption, waste gas generation and the like, and also has the problems of flammability, explosiveness and easy coking and blockage of equipment. Various reagents used in the thermochemical demulsification method have certain effect on simple high-water-content oil sludge, and have no obvious demulsification effect on high-water-content oil sludge with complex components, high viscosity, more colloid and more asphaltene. The microwave treatment method is only researched in a laboratory at present and also has the defects of high energy consumption, high safety risk of an operation site and the like. The microbial method occupies a large area, has a long treatment period, is limited by the environmental climate temperature, can only treat the oil sludge with the oil content of less than 5 percent, and is limited in treatment.
In recent years, some domestic enterprises adopt a method of acidifying with sulfuric acid and then drying to reduce the amount of the oil sludge, but cannot continue to operate due to the problems of generation of hydrogen sulfide, flammable and explosive low-flash-point substances and other safety risks. Generally, no more mature treatment method exists in China, and particularly, a treatment method capable of achieving long, stable, safe, full and optimal operation is available.
Disclosure of Invention
The invention aims to provide a phase transfer agent of high-water-content oil sludge, which overcomes the defects in the prior art and can reduce the pollution influence of the oil sludge on the environment; and secondly, the oil and water in the oil sludge can be recovered, so that the aim of recycling value of resources is fulfilled.
The invention is realized by the phase transfer agent of the high water content oil sludge, which comprises free water, capillary water and emulsified water of oil-in-water/oil-in-water type in the high water content oil sludge, transferred into the phase transfer agent from a stable high water content oil sludge colloid system, wherein the weight percentage of the alcohol Rm- (OH) n or low carbon alcohol ether solvent is 10-80% according to the higher water content 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 and the charge in the system and the colloid and the asphaltene in the oil content are eliminated, thereby the original phase balance of the high water content oil sludge colloid system is destroyed, the colloid system is reconstructed, and the weight percentage of the aromatic hydrocarbon solvent or the mineral oil is higher according to the higher oil content of the high water content oil sludge, the weight percentage is 20-90%.
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 the mineral oil and plays roles of demulsification, oil displacement and auxiliary phase transfer in a high-water-content oil sludge system, 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 the mineral oil.
The further technical scheme of the invention is as follows: the phase transfer agent also comprises an organic phenol antioxidant and a polymerization inhibitor for preventing the high-water-content oil sludge from coking and scaling in the process of drying and recovering oil and water, and the weight percentage of the organic phenol 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 further technical scheme of the invention is as follows: 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 further technical scheme of the invention is as follows: 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 further technical scheme of the invention is as follows: the surfactant comprises one or more of propylene glycol embedded polyether, alkylphenol polyoxyethylene ether, castor oil/hydrogenated castor oil polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, phenol-amine resin polyoxypropylene polyoxyethylene ether or acrylamide modified copolymer.
The further technical scheme of the invention is as follows: 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 phase transfer agent is used for carrying out phase transfer separation drying treatment on oil sludge with high water content in an oil refinery, the problems of large consumption and high consumption of hydrogen sulfide gas and an extracting agent discharged by acidification tempering are effectively eliminated, the phase transfer agent can be recycled, the drying effect is good, and the phase transfer agent has the characteristics of simplicity in operation, low safety risk, low energy consumption, low investment, and remarkable reduction and recycling effects.
Detailed Description
The invention provides a phase transfer agent for high-water-content oil sludge, which comprises free water, capillary water and oil-in-water/water-in-oil emulsified water in the high-water-content oil sludge are transferred into the phase transfer agent from a stable high-water-content oil sludge colloid system, and according to the higher water content of the high water-containing oil sludge, the higher weight percentage of alcohol Rm- (OH) n or low carbon alcohol ether solvent is 10-80 percent, wherein m =1-4, n =1-3, and dissolves oil component in high water content oil sludge colloid system and eliminates electric charge in the system, colloid and asphaltene in the oil component, thus destroying the original phase balance of the high water-containing oil sludge colloid system, reconstructing the oil sludge colloid system, and according to the fact that the higher the oil content in the high water-containing oil sludge, the higher the weight percentage of the oil sludge is, the aromatic hydrocarbon solvent or mineral oil accounts for 20-90 percent. In the process of reconstructing the oil sludge colloid system, electric double layers and interface films of various colloidal particles are broken, so that oil molecules are favorably transferred into the phase transfer agent on one hand, the effect that the oil molecules are transferred into the phase transfer agent liquid from the surface of a solid body and the inside of the solid body in a wrapping mode is achieved, the oil molecules are favorably recovered, on the other hand, the solid body such as silt, dust, solid biomass and the like is favorably gathered and settled, and according to the general composition of the existing oil sludge, the weight percentage of the alcohol Rm- (OH) n or low-carbon alcohol ether solvent is preferably within the range of 40-65%. Preferably, the weight percentage of the aromatic hydrocarbon solvent or mineral oil is in the range of 35% to 60% according to the currently prevailing composition of the oil sludge.
