WO2019011044A1 - 一种含油污泥用乳液型水基清洗剂及其制备方法和使用方法 - Google Patents

一种含油污泥用乳液型水基清洗剂及其制备方法和使用方法 Download PDF

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WO2019011044A1
WO2019011044A1 PCT/CN2018/085284 CN2018085284W WO2019011044A1 WO 2019011044 A1 WO2019011044 A1 WO 2019011044A1 CN 2018085284 W CN2018085284 W CN 2018085284W WO 2019011044 A1 WO2019011044 A1 WO 2019011044A1
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oil
cleaning agent
type water
water
based cleaning
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English (en)
French (fr)
Inventor
吴涛
王茂鑫
朱亚超
孙德军
周建华
卫鹏程
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Shouguang Xinhai Energy Technology Co Ltd
Shandong University
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Shouguang Xinhai Energy Technology Co Ltd
Shandong University
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Priority to US16/603,954 priority Critical patent/US20200123478A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0217—Separation of non-miscible liquids by centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • 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
    • 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
    • C02F11/004—Sludge detoxification
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C11D3/187—Hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/06—Sludge reduction, e.g. by lysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the invention relates to an emulsion type water-based cleaning agent for oily sludge cleaning, and relates to a preparation method and a using method of the water-based cleaning agent, and belongs to the technical field of oily sludge cleaning.
  • Oily sludge is a solid waste generated during the process of oil exploitation, storage and transportation, refining and oily sewage treatment. In addition to petroleum hydrocarbons, it also contains toxic substances such as benzene, phenols and heavy metal salts. Occupying land and space, and if directly discharged without treatment, it will seriously pollute the air, soil and groundwater, and has been included in the “National Hazardous Waste List”, which restricts the development of domestic oilfield production to a certain extent. At the same time, oily sludge is a kind of resource. If it can develop a treatment technology that can eliminate the harm of oily sludge to the environment and recycle its useful resources, it will have important practical significance for the sustainable development of oilfields.
  • the methods for treating oily sludge at home and abroad mainly include resource recovery technology, harmless treatment technology and comprehensive utilization technology.
  • the resource recovery technology includes solvent extraction method, hot washing method, surfactant aqueous solution cleaning method, microemulsion washing method, chemical demulsification method and solid-liquid separation method, etc.
  • harmless treatment technology includes curing treatment method, biological treatment method And incineration methods
  • comprehensive utilization technologies include thermal decomposition and brick paving, but each treatment method has its advantages and disadvantages.
  • the more commonly used solvent extraction method can recover most of the oil phase in the sludge, but the extractant is relatively expensive, inevitably causing certain losses during the treatment process, and there are still safety hazards;
  • the incineration method can The organic matter is thoroughly treated and can effectively utilize the heat energy generated during the incineration process, but the treatment process requires a certain amount of fuel oil and a special incineration device, and also emissions of waste gas and waste residue, which may cause secondary pollution.
  • the hot washing method, the surfactant aqueous solution cleaning method, the microemulsion washing method and the like have the advantages of simple operation method, less equipment investment, lower requirements on experimental conditions, and the like, and can effectively recover the oil phase in the sludge, in the industry. Have a certain application.
  • an oily sludge treatment agent disclosed in Chinese Patent Publication No. CN104310734A can effectively reduce the oil-water interfacial tension at room temperature, and the treatment effect of the oily sludge is relatively good, and the oil phase recovery rate can reach 96% or more, but
  • the enzyme solution of the oily sludge treatment agent is added with biological enzymes such as protease and lipase, which makes it sensitive to temperature changes and is not conducive to the performance of the drug.
  • Chinese patent document CN106277709A discloses an environmentally-friendly cleaning agent for treating oily sludge.
  • US Patent No. US20150068950A1 describes a water-in-oil type nanoemulsion prepared from an alkyl glycoside surfactant for treating oily sludge, the nanoemulsion has a lower interfacial tension, and nanometer-sized water droplets in the emulsion are easier.
