CN110387257B - Demetallizing agent suitable for demetallizing clear tank oil, composition thereof and method for treating clear tank oil - Google Patents
Demetallizing agent suitable for demetallizing clear tank oil, composition thereof and method for treating clear tank oil Download PDFInfo
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- CN110387257B CN110387257B CN201810356264.9A CN201810356264A CN110387257B CN 110387257 B CN110387257 B CN 110387257B CN 201810356264 A CN201810356264 A CN 201810356264A CN 110387257 B CN110387257 B CN 110387257B
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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Abstract
The invention relates to the field of clear tank oil treatment, in particular to a demetallizing agent suitable for clear tank oil demetallization, a composition thereof and a treatment method of clear tank oil. The composition contains a sterilization component, a cocatalyst component, an organic carboxylic acid component and a wetting modification component; the bactericidal component is one or more of oilfield bactericides; the cocatalyst component is one or more of carboxylic acid ammonium salt; the wetting modification component is a combination of polyoxyethylene ether surfactant and saturated straight-chain alcohol with more than 6 carbon atoms. The demetallizing agent containing the composition can effectively remove metal impurities in the clear tank oil through the synergistic effect of the components in the composition and the operation of the treatment method of the invention when being applied to the treatment of the clear tank oil.
Description
Technical Field
The invention relates to the field of clear tank oil treatment, in particular to a demetallizing agent suitable for clear tank oil demetallization, a composition thereof and a treatment method of clear tank oil.
Background
In the long-time storage and transportation production of the crude oil storage tank, high-melting-point wax, colloid, asphaltene, entrained metal compounds, mechanical impurities, water and the like in the crude oil naturally settle due to density difference and accumulate at the bottom of the oil tank to form a black and thick colloid substance layer, namely oil sludge at the bottom of the tank. The effective volume of the storage tank is reduced by the oil sludge at the bottom of the tank, and the oil sludge with the saline water can aggravate the corrosion of the inner wall of the storage tank; after long-term storage, the crude oil also generates oxidation, condensation and other reactions under the action of air and light, so that the amount of oil sludge is increased. The tank bottom oil sludge increases along with the extension of continuous storage and transportation time, seriously influences the storage, transportation and production of the oil tank over time, and must be removed periodically. According to general regulations in the petrochemical industry of China, a crude oil storage tank needs to be cleaned and overhauled at intervals of 5-6 years. Tank bottom sludge is generally rich in about 70% of oil substances.
The crude oil storage tank mechanical cleaning technology has the advantages of high oil recovery rate, short tank cleaning construction period, high safety and the like, and is widely applied to industry at present. The technology generally adopts crude oil with the same kind or similar properties as cleaning oil, and the cleaning oil is injected into a storage tank through cleaning equipment for closed cleaning. Firstly, crushing oil sludge at the bottom of a tank by using cleaning oil sprayed at a high speed, dissolving petroleum substances in the oil sludge, and washing the inner wall of the tank; then, the mixed fluid generated in the tank is subjected to solid-liquid filtration separation and oil-water separation in sequence, and the recovered petroleum substance is the 'clear tank oil'. The amount of clear tank oil produced during mechanical cleaning of the tank is large, e.g. 1 station 10 km3The crude oil storage tank of (1) will produce about 5000 tons of clean oil when mechanically cleaned.
The clear tank oil has the characteristics of high metal content (especially iron element mainly existing in the form of solid particles of a sulfur-iron compound), high viscosity, complex composition, high water content, stable emulsification, high mechanical impurity content and the like. The sulphur iron compound particles in the pig oil are mainly due to the corrosive action of sulphate reducing bacteria in the bottom sludge of the tank, and comprise various compositions and morphologies, for example, mackenoite (FeS)1-x) Cubic ferrous sulfide (FeS), merle ferro-sulphur (FeS), pyrrhotite (Fe)(1-x)S)、Fe3S4And pyrite (FeS)2) And the like.