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 mutual solubility of the alcohol Rm- (OH) n or low-carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mineral oil and plays roles of demulsification, oil displacement and auxiliary phase transfer in a high-water-content oil sludge system, 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 the mineral oil. The surfactant comprises one or more of propylene glycol embedded polyether, alkylphenol polyoxyethylene ether, castor oil/hydrogenated castor oil polyoxyethylene ether, polyoxyethylene polyoxypropylene ether, phenol-amine resin polyoxypropylene polyoxyethylene ether or acrylamide modified copolymer and the like.
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 antioxidant and the polymerization inhibitor are one or more of p-phenylenediamine, hydroquinone, p-tert-butyl catechol, p-benzyl aminophenol and the like.
Specific examples of phase transfer agents using such high water content sludge.
The first embodiment.
The sample treated in this example is high water content oil sludge (water content 88.74%, oil content 7.79%, solid content 3.47%) of a certain petrochemical plant in Lanzhou, and the phase transfer agent is (by weight): 80% of diethylene glycol dimethyl ether, 20% of mixed xylene, 1.5% of propylene glycol block polyether and 0.5% of p-phenylenediamine.
In this embodiment S1, 300g and 150g of the special phase transfer agent are weighed and added into a 1000ml open container, the temperature is raised to 50 ℃, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for 5min to obtain a phase transfer mixture;
in this example S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged at room temperature to obtain 264.4g of a clear oil-water-agent mixture and 183.2g of reconstituted sludge.
In this example, S3, the mixed supernatant obtained in S2 was allowed to stand at room temperature for 24 hours to separate the oil phase and the aqueous phase, and 137g of the upper oil phase and 125.5g of the lower aqueous phase were separated;
in this embodiment, S4, 180.1g of the reconstructed oil sludge obtained by separation in S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 240 ℃ to perform drying treatment, so as to obtain 145.2g of distillate and 32.88g of dried oil sludge;
in this example S5, 145.2g of distillate obtained by separating the oil phase 137g from S3 and S4 was put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 150 ℃ to recover 145.19g of phase transfer agent, 109.3g of waste water, and 16.2g of residual oil from distillation.
In the embodiment, the weight of the high water-bearing oil sludge is reduced to more than 88.85%, the oil component in the recovered high water-bearing oil sludge is nearly 70%, and the reduction and recycling effects are obvious.
Example two.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): 70% of diethylene glycol dimethyl ether, 30% of mixed xylene, 0.5% of propylene glycol block polyether and 0.5% of p-phenylenediamine.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example, S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged at room temperature to obtain 229g of a clear oil, water and agent mixture solution and 217.5g of a reconstituted sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to 50 ℃ and left standing for 8 hours to separate the oil phase from the aqueous phase, and 157g of the upper oil phase and 72g of the lower aqueous phase were separated;
in this embodiment, in step S4, 212.3g of the reconstructed oil sludge obtained by separation in step S2 is dried in a 500ml rotary evaporator under vacuum, the vacuum degree is controlled to be-0.09 MPPa, the temperature is slowly increased, the final temperature is controlled to be 120 ℃ for drying treatment, 132.3g of distillate is obtained, and 79.4g of dried oil sludge is obtained;
in this example S5, 157g of oil phase obtained by separating S3 and 132.3g of distillate obtained by separating S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃ to recover 143.7g of phase transfer agent, 103.4g of waste water and 32.1g of residual oil from distillation.
In this example, the solid content of the high water content sludge itself was high, and therefore the weight reduction of the high water content sludge after the treatment was 72.88%, but the oil content in the recovered high water content sludge exceeded 63.65%, and the effect of reduction and recycling was significant.