  • US Patent Publication No. 20090221456A1 reports a microemulsion method for cleaning oily sediments, which can reduce the oil content of oil sands to a minimum when the surfactant is added in an amount of 1 to 5 wt%. 0.52%, but if the temperature rises to the cloud point of the surfactant solution, phase separation will occur and the cleaning efficiency will be significantly reduced.
  • the microemulsion system is sensitive to temperature changes.
  • oily sludge cleaning agent is an aqueous surfactant solution.
  • the invention aims at the shortage of the existing oily sludge treatment agent, and provides an emulsion type water-based cleaning agent for oily sludge with stable property, safety, high efficiency and good cleaning effect, and provides a preparation method and a using method of the cleaning agent.
  • the emulsion type water-based cleaning agent for oil-containing sludge of the present invention comprises 2 to 10 parts of a surfactant, 3 to 10 parts of an oil-soluble component, and the balance is an aqueous phase in terms of 100 parts by weight.
  • the surfactant comprises a fatty alcohol polyoxyethylene ether sulfate and a super amphiphilic emulsifier, and the mass ratio between the two is 1:4 to 4:1, and preferably the mass ratio is 1:1 to 2:1.
  • the super amphiphilic molecule may be a super amphiphilic emulsifier in the responsive super amphiphilic emulsifier, emulsion and preparation method thereof disclosed in Chinese Patent Publication No. CN105542149A.
  • the oil soluble component is toluene, xylene, mixed benzene, diesel, paraffinic oil or kerosene.
  • the aqueous phase is pure water, or a NaCl solution having a concentration of less than 1 wt%, or a CaCl 2 solution having a concentration of less than 0.1 wt%, or a mixed solution of NaCl and CaCl 2 , wherein the concentration of NaCl in the mixed solution is less than 1 wt%, CaCl The concentration of 2 is less than 0.1% by weight.
  • the preparation method of the above emulsion type water-based cleaning agent for oily sludge characterized in that the method comprises the following steps:
  • aqueous phases In terms of 100 parts by weight, 2 to 10 parts of the surfactant, 3 to 10 parts of the oil-soluble component, and the rest are aqueous phases; the above components are mixed and stirred uniformly to obtain a uniform and stable emulsion-type water-based cleaning agent.
  • the stirring speed is 150 to 500 rpm, the stirring time is 25 to 40 minutes, and the stirring temperature is room temperature.
  • the oily sludge is mixed with the emulsion type water-based cleaning agent at a mass ratio of 1:3 to 1:8, and stirred at 60 to 80 ° C to wash the oily sludge, and the mixture after the cleaning is oily.
  • the solid phase is separated by three phases, and finally the solid phase is washed with hot water at the same temperature as the stirring temperature.
  • the stirring time is 10 to 40 minutes, the stirring rotation speed is 200 to 500 rpm, and the rotation speed at the time of the three-phase separation is 1,500 to 2,500 rpm.
  • the emulsion type water-based cleaning agent for oily sludge prepared by the invention is safe and efficient, has simple preparation method, wide application range, and is easy to realize industrial application. Experiments show that the treatment effect on oily sludge is better.
  • FIG. 1 is a sample view showing an emulsion type water-based cleaning agent for oily sludge prepared in Example 1 of the present invention.
  • Fig. 2 is a comparison diagram of the effects of use of the embodiment 1 of the present invention.
  • (a) is the original picture of the oily sludge
  • (b) is the picture of the sludge after the treatment.
  • Fig. 3 is a comparison diagram of the effects of use of the embodiment 5 of the present invention.
  • (a) is the original picture of the oily sludge
  • (b) is the picture of the sludge after the treatment.
  • AES fatty alcohol polyoxyethylene ether sulfate
  • super amphiphilic emulsifier fatty alcohol polyoxyethylene ether sulfate
  • the reactor was stirred at room temperature for 400 minutes at 500 rpm to form a uniformly stable emulsion type water-based cleaning agent.