The content of iron element existing in the form of sulphur iron compound particles in the clear tank oil can reach hundreds or even thousands of mg/kg, which is far higher than the sum (several to tens of mg/kg) of the content of common water-soluble iron (existing in the form of sulfate, hydrochloride and the like) and oil-soluble iron (existing in the form of carboxylate, naphthenate, porphyrin compound, organic complex and the like) in the crude oil; under the action of density difference, the distribution of the ferro-sulphur compound particles in the clear tank oil is not uniform, and the content of the ferro-sulphur compound particles is gradually increased from top to bottom in the longitudinal direction. In the common electric desalting process of a refinery, the water-soluble metal compound is easy to be removed by washing; by adding a medium-strong acid demetallizing agent, the oil-soluble metal compounds existing in the forms of carboxylate and naphthenate can be removed to a certain extent; the sulfur iron compound particles which are insoluble in water and oil can hardly be removed by water washing, and the sulfur iron compound particles in the clear tank oil are difficult to remove by adding a large amount of medium-strong acid demetallizing agent from the aspects of equipment corrosion prevention and control and economy. On the other hand, the surface wettability and conductivity of the pyrite compound make it difficult to process the pig oil through the electro-desalting unit, mainly because: (1) because the surface energy is lower, the surface of the ferro-sulphur compound particles has certain lipophilicity, and the ferro-sulphur compound particles have the characteristics of oil-water amphipathy on the whole, are easy to enrich in an oil-water interface and are difficult to settle into a water phase. When a small amount of pyrite compound particles are deposited on the surfaces of other fine particles of mechanical impurities (such as silt and the like) which originally have good water wettability, the surfaces of the mechanical impurities have oil-water double wettability similar to that of the pyrite compound particles, and are easy to be adsorbed on an oil-water interface. The sulfur iron compound particles and the mechanical impurity particles enriched on the oil-water interface are barriers for preventing oil droplets or water droplets from being mutually combined, and are the main reason that the oil-water emulsion is difficult to break emulsion and dewater. (2) The existence of a large amount of high-conductivity pyrite compound particles enables the conductivity of the tank cleaning oil to be strong, so that the tank cleaning oil is easy to break down under the action of an electric field to cause short circuit. Therefore, if the clean oil is processed by a normal pressure reducing device, the current of the electric desalting tank is increased, an electric field is broken, even tripping is caused, and an oil-water interface in the electric desalting tank is induced to form a thick emulsifying layer, so that the cut water contains oil and blackens. In addition, a large amount of sulfur iron compound particles in the clear tank oil are difficult to be effectively removed in the electric desalting unit by adopting a conventional method, and after atmospheric and vacuum distillation, iron elements in the sulfur iron compound can be enriched in heavy distillate oil and residual oil, so that the stable operation of subsequent oil refining devices such as catalytic cracking, residual oil hydrogenation and the like is not facilitated.
At present, the common method for treating the clear tank oil in the industry is to send the clear tank oil to a delayed coking device for direct blending, but the economic efficiency is poor, and the economic value maximization of the clear tank oil cannot be realized.
Disclosure of Invention
The invention aims to provide a demetallizing agent which can effectively remove metal impurities in clear tank oil and is suitable for demetallizing the clear tank oil, a composition thereof and a treatment method of the clear tank oil.
In order to achieve the above object, the present invention provides a demetallizing agent composition for demetallizing clear can oil, which comprises a bactericidal component, a co-catalytic component, an organic carboxylic acid component and a wetting modification component;
wherein the bactericidal component is one or more of oilfield bactericides;
the cocatalyst component is one or more of carboxylic acid ammonium salt;
the wetting modification component is a combination of polyoxyethylene ether surfactant and saturated straight-chain alcohol with more than 6 carbon atoms.
In a second aspect, the present invention provides a demetallizing agent comprising the above composition.
In a third aspect, the present invention provides a method for processing clear tank oil, wherein the clear tank oil contains pyrite compound particles, the method comprising: mixing the clear tank oil, the crude oil, the demulsifier, the demetallization agent and water to obtain an oil-water emulsion; under the condition of electric desalting, carrying out electric desalting treatment on the oil-water emulsion to separate cut water and dehydrated oil;
wherein the demetallization agent is the demetallization agent provided by the second aspect.
The demetallizing agent containing the composition can effectively remove metal impurities in the clear tank oil through the synergistic effect of the components in the composition and the operation of the treatment method of the invention, for example, metal elements such as iron, calcium, sodium, potassium, magnesium, aluminum and the like can be effectively removed, and the removal rate of various metals can reach more than 90%. The method for treating the clear tank oil also has the advantages of low cost and simple operation. In addition, because the demetallizing agent adopted by the invention has excellent water solubility and basically does not remain in the oil phase, the demetallizing agent does not cause harm to subsequent oil refining devices such as catalytic cracking, residual oil hydrogenation and the like.