Example three.
The sample treated in this example is high water content oil sludge (water content 88.74%, oil content 7.79%, solid content 3.47%) of a certain petrochemical plant in Lanzhou, and the phase transfer agent is (by weight): 60% of diethylene glycol dimethyl ether, 40% of mixed xylene, 1.5% of propylene glycol block polyether and 0.5% of p-phenylenediamine.
In this embodiment S1, 300g and 150g of the special phase transfer agent are weighed and added into a 1000ml open container, the temperature is raised to 50 ℃, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for 5min to obtain a phase transfer mixture;
in this example, S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged at room temperature to obtain 262.4g of a clear liquid of oil, water and agent mixture and 184.2g of reconstituted sludge.
In this example, S3, the mixed supernatant obtained in S2 was allowed to stand at room temperature for 24 hours to separate the oil phase and the aqueous phase, and 137.8g of the upper oil phase and 124.5g of the lower aqueous phase were separated;
in this embodiment, in step S4, 176.1g of the reconstructed oil sludge obtained by separation in step S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 240 ℃ to perform drying treatment, so as to obtain 144.2g of distillate and 27.7g of dried oil sludge;
in this example S5, 137.8g of oil phase separated in S3 and 144.2g of distillate separated in S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 150 ℃ to recover 142.57g of phase transfer agent, 111.6g of waste water and 16.44g of residual oil from distillation.
In the embodiment, the weight reduction of the high water content oil sludge is 90.34%, the oil component in the recovered high water content oil sludge exceeds 70%, and the reduction and recycling effects are obvious.
Example four.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): 50% of diethylene glycol dimethyl ether, 50% of mixed xylene, 0.5% of propylene glycol block polyether and 0.5% of p-phenylenediamine.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example, in S2, 450g of the phase transfer mixture containing the phase transfer agent prepared in S1 was centrifuged at room temperature for 20min to obtain 227g of clear oil, water and agent mixture liquid and 217.8g of reconstituted oil sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to 50 ℃ and left standing for 8 hours to separate the oil phase from the aqueous phase, and 156g of the upper oil phase and 71g of the lower aqueous phase were separated;
in this embodiment, in step S4, 214.8g of the reconstituted product obtained by separation in step S2 is dried in a 500ml rotary evaporator under vacuum, the vacuum degree is controlled at-0.09 MPPa, the temperature is slowly increased, the final temperature is controlled at 120 ℃ for drying treatment, 134.3g of distillate and 68.1g of dried oil sludge are obtained;
in this example S5, 134.3g of the oil phase 156g separated in S3 and the distillate 134.3g separated in S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃ and a phase transfer agent 144.2g, a waste water 100.5g and a residual oil 35.65g were recovered.
In this example, the solid content of the high water content oil sludge is high, and the weight reduction of the treated high water content oil sludge is only 76.98%, but the oil component in the recovered high water content oil sludge still exceeds 70%, so the weight reduction and resource utilization effects are significant.
Example five.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): ethylene glycol monomethyl ether 40%, mixed xylene 60%, acrylamide xylene sulfonamide copolymer 1.0%, and p-benzylaminophenol 0.5%.
In this example S1, 300g and 150g of the above-mentioned high-water content oil sludge and the special phase transfer agent are weighed and added into a 1000ml open container, and put into a homogenizer at a rotation speed of 5000rpm for 5min at room temperature to prepare a phase transfer mixture.
In this example, S2, 450g of the phase transfer mixture containing the phase transfer agent prepared in S1 was vacuum filtered for 20min under a condition of room temperature under a vacuum degree of-0.075 MPPa, to obtain 223.1g of oil, water and agent mixed clear liquid and 221g of reconstituted oil sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to room temperature and left to stand for 24 hours to separate the oil phase from the aqueous phase, and 159.5g of the upper oil phase and 83.6g of the lower aqueous phase were separated;
in this embodiment, in step S4, 214.5g of the reconstituted oil obtained by separation in step S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 200 ℃ to perform drying treatment, so as to obtain 139.2g of distillate and 69.4g of dried oil sludge;
in this example S5, 159.5g of oil phase obtained by separating S3 and 139.2g of distillate obtained by separating S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃ to recover 142.7g of phase transfer agent, 112.2g of waste water and 32.65g of residual oil from distillation.