  • the sample is shown in Fig. 1.
  • the oily sludge was taken from Liaohe Oilfield. The initial parameters were oil content of 57.20%, solid content of 38.98%, and water content of 3.82% (percentage by weight). The macro photograph is shown in Figure 2(a). .
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, cleaned twice with detergent at 80 °C for 30 minutes, the speed is 500 rev / min, then rinsed with hot water at 80 ° C. After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out with a centrifuge (the centrifuge speed is 2500 rpm, the centrifugation time is 6 minutes), and finally the sludge is at 105 ⁇ Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • the treated sludge can be used in Tongjing Road and Drilling Well.
  • AES fatty alcohol polyoxyethylene ether sulfate
  • super amphiphilic emulsifier 6 parts of surfactant (AES and super two) are weighed in an amount of 2:1 or 1:4 or 4:1 by mass ratio of AES (fatty alcohol polyoxyethylene ether sulfate) and super amphiphilic emulsifier in 100 parts by weight.
  • the pro-molecular emulsifiers were 4 parts and 2 parts, 1.2 parts and 4.8 parts, 4.8 parts and 1.2 parts, respectively, 8.5 parts of toluene and 85.5 parts of pure water.
  • Surfactant, toluene and pure water were placed in the reactor in sequence, and stirred at 300 rpm for 30 minutes at room temperature to form an emulsion type water-based cleaning agent having three different surfactant mass ratios.
  • the oily sludge was taken from Liaohe Oilfield. The initial parameters were oil content of 57.20%, solid content of 38.98%, and water content of 3.82% (percentage by weight). The macro photograph is shown in Figure 2(a). .
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, cleaned twice with detergent at 80 °C for 30 minutes, speed 350 rpm, then rinsed with hot water at 80 °C 1 After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out with a centrifuge (centrifuge speed is 2000 rpm, centrifugation time is 6 minutes), and finally sludge is at 105 ⁇ Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • AES fatty alcohol polyoxyethylene ether sulfate
  • super amphiphilic emulsifier 3 parts of oil-soluble component, oil-soluble component, respectively, in a mass ratio of 1:1 It is a mixture of benzene or xylene or paraffin oil or kerosene oil or diesel oil, 95 parts of pure water.
  • AES, super amphiphilic emulsifier, an oil-soluble component and an aqueous phase were sequentially placed in the reactor, and stirred at 150 rpm for 25 minutes at room temperature to form emulsion water of 5 different oil-soluble components.
  • Base cleaning agent
  • the oily sludge was taken from Shengli Oilfield. The initial parameters were oil content of 8.13%, solid content of 41.59% and water content of 50.28%. The macroscopic photograph is shown in Fig. 3(a).
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, cleaned with cleaning agent at 60 °C for 10 times, the speed is 300 rev / min, then rinsed with hot water at 60 ° C. After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out by a centrifuge (the centrifuge speed is 1500 rpm, the centrifugation time is 6 minutes), and finally the sludge is at 105 ⁇ . Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • Oil soluble component Residual oil rate /% (g / 100g dry sludge) Degreasing efficiency /% Mixed benzene 1.33 93.20 Xylene 1.37 92.99 Paraffin oil 8.49 56.57 Gas oil 9.61 50.84 Diesel 11.14 43.01
  • the oily sludge was taken from Shengli Oilfield. The initial parameters were oil content of 8.13%, solid content of 41.59% and water content of 50.28%. The macroscopic photograph is shown in Fig. 3(a).
  • the mass ratio of oily sludge to water-based cleaning agent is 1:3 or 1:5 or 1:8, and it is washed once with 60 ° C for 10 minutes, the speed is 200 rev / min, then Rinse with hot water at 60 °C once, after each cleaning agent and after hot water rinsing, use a centrifuge to separate oil, water and solid three phases (centrifuge speed is 2000 rev / min, centrifugation time is 6 minutes) Finally, the sludge was dried at 105 ⁇ 1 ° C, and the residual oil rate was measured. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • the oily sludge was taken from Shengli Oilfield. The initial parameters were oil content of 8.13%, solid content of 41.59% and water content of 50.28%. The macroscopic photograph is shown in Fig. 3(a).