Drawings
FIG. 1 is a schematic diagram of a system structure adopted in the method for processing the boiled oil according to the present invention.
FIG. 2 is a schematic view of another system structure adopted in the method for processing the boiled oil according to the present invention.
Description of the reference numerals
1-a pump; 2-a heater; 3-pump; 4-a mixer;
5-a mixing valve; 6-electric desalting tank; 7-pump;
8-a mixer; 9-a mixing valve; 10-electric desalting tank;
a-clear tank oil; b-crude oil; c-mixed oil; d, primary water injection;
e-a first oil-water emulsion; f, first-stage dewatering oil; g, primary cutting water;
h-secondary water injection; i-a secondary oil-water emulsion; k-secondary cutting water;
j-secondary dewatering oil.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a demetallization agent composition for clear tank oil demetallization, which comprises a sterilization component, a cocatalyst component, an organic carboxylic acid component and a wetting modification component;
wherein the bactericidal component is one or more of oilfield bactericides;
the cocatalyst component is one or more of carboxylic acid ammonium salt;
the wetting modification component is a combination of polyoxyethylene ether surfactant and saturated straight-chain alcohol with more than 6 carbon atoms.
According to the present invention, the synergistic effect between the respective active ingredients of the composition of the present invention enables the demetallizing agent comprising the composition of the present invention to efficiently remove metal impurities in the can varnish when used in the electrical desalting treatment of the can varnish, and thus, metal elements such as iron, calcium, sodium, potassium, magnesium, aluminum, and the like can be effectively removed. In order to obtain a better demetallization effect, it is preferable that the content of the co-catalyst component is 10 to 150 parts by weight, the content of the organic carboxylic acid component is 20 to 100 parts by weight, and the content of the wetting modification component is 0.1 to 20 parts by weight, based on 100 parts by weight of the germicidal component.
Preferably, the content of the catalysis-promoting component is 20-120 parts by weight, the content of the organic carboxylic acid component is 25-80 parts by weight, and the content of the wetting modification component is 0.5-15 parts by weight based on 100 parts by weight of the sterilization component.
More preferably, the co-catalyst component is contained in an amount of 22 to 100 parts by weight, the organic carboxylic acid component is contained in an amount of 30 to 75 parts by weight, and the wetting modification component is contained in an amount of 0.5 to 10 parts by weight, based on 100 parts by weight of the germicidal component.
In a preferred embodiment of the present invention, the content of the co-catalyst component is 24 to 100 parts by weight, the content of the organic carboxylic acid component is 35 to 70 parts by weight, and the content of the wettability-modifying component is 1.5 to 8.5 parts by weight, based on 100 parts by weight of the fungicidal component.
According to the invention, the sterilization component is one or more of oilfield bactericides, so that the sterilization component can help to kill or inhibit bacteria such as sulfate reducing bacteria, iron bacteria and the like in the clear tank oil, thereby weakening or eliminating the barrier effect of bacterial thalli adsorbed on an oil-water interface on mutual coalescence of oil droplets or water droplets. Such oilfield biocides may be, for example, one or more of quaternary phosphonium salt biocides, organic guanidine biocides, quaternary ammonium salt biocides and isothiazolinone biocides. Preferably, the oilfield bactericide is one or more of tetrakis hydroxymethyl phosphonium sulfate, dodecylguanidine acetate, dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium bromide, hexadecylpyridinium chloride, dicumyl dimethyl ammonium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one. Wherein, when the oilfield bactericide is tetrakis (hydroxymethyl) phosphonium sulfate, the obtained composition can be more beneficial to removing metal impurities, particularly sulphur-iron compound particles.
According to the invention, the promoting component will favour the formation of water-soluble complexes of the metallic impurities, and in the present invention the promoting component is one or more of ammonium carboxylate salts, suitably selected from ammonium salts of a wide variety of carboxylic acids, preferably one or more of ammonium acetate, ammonium propionate, ammonium oxalate, ammonium malonate, ammonium malate, ammonium succinate and ammonium citrate. The inventors of the present invention have found that when a combination of ammonium oxalate and ammonium citrate is used as the co-promoting component, that is, when the ammonium carboxylate salt is a combination of ammonium oxalate and ammonium citrate, it can be better combined with other effective ingredients of the composition of the present invention to obtain a higher metal removal rate.