In this example, the solid content of the high water content oil sludge is high, so that the weight of the treated high water content oil sludge is reduced by 76.16%, but the oil component in the recovered high water content oil sludge is only 64.7%, and the reduction and recycling effects are significant.
Example six.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): 30% of ethylene glycol monomethyl ether, 70% of mixed xylene, 1.0% of acrylamide xylene sulfonamide copolymer and 0.5% of p-benzylaminophenol.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example, S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged in a centrifuge at room temperature for 20min to separate 224.6g of the oil, water and agent mixture clear solution and 219.7g of reconstituted sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to room temperature and left to stand for 24 hours to separate the oil phase from the aqueous phase, and 163.6g of the upper oil phase and 79.5g of the lower aqueous phase were separated;
in this embodiment, in step S4, 214.7g of the reconstituted oil obtained by separation in step S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 200 ℃ to perform drying treatment, so as to obtain 137.2g of distillate and 77.4g of dried oil sludge;
in this example S5, 163.6g of oil phase obtained by separating S3 and 137.2g of distillate obtained by separating S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃ to recover 144.6g of phase transfer agent, 102.1g of waste water and 35.1g of residual oil from distillation.
In the embodiment, the solid content of the high-water-content oil sludge is high, so that the weight reduction of the treated high-water-content oil sludge is only 73.6%, the oil component in the high-water-content oil sludge is recovered by 69.6%, and the reduction and recycling effects are obvious.
Example seven.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): ethylene glycol monomethyl ether 20%, mixed xylene 80%, acrylamide xylene sulfonamide copolymer 1.0%, and p-benzylaminophenol 0.5%.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example, S2, 450g of the phase transfer mixture containing the phase transfer agent prepared in S1 was vacuum filtered at room temperature under-0.075 MPPa for 20min to obtain 221.4g of oil, water and agent mixed clear liquid and 222.3g of reconstituted oil sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to room temperature and left to stand for 24 hours to separate an oil phase and an aqueous phase, and 147.4g of an upper oil phase and 73.7g of a lower aqueous phase were separated;
in this embodiment, in step S4, 222.3g of the reconstituted oil obtained by separation in step S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 200 ℃ to perform drying treatment, so as to obtain 140.2g of distillate and 60.4g of dried oil sludge;
in this example S5, 147.4g of oil phase separated in S3 and 140.2g of distillate separated in S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃ to recover 143.7g of phase transfer agent, 104.9g of waste water and 34.95g of residual oil from distillation.
In this example, the solid content of the high water content oil sludge is high, so the weight reduction of the high water content oil sludge after treatment is only 72.8%, the oil component in the recovered high water content oil sludge is nearly 70%, and the reduction and recycling effects are significant.
Example eight.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of a certain petrochemical plant in jiujiang, and the phase transfer agent is (by weight): 10% of ethylene glycol monomethyl ether, 90% of mixed xylene, 1.0% of acrylamide xylene sulfonamide copolymer and 0.5% of p-benzylaminophenol.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged at room temperature to obtain 213.1g of a clear oil-water-agent mixture and 235.7g of a reconstituted sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to room temperature and left to stand for 24 hours to separate the oil phase from the aqueous phase, and 152g of the upper oil phase and 81g of the lower aqueous phase were separated;
in this example, S4, 227.1g of the reconstituted oil obtained by separation in S2 was dried in a 500ml rotary evaporator under normal pressure, the temperature was slowly raised, and the final temperature was controlled at 200 ℃ to perform drying treatment, so as to obtain 131.5g of distillate and 79.9g of dried oil sludge;
in this example S5, 152g of oil phase obtained by separating S3 and 131.5g of distillate obtained by separating S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃, 142.4g of phase transfer agent, 99.7g of waste water and 34.3g of residual oil after distillation were recovered.
In this example, the solid content of the high water content oil sludge itself was high, and the weight reduction of the high water content oil sludge after the treatment was only 72.36%, but the oil component in the recovered high water content oil sludge was 68%, and the reduction and recycling effects were better than those of other methods, but the effects were not as good as those of other blending ratios.
Example nine.