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, and it is washed once with 60°C cleaning agent for 40 minutes, the speed is 200 rev/min, then rinsed with hot water of 60°C. After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out with a centrifuge (centrifuge speed is 2000 rpm, centrifugation time is 6 minutes), and finally sludge is at 105 ⁇ Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • AES fatty alcohol polyoxyethylene ether sulfate
  • super amphiphilic emulsifier fatty alcohol polyoxyethylene ether sulfate
  • the reactor was stirred at room temperature for 30 minutes at 400 rpm to form a uniformly stable emulsion type water-based cleaning agent.
  • the oily sludge was taken from Liaohe Oilfield. The initial parameters were oil content of 57.20%, solid content of 38.98%, and water content of 3.82% (percentage by weight). The macro photograph is shown in Figure 2(a). .
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, cleaned with cleaning agent at 70 °C for 2 times, each time for 30 minutes, the speed is 300 rev / min, then rinsed with 70 ° C hot water 1 After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out with a centrifuge (centrifuge speed is 2000 rpm, centrifugation time is 6 minutes), and finally sludge is at 105 ⁇ Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).
  • AES fatty alcohol polyoxyethylene ether sulfate
  • super amphiphilic emulsifier 7 parts of toluene and 88.5 parts of water phase were weighed in a ratio of 1:1 by mass.
  • the aqueous phase is respectively 0.3wt% NaCl solution, 0.5wt% NaCl solution, 1.0wt% NaCl solution, 0.01wt% CaCl 2 solution, 0.07wt% CaCl 2 solution, 0.10wt% CaCl 2 solution, NaCl.
  • a mixed solution with CaCl 2 (the NaCl concentration in the mixed solution was 0.3 wt%, and the CaCl 2 concentration was 0.05 wt%).
  • AES a super amphiphilic emulsifier, toluene and an aqueous phase were placed in the reactor in sequence, and stirred at 400 rpm for 30 minutes at room temperature.
  • An emulsion type water-based cleaner which forms seven different aqueous phases.
  • the oily sludge was taken from Liaohe Oilfield. The initial parameters were oil content of 57.20%, solid content of 38.98%, and water content of 3.82% (percentage by weight). The macro photograph is shown in Figure 2(a). .
  • the mass ratio of oily sludge to water-based cleaning agent is 1:4, cleaned twice with detergent at 60 °C for 15 minutes, the speed is 300 rpm, then rinsed with hot water at 60 °C. After that, each time the cleaning agent is cleaned and after the hot water is rinsed, the oil, water and solid three-phase separation is carried out with a centrifuge (centrifuge speed is 2000 rpm, centrifugation time is 6 minutes), and finally sludge is at 105 ⁇ Dry at 1 ° C and measure the residual oil rate. among them:
  • Extractant carbon tetrachloride (Tianjin Guangfu Fine Chemical Research Institute (infrared oil testing)).