When a combination of ammonium oxalate and ammonium citrate is used as the co-catalyst component, preferably the weight ratio of ammonium oxalate to ammonium citrate is 1: 0.5 to 10, preferably 1: 1-5.
According to the present invention, the organic carboxylic acid component may be one or more of a di-organic carboxylic acid and a tri-organic carboxylic acid, preferably a combination of a di-organic carboxylic acid and a tri-organic carboxylic acid. Wherein, the dibasic organic carboxylic acid is preferably one or more of oxalic acid, malonic acid, malic acid and succinic acid, and the tribasic organic carboxylic acid is preferably one or more of citric acid, 1, 2-ethyltricarboxylic acid, 1,2, 3-propyltricarboxylic acid and trimesic acid. When a combination of a di-organic carboxylic acid and a tri-organic carboxylic acid is used as the organic carboxylic acid component of the present invention, it is preferable that the weight ratio of the di-organic carboxylic acid to the tri-organic carboxylic acid is 1: 0.5 to 10, preferably 1: 1-4.
In the present invention, the inventors of the present invention have found that when a combination of citric acid and oxalic acid is used as the organic carboxylic acid component of the present invention, it can be better compounded with other effective ingredients of the composition of the present invention to obtain a better demetallization effect and less contamination of the oil phase after dehydration.
According to the invention, the wetting modification component is the combination of polyoxyethylene ether surfactant and saturated straight-chain alcohol with more than 6 carbon atoms, so that the combined wetting modification component is helpful for inverting the oil-water double wettability of the surface of the pyrite compound particles in the clear tank oil into hydrophilicity, and is further helpful for the pyrite compound to enter a water phase for being removed. Wherein, the polyoxyethylene ether surfactant is preferably one or more of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether. The fatty alcohol-polyoxyethylene ether has an oxyethylene ether structure polymerization degree of 4-6, and the carbon atom number of the group provided by the fatty alcohol is 6-14, such as one or more of isodecyl alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, isomeric tridecyl alcohol polyoxyethylene ether, and the like. The polymerization degree of the structure of the polyoxyethylene ether in the alkylphenol polyoxyethylene is 4-6, and the carbon atom number of the group provided by the alkyl is 8 or 9. Preferably, the polyoxyethylene ether surfactant is one or more of alkylphenol polyoxyethylene, more preferably octyl phenol polyoxyethylene ether and/or nonyl phenol polyoxyethylene ether.
Wherein, the saturated straight-chain alcohol is preferably one or more of saturated straight-chain alcohols of C7-C14, and more preferably one or more of n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol and n-tetradecanol.
In a preferred embodiment of the present invention, the polyoxyethylene ether-based surfactant is nonylphenol polyoxyethylene ether, and the saturated linear alcohol is n-octanol. The wetting modifying component in such embodiments can be better complexed with other active ingredients of the composition of the present invention to achieve a more excellent demetallization effect.
According to the present invention, in the wetting modification component, the ratio of the polyoxyethylene ether surfactant to the saturated linear alcohol may vary within a wide range, and preferably, the weight ratio of the polyoxyethylene ether surfactant to the saturated linear alcohol is 1: 0.5 to 10, preferably 1: 1-3.
According to the invention, the composition can also contain a cosolvent so as to facilitate the dissolution and uniform mixing of the active ingredients of the composition, thereby better exerting the coordination effect among the components. Preferably, the co-solvent is a mixture of an alcoholic solvent and water. The alcohol solvent may be a small molecule alcohol solvent, such as an alcohol solvent of C1-C4, and specific examples thereof may be one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, preferably ethanol.
According to the present invention, the ratio of the alcohol solvent to water can be varied within a wide range, and in order to obtain a better dissolving and mixing effect, the weight ratio of the alcohol solvent to water is preferably 1: 0.5 to 10, preferably 1: 1-6.
According to the present invention, the content of the co-solvent may be appropriately adjusted as needed, and preferably, the content of the co-solvent is 50 to 500 parts by weight, preferably 60 to 450 parts by weight, based on 100 parts by weight of the bactericidal component.