The sample treated in this example is high water content oil sludge (water content of 68.58%, oil content of 16.81%, solid content of 14.61%) of some petrochemical plant in jiujiang, and the phase transfer agent is: the recovered phase transfer agent of example four was used at 90% and the fresh phase transfer agent was replenished at 10%.
In this embodiment S1, 300g and 150g of the special phase transfer agent for the high water content oil sludge are weighed and added into a 1000ml open container, and the mixture is put into a homogenizer at a rotation speed of 5000rpm for homogenization for 5min at room temperature to obtain a phase transfer mixture;
in this example, S2, 450g of the phase transfer mixture containing the phase transfer agent obtained in S1 was centrifuged in a centrifuge at room temperature for 20min to separate 224g of the oil, water and agent mixture clear solution and 222.2g of the reconstituted oil sludge.
In this example, S3, the mixed clear solution obtained in S2 was heated to room temperature and left to stand for 24 hours to separate the oil phase from the aqueous phase, and 155g of the upper oil phase and 69g of the lower aqueous phase were separated;
in this embodiment, in step S4, 220.2g of the reconstructed oil sludge obtained by separation in step S2 is dried in a 500ml rotary evaporator under normal pressure, the temperature is slowly raised, and the final temperature is controlled at 200 ℃ to perform drying treatment, so as to obtain 140.3g of distillate and 72.9g of dried oil sludge;
in this example S5, 155g of oil phase obtained by separating S3 and 140.3g of distillate obtained by separating S4 were put into a 500ml vacuum rotary evaporator, the vacuum degree was controlled at-0.09 MPPa, the temperature was slowly raised to 120 ℃, 142.3g of phase transfer agent, 108.1g of waste water and 35.7g of residual oil were recovered.
The weight reduction of the high-water-content oil sludge used in the embodiment after treatment still reaches 75.47%, the oil component in the recovered high-water-content oil sludge exceeds 70%, and the weight reduction and recycling effects are quite obvious.
The phase transfer agent is used for carrying out phase transfer separation drying treatment on oil sludge with high water content in an oil refinery, the problems of large consumption and high consumption of hydrogen sulfide gas and an extracting agent discharged by acidification tempering are effectively eliminated, the phase transfer agent can be recycled, the drying effect is good, and the phase transfer agent has the characteristics of simplicity in operation, low safety risk, low energy consumption, low investment, and remarkable reduction and recycling effects.
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 (9)
1. A phase transfer agent for high water content oil sludge is characterized in that the phase transfer agent comprises an alcohol Rm- (OH) n or low carbon alcohol ether solvent which transfers free water, capillary water and emulsified water of oil-in-water/water-in-oil type in the high water content oil sludge from a stable high water content oil sludge colloid system to the phase transfer agent, the weight percentage of the alcohol Rm- (OH) n or low carbon alcohol ether solvent is 10-80% according to the higher water content of the high water content oil sludge, wherein m =1-4 and n =1-3, and the oil content in the high water content oil sludge colloid system is dissolved, the electric 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 colloid system is reconstructed, and the weight percentage of the aromatic hydrocarbon solvent or mineral oil is higher according to the higher oil content of the high water content oil sludge, the weight percentage is 20-90%.
2. The phase transfer agent of claim 1, further comprising a surfactant for promoting the mutual solubility of the alcohol Rm- (OH) n or the low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mineral oil, and for performing demulsification, oil displacement and auxiliary phase transfer in a high water content oil sludge system, wherein the weight percentage of the surfactant is 0.2-2% of the total amount of the alcohol Rm- (OH) n or the low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or the mineral oil.
3. The phase transfer agent according to claim 2, further comprising organic phenol, amine antioxidant and polymerization inhibitor for preventing coking and scaling of high water content oil sludge in the process of drying and recovering oil and water, wherein the weight percentage of the organic phenol, amine antioxidant and polymerization inhibitor is 0.2-1% of the total amount of the alcohol Rm- (OH) n or low carbon alcohol ether solvent and the aromatic hydrocarbon solvent or mineral oil.
4. The phase transfer agent according to claim 3, wherein the alcohol Rm- (OH) n or the lower alcohol ether solvent is 40 to 65% by weight.
5. The phase transfer agent according to claim 4, wherein the weight percentage of the aromatic hydrocarbon solvent or mineral oil is 35-60%.