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Abstract

一种含油污泥用乳液型水基清洗剂及其制备方法和使用方法。该乳液型水基清洗剂由以下质量百分含量的成分组成，以100重量份计，表面活性剂2～10份，油溶性组分3～10份，其余为水相。其制备方法是，室温下将表面活性剂、油溶性组分和水相搅拌混合均匀，得到均一稳定的乳液型水基清洗剂。使用时，首先将含油污泥与乳液型水基清洗剂混合，在一定温度下搅拌，清洗结束后对混合物进行油、水、固三相分离，最后将固相用相同温度的热水冲洗一次。

Description

一种含油污泥用乳液型水基清洗剂及其制备方法和使用方法 技术领域
本发明涉及一种用于含油污泥清洗的乳液型水基清洗剂，同时涉及该水基清洗剂的制备方法和使用方法，属于含油污泥清洗技术领域。
背景技术
含油污泥是石油开采、储运、炼制及含油污水处理过程中产生的固体废弃物，除含有石油烃类物质外，还含有苯系物、酚类以及重金属盐类等有毒有害物质，不仅占用土地和空间，而且若未经处理直接排放会严重的污染空气、土壤和地下水，已被列入《国家危险废物名录》，在一定程度上制约了国内油田生产的发展。同时，含油污泥又是一种资源，若能开发一种既能消除含油污泥对环境的危害又可回收利用其有用资源的处理技术，将对油田的可持续发展具有重要的实际意义。
含油污泥的处理技术多种多样，现在已知国内外处理含油污泥的方法主要包括资源回收技术、无害化处理技术以及综合利用技术。其中，资源回收技术包括溶剂萃取法，热洗涤法，表面活性剂水溶液清洗法，微乳洗涤法，化学破乳法及固液分离法等；无害化处理技术包括固化处理法，生物处理法和焚烧法等；综合利用技术包括热分解和制砖铺路等，但是每种处理方法都有其优缺点。例如，比较常用的溶剂萃取法虽然可以回收油泥中绝大部分的油相，但是萃取剂价格比较昂贵，在处理过程中不可避免的会造成一定损失，而且还存在着安全隐患问题；焚烧法可以将有机物处理彻底且能有效利用焚烧过程中产生的热能，但该处理过程需要一定量的助燃油和专门的焚烧装置，而且还有废气和废渣的排放，可能会造成二次污染。而热洗涤法、表面活性剂水溶液清洗法、微乳洗涤法等方法具有操作方法简单，设备投资少，对实验条件的要求比较低等优点，还能够有效回收油泥中的油相，在工业上有了一定的应用。
国内外相关含油污泥处理技术的应用实例较多。例如，中国专利文献CN104310734A公开的一种含油污泥处理药剂，该药剂能在室温下有效地降低油水界面张力，而且含油污泥的处理效果比较好，油相回收率能达到96％以上，但是该含油污泥处理药剂配方中加入了蛋白酶和脂肪酶等生物酶，导致其对温度的变化比较敏感，不利于药剂性能的发挥。中国专利文献CN106277709A公开的一种处理含油污泥的环保型清洗剂，该清洗剂的加入量占油泥的质量百分比为2wt％时，最终的油回收率达到了95.9％，处理效果比较好，不足之处是清洗剂中加入的物质比较多，表面活性剂更是多达3种，而且水与油泥之间的比值比较大，这在一定程度上增加了处理过程的难度并造成了资源的浪费。美国专利文献US20150068950A1介绍了一种由烷基糖苷类表面活性剂制备的油包水型纳米乳液用于处理含油污泥，该纳米乳液具有较低的界面张力，而且乳液中纳米尺寸的水滴更容易扩散和吸附到固体的表面，从而促进油相的回收，但是将其用于处理几种不同的含油污泥时，除油效果并不明显，除油效率最高只有 65.8％，最低则仅为10.3％，限制了其进一步的应用；美国专利文献US20090221456A1报道了一种微乳液清洗含油泥沙的方法，在表面活性剂的加入量为1～5wt％时，能将油砂的含油率最低降至0.52％，但是若温度上升至该表面活性剂溶液的浊点时，会出现相分离，清洗效率会显著降低，该微乳液体系对温度的变化比较敏感。
目前绝大部分含油污泥清洗剂为表面活性剂水溶液。
发明内容
本发明针对现有含油污泥处理药剂存在的不足，提供一种性质稳定、安全高效、清洗效果好的含油污泥用乳液型水基清洗剂，同时提供该清洗剂的制备方法和使用方法。
本发明的含油污泥用乳液型水基清洗剂，以100重量份计，包含表面活性剂2～10份，油溶性组分3～10份，其余为水相。
所述表面活性剂包含脂肪醇聚氧乙烯醚硫酸钠和超两亲分子乳化剂，两者之间的质量比为1:4～4:1，优选质量比为1:1～2:1。所述脂肪醇聚氧乙烯醚硫酸钠(AES)别名为乙氧基化烷基硫酸钠或脂肪醇醚硫酸钠，其结构式为RO(CH 2CH 2O) nSO 3Na(R为C12～14烷基，n＝2～3)，质量标准参照GB/T 13529-2011《乙氧基化烷基硫酸钠》，活性物含量为68～72％。所述超两亲分子可采用中国专利文献CN105542149A公开的《具有响应性的超两亲分子乳化剂、乳状液及其制备方法》中的超两亲分子乳化剂。