In a second aspect, the present invention provides a demetallizing agent comprising the above composition.
The demetallization agent preferably consists of the bactericidal component, the cocatalyst component, the organic carboxylic acid component, the wetting modification component and the cosolvent. In this case, in a preferred embodiment of the present invention, the germicidal component is present in an amount of 10 to 40 wt%, the co-catalytic component is present in an amount of 5 to 20 wt%, the organic carboxylic acid component is present in an amount of 6 to 25 wt%, the wettability modifying component is present in an amount of 0.1 to 5 wt%, and the co-solvent is present in an amount of 20 to 65 wt%, based on the total weight of the demetallizing agent.
According to the invention, the demetallization agent can be prepared by mixing the components, or can be prepared by mixing the cosolvent and the cocatalyst, and then introducing the sterilization component, the organic carboxylic acid component and the wetting modification component for mixing.
In a third aspect, the present invention provides a method for processing clear tank oil, wherein the clear tank oil contains pyrite compound particles, the method comprising: mixing the clear tank oil, the crude oil, the demulsifier, the demetallization agent and water to obtain an oil-water emulsion; under the condition of electric desalting, carrying out electric desalting treatment on the oil-water emulsion to separate cut water and dehydrated oil;
wherein the demetallization agent is the demetallization agent provided by the second aspect.
According to the invention, the sequence of mixing the clear tank oil, the crude oil, the demulsifier, the demetallizing agent and the water can be carried out in various feasible ways, for example, the clear tank oil and the crude oil can be mixed to obtain mixed oil, and then the mixed oil is mixed with the demulsifier, the demetallizing agent and the water to obtain the oil-water emulsion; or mixing the demetallization agent with water to form an aqueous solution containing the demetallization agent, and then contacting and mixing with the demulsifier and the mixed oil to obtain the oil-water emulsion; or, the demetallization agent, the demulsifier and water are mixed in advance to form an aqueous solution containing the demetallization agent and the demulsifier, and then the aqueous solution is contacted and mixed with the mixed oil to obtain the oil-water emulsion; or the demetallization agent, the demulsifier and the water are respectively added into the mixed oil to be mixed and contacted together, so as to obtain the oil-water emulsion.
Preferably, the method comprises: mixing the clear tank oil, the crude oil and water to obtain an oil-water emulsion; wherein the water injection is an aqueous solution containing a demulsifier and a demetallization agent.
More preferably, the method comprises: mixing the clear tank oil and the crude oil to obtain mixed oil, and mixing the mixed oil with water to obtain the oil-water emulsion. In this case, more preferably, the method further includes: heating the mixed oil to 70-90 ℃, and then mixing with water injection.
According to the invention, the content of the demulsifier and the demetallizer in the water injection can vary within a wide range, and preferably the content of the demulsifier in the water injection is 0.01 to 0.2 wt% and the content of the demetallizer in the water injection is 0.05 to 5 wt%.
According to the invention, the dosage of the water injection can be properly adjusted according to requirements, the invention can obtain better treatment effect of the clear tank oil under the condition of lower dosage of the water injection, and preferably, the dosage of the water injection is 5-10 parts by weight based on 100 parts by weight of the total weight of the clear tank oil and the crude oil.
According to the invention, the demulsifier can be a demulsifier which is conventionally used for clear tank oil demulsification, can be a water-soluble demulsifier or an oil-soluble demulsifier, and has a good demulsification effect on the mixed oil to be treated, and specific examples of the demulsifier can be one or more of a polyoxyethylene polyoxypropylene ether demulsifier, a polyalkylene glycol alkyd resin demulsifier, a polyester demulsifier, a multipolymer demulsifier, a dendritic polyamide-amine demulsifier, a cationic demulsifier and the like.
According to the invention, the clear tank oil is the petroleum substance recovered in the mechanical cleaning process of the crude oil storage tank, has higher metal element content, and has the characteristics of large viscosity, complex composition, high water content, stable emulsification, high mechanical impurity content and the like, and the clear tank oil can be treated by the method disclosed by the invention to reduce the metal element content, particularly the content of the ferro-sulphur compound particles, for example, the clear tank oil has the Fe element content of 200-2000Mg/kg, the Ca element content of 50-500Mg/kg, the Na element content of 50-500Mg/kg, the K element content of 5-20Mg/kg, the Mg element content of 10-50Mg/kg and the Al element content of 20-100 Mg/kg; usually, most of the Fe element exists in the form of solid particles of the pyrite compound.