6. The phase transfer agent according to any one of claims 1 to 5, wherein the alcohol Rm- (OH) n is one or more of ethanol, isopropanol, ethylene glycol or diethylene glycol, and the lower 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.
7. The phase transfer agent of claim 6, wherein 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.
8. The phase transfer agent of claim 2, wherein the surfactant comprises one or more of a propylene glycol block polyether, an alkylphenol ethoxylate, castor oil/hydrogenated castor oil ethoxylate, polyoxyethylene polyoxypropylene, phenol-amine resin polyoxypropylene ethoxylate, or an acrylamide modified copolymer.
9. The phase transfer agent of claim 3, wherein the organic phenol, amine antioxidant, and polymerization inhibitor is one or more of p-phenylenediamine, hydroquinone, p-tert-butylcatechol, and p-benzylaminophenol.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5125966A (en) * | 1990-12-20 | 1992-06-30 | Nalco Chemical Company | Process for de-oiling mill sludge |
| JPH09234307A (en) * | 1996-02-29 | 1997-09-09 | Sannopuko Kk | Deforming composition |
| CN1185479A (en) * | 1996-12-20 | 1998-06-24 | 中国科学院广州能源研究所 | Heavy-oil emulsifying agent and application thereof |
| WO2009072007A2 (en) * | 2007-12-07 | 2009-06-11 | Foamix Ltd. | Carriers, formulations, methods for formulating unstable active agents for external application and uses thereof |
| US20110253598A1 (en) * | 2010-04-14 | 2011-10-20 | General Electric Company | Composition and method for breaking water in oil emulsions |
| CN104556626A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Oil sludge demulsifier and oil sludge resourceful treatment process |
| CN105236698A (en) * | 2015-10-09 | 2016-01-13 | 中国科学院南京土壤研究所 | Microemulsion detergent for resource treatment of oil-containing solid waste, and preparation method and application thereof |
| CN106630545A (en) * | 2017-02-06 | 2017-05-10 | 天津市环境保护技术开发中心设计所 | Drying treatment method of oil-containing sludge |
| CN106810030A (en) * | 2017-01-04 | 2017-06-09 | 克拉玛依金鑫油田环保工程有限公司 | The security processing of greasy filth |
| US20190300795A1 (en) * | 2018-04-03 | 2019-10-03 | Hang Ren | Treatment Process for Polluted Oil Sludge |
| CN110760328A (en) * | 2019-10-30 | 2020-02-07 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
-
2020
- 2020-12-03 CN CN202011394525.XA patent/CN113955919B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5125966A (en) * | 1990-12-20 | 1992-06-30 | Nalco Chemical Company | Process for de-oiling mill sludge |
| JPH09234307A (en) * | 1996-02-29 | 1997-09-09 | Sannopuko Kk | Deforming composition |
| CN1185479A (en) * | 1996-12-20 | 1998-06-24 | 中国科学院广州能源研究所 | Heavy-oil emulsifying agent and application thereof |
| WO2009072007A2 (en) * | 2007-12-07 | 2009-06-11 | Foamix Ltd. | Carriers, formulations, methods for formulating unstable active agents for external application and uses thereof |
| US20110253598A1 (en) * | 2010-04-14 | 2011-10-20 | General Electric Company | Composition and method for breaking water in oil emulsions |
| CN104556626A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Oil sludge demulsifier and oil sludge resourceful treatment process |
| CN105236698A (en) * | 2015-10-09 | 2016-01-13 | 中国科学院南京土壤研究所 | Microemulsion detergent for resource treatment of oil-containing solid waste, and preparation method and application thereof |
| CN106810030A (en) * | 2017-01-04 | 2017-06-09 | 克拉玛依金鑫油田环保工程有限公司 | The security processing of greasy filth |
| CN106630545A (en) * | 2017-02-06 | 2017-05-10 | 天津市环境保护技术开发中心设计所 | Drying treatment method of oil-containing sludge |
| US20190300795A1 (en) * | 2018-04-03 | 2019-10-03 | Hang Ren | Treatment Process for Polluted Oil Sludge |
| CN110760328A (en) * | 2019-10-30 | 2020-02-07 | 中国石油化工股份有限公司 | Method for cleaning oil sludge sand and recovering crude oil |
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