所述油溶性组分为甲苯、二甲苯、混和苯、柴油、石蜡油或气质油。
所述水相为纯水，或浓度小于1wt％的NaCl溶液，或浓度小于0.1wt％的CaCl 2溶液，或者是NaCl和CaCl 2的混合溶液，该混合溶液中NaCl的浓度小于1wt％，CaCl 2的浓度小于0.1wt％。
上述含油污泥用乳液型水基清洗剂的制备方法，其特征是，包括以下步骤：
以100重量份计，取表面活性剂2～10份，油溶性组分3～10份，其余为水相；将上述各组分混合搅拌均匀，得到均一稳定的乳液型水基清洗剂。所述搅拌转速为150～500转/分钟，搅拌时间为25～40分钟，搅拌温度为室温。
上述含油污泥用乳液型水基清洗剂的使用方法，是：
将含油污泥与所述乳液型水基清洗剂按质量比1:3～1:8的比例混合，并在60～80℃搅拌，对含油污泥进行清洗，对清洗结束后的混合物进行油水固三相分离，最后将固相用与搅拌温度相同的温度下的热水冲洗。所述搅拌时间为10～40分钟，搅拌转速为200～500转/分钟，所述三相分离时的转速为1500～2500转/分钟。
本发明制备的含油污泥用乳液型水基清洗剂安全高效，制备方法简单，适用范围广，易于实现工业应用，实验表明，对含油污泥的处理效果较好。
附图说明
图1是本发明实施例1制备的含油污泥用乳液型水基清洗剂的样品图。
图2是本发明实施例1的使用效果对比图。(a)为含油污泥原始图片，(b)为处理之后 的污泥图片。
图3是本发明实施例5的使用效果对比图。(a)为含油污泥原始图片，(b)为处理之后的污泥图片。
具体实施方式
实施例1
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各5份，甲苯10份，纯水80份，依次放入反应器，室温下以500转/分钟的转速搅拌40分钟，形成均一稳定的乳液型水基清洗剂，其样品见图1。
含油污泥取自辽河油田，其初始参数为含油率为57.20％，含固率为38.98％，含水率为3.82％(百分含量以重量为基准)，其宏观照片见图2中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在80℃下用清洗剂清洗2次，每次30分钟，转速500转/分钟，然后用80℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2500转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
清洗结果如下表所示，处理之后的污泥见图2中(b)。
初始含油率/％ 57.20
残油率/％(g/100g干污泥) 0.33
除油效率/％ 99.78
根据黑龙江省质量技术监督局发布的地方标准《DB23/T 1413-2010油田含油污泥综合利用污染控制标准》，经过处理后的污泥可用于通井路和垫井场。
实施例2
以100重量份计，按AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂质量比2:1或1:4或4:1称取表面活性剂6份(AES和超两亲分子乳化剂分别为4份和2份，1.2份和4.8份，4.8份和1.2份)，甲苯8.5份，纯水85.5份。
将表面活性剂、甲苯和纯水依次放入反应器，室温下以300转/分钟的转速搅拌30分钟，形成3种不同表面活性剂质量比的乳液型水基清洗剂。
含油污泥取自辽河油田，其初始参数为含油率为57.20％，含固率为38.98％，含水率为3.82％(百分含量以重量为基准)，其宏观照片见图2中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在80℃下用清洗剂清洗2次，每次30分钟，转速350转/分钟，然后用80℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2000转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
三种不同表面活性剂质量比的乳液型水基清洗剂对含油污泥的清洗结果如下表所示。
质量比 AES/份 超两亲分子乳化剂/份 残油率/％(g/100g干污泥) 除油效率/％
2:1 4 2 0.71 99.52
1:4 1.2 4.8 1.74 98.81
4:1 4.8 1.2 2.45 98.33
实施例3
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各1份，油溶性组分3份，油溶性组分为混合苯或二甲苯或石蜡油或气质油或柴油，纯水95份。
将AES、超两亲分子乳化剂、一种油溶性组分和水相依次放入反应器，室温下以150转/分钟的转速搅拌25分钟，形成5种不同油溶性组分的乳液型水基清洗剂。
含油污泥取自胜利油田，其初始参数为含油率为8.13％，含固率为41.59％，含水率为50.28％，其宏观照片见图3中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在60℃下用清洗剂清洗1次，每次10分钟，转速300转/分钟，然后用60℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为1500转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
不同油溶性组分的乳液型水基清洗剂对含油污泥的清洗结果如下表所示。
油溶性组分 残油率/％(g/100g干污泥) 除油效率/％
混合苯 1.33 93.20
二甲苯 1.37 92.99
石蜡油 8.49 56.57
气质油 9.61 50.84
柴油 11.14 43.01
实施例4
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各1份，甲苯3份，纯水95份，依次放入反应器，室温下以250转/分钟的转速搅拌25分钟，即可形成均一稳定的乳液型水基清洗剂。
含油污泥取自胜利油田，其初始参数为含油率为8.13％，含固率为41.59％，含水率为50.28％，其宏观照片见图3中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:3或1:5或1:8，在60℃下用清洗剂清洗1次，每次10分钟，转速200转/分钟，然后用60℃的热水冲洗1次，每次清洗剂清 洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2000转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
不同含油污泥与水基清洗剂质量比下含油污泥的清洗结果如下表所示。
含油污泥与水基清洗剂质量比 残油率/％(g/100g干污泥) 除油效率/％
1:3 1.48 92.43
1:5 1.10 94.37
1:8 0.56 97.14
实施例5
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各1份，甲苯3份，纯水95份，依次放入反应器，室温下以250转/分钟的转速搅拌25分钟，即可形成均一稳定的乳液型水基清洗剂。
含油污泥取自胜利油田，其初始参数为含油率为8.13％，含固率为41.59％，含水率为50.28％，其宏观照片见图3中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在60℃下用清洗剂清洗1次，每次40分钟，转速200转/分钟，然后用60℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2000转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
含油污泥的清洗结果如下表所示,处理之后的污泥见图3中(b)。
初始含油率/％ 8.13
残油率/％(g/100g干污泥) 1.74
除油效率/％ 91.10
实施例6
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各2.25份，甲苯7份，纯水88.5份，依次放入反应器，室温下以400转/分钟的转速搅拌30分钟，即可形成均一稳定的乳液型水基清洗剂。
含油污泥取自辽河油田，其初始参数为含油率为57.20％，含固率为38.98％，含水率为3.82％(百分含量以重量为基准)，其宏观照片见图2中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在70℃下用清洗剂清洗2次，每次30分钟，转速300转/分钟，然后用70℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2000转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
含油污泥的清洗结果如下表所示。
初始含油率/％ 57.20
残油率/％(g/100g干污泥) 1.21
除油效率/％ 99.18
实施例7
以100重量份计，按质量比1:1的比例分别称取AES(脂肪醇聚氧乙烯醚硫酸钠)和超两亲分子乳化剂各2.25份，甲苯7份，水相88.5份。水相分别为浓度0.3wt％NaCl溶液，浓度0.5wt％NaCl溶液，浓度1.0wt％NaCl溶液，浓度0.01wt％CaCl 2溶液，浓度0.07wt％CaCl 2溶液，浓度0.10wt％CaCl 2溶液，NaCl与CaCl 2的混合溶液(混合溶液中NaCl浓度为0.3wt％，CaCl 2浓度为0.05wt％)。
将AES、超两亲分子乳化剂、甲苯和一种水相依次放入反应器，室温下以400转/分钟的转速搅拌30分钟。形成7种不同水相的乳液型水基清洗剂。
含油污泥取自辽河油田，其初始参数为含油率为57.20％，含固率为38.98％，含水率为3.82％(百分含量以重量为基准)，其宏观照片见图2中(a)。
清洗效果测试：含油污泥与水基清洗剂质量比为1:4，在60℃下用清洗剂清洗2次，每次15分钟，转速300转/分钟，然后用60℃的热水冲洗1次，每次清洗剂清洗后和热水冲洗后均用离心机进行油、水、固三相分离(离心机转速为2000转/分钟，离心时间为6分钟)，最后将污泥在105±1℃下烘干，测定其残油率。其中：
仪器：Oil 460型红外分光测油仪；
萃取剂：四氯化碳(天津市光复精细化工研究所(红外测油专用))。
不同水相的乳液型水基清洗剂对含油污泥的清洗结果如下表所示。
Figure PCTCN2018085284-appb-000001
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它任何未背离本发明的精神实质与原理下所作的任何改变、修饰、组合、简化、改进等，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种含油污泥用乳液型水基清洗剂，其特征是，以100重量份计，表面活性剂2～10份，油溶性组分3～10份，其余为水相。
  2. 根据权利要求1所述的含油污泥用乳液型水基清洗剂，其特征是，所述表面活性剂包含脂肪醇聚氧乙烯醚硫酸钠和超两亲分子乳化剂，两者质量比为1:4～4:1。
  3. 根据权利要求1所述的含油污泥用乳液型水基清洗剂，其特征是，所述表面活性剂包含脂肪醇聚氧乙烯醚硫酸钠和超两亲分子乳化剂，两者质量比为1:1～2:1。
  4. 根据权利要求1所述的含油污泥用乳液型水基清洗剂，其特征是，所述油溶性组分为甲苯、二甲苯、混和苯、柴油、石蜡油或气质油。
  5. 根据权利要求1所述的含油污泥用乳液型水基清洗剂，其特征是，所述水相为纯水，或浓度小于1wt％的NaCl溶液，或浓度小于0.1wt％的CaCl 2溶液，或者是NaCl和CaCl 2的混合溶液，该混合溶液中NaCl的浓度小于1wt％，CaCl 2的浓度小于0.1wt％。
  6. 一种权利要求1所述含油污泥用乳液型水基清洗剂的制备方法，其特征是，包括以下步骤：
    以100重量份计，称取表面活性剂2～10份，油溶性组分3～10份，其余为水相；将上述各组分混合搅拌均匀，得到均一稳定的乳液型水基清洗剂。
  7. 根据权利要求6所述含油污泥用乳液型水基清洗剂的制备方法，其特征是，所述搅拌转速为150～500转/分钟，搅拌时间为25～40分钟，搅拌温度为室温。
  8. 一种权利要求1-5所述的任意一种含油污泥用乳液型水基清洗剂的使用方法，其特征是，将含油污泥与所述乳液型水基清洗剂按质量比1:3～1:8的比例混合，并在60～80℃搅拌，对含油污泥进行清洗，对清洗结束后的混合物进行油水固三相分离，最后将固相用相同温度下的热水冲洗。
  9. 根据权利要求8所述的含油污泥用乳液型水基清洗剂的使用方法，其特征是，所述搅拌时间为10～40分钟，搅拌转速为200～500转/分钟。
  10. 根据权利要求8所述的含油污泥用乳液型水基清洗剂的使用方法，其特征是，所述三相分离时的转速为1500～2500转/分钟。
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