According to the invention, the crude oil is used for diluting the clear tank oil so as to reduce the concentration of metal elements in the obtained mixed oil, thereby facilitating the electric desalting treatment; the crude oil has a lower content of metallic elements than that of the clear tank oil and can be treated by the method of the invention as long as required.
According to the invention, the quantities of the clear tank oil and the crude oil can vary within wide limits, preferably in a weight ratio of 1 to 25: 100.
according to the present invention, the electric desalting treatment can be appropriately adjusted according to the quality of the boiled oil to be treated, for example, the conditions of the electric desalting treatment include: the temperature is 100-130 ℃, the electric field intensity is 700-1200V/cm (referring to the electric field intensity of the strong electric field area), and the pressure is 0.3-0.8 MPa. The electric desalting treatment is usually carried out in an electric desalting tank, and the electric desalting tank is not particularly limited in the present invention, and an electric desalting tank conventionally used in the art may be used. For this reason, the residence time in the electrodesalting tank may be suitably adjusted according to the requirements of the electrodesalting process, for example, the residence time in the electrodesalting tank is 20 to 40 min.
According to the invention, when the clear tank oil is blended with the crude oil according to a lower proportion, the mixed oil only needs one-time demetallization treatment to reduce the content of metal impurities to a required level; however, when the blending ratio of the clean tank oil to the crude oil is high, multistage demetallization operation is required until the metal content meets the requirement. For example, when the blending ratio of the clean oil to the crude oil is high, the content of the metal element can be reduced to a low level through the secondary demetallization treatment. For this reason, in the case of using the secondary demetallization treatment, preferably, the method comprises:
(1) mixing the clear tank oil, the crude oil and primary water injection to obtain primary oil-water emulsion;
(2) under the condition of first-stage electric desalting, carrying out first-stage electric desalting treatment on the first-stage oil-water emulsion to separate first-stage cut water and first-stage dehydrated oil;
(3) mixing the first-stage dehydrated oil and the second-stage injected water to obtain a second-stage oil-water emulsion;
(4) and under the condition of secondary electric desalting, carrying out secondary electric desalting treatment on the secondary oil-water emulsion to separate and obtain secondary cut water and secondary dehydrated oil.
According to the present invention, the primary water injection and the secondary water injection may be the water injection described above, and the amounts thereof may be independently selected from the amounts described above. The primary and secondary electro-desalting processes are also as described above and the present invention is not described in detail herein.
Because the content of metal elements in the secondary cut water is low, and part of the metal elements still have the effect of a demetallization agent and a demulsifier; for this reason, although fresh water may be used as the primary water injection, from the viewpoint of cost saving, it is more preferable to use part of the secondary cut-off water as the primary water injection by mixing with the fresh water injection, or to use part of the secondary cut-off water alone as the entire primary water injection, that is, it is preferable to recycle at least part of the secondary cut-off water as part of the primary water injection.
Wherein, if only one-stage demetallization treatment is adopted, the system and the related flow shown in FIG. 1 can be adopted to carry out electric desalting treatment, specifically, clear tank oil is mixed with crude oil to form mixed oil, and the mixed oil enters a heater 2 through a pump 1 to be preheated; the injected water is converged with the preheated mixed oil in a pipeline through a pump 3, then the injected water sequentially enters a mixer 4 and a mixing valve 5, and the oil phase and the water phase are fully mixed to form an oil-water emulsion; the oil-water emulsion enters an electric desalting tank 6 for electric desalting treatment, cut water and dehydrated oil are separated under the action of an electric field and a gravitational field, the cut water is discharged from an outlet at the bottom of the electric desalting tank 6 and the dehydrated oil is discharged from an outlet at the top of the electric desalting tank 6.
Wherein, if the secondary demetallization treatment is adopted, the system and the related flow shown in FIG. 2 can be adopted to carry out the electric desalting treatment, specifically, the clear tank oil b is mixed with the crude oil a to form the mixed oil c, and the mixed oil is preheated by the heater 2 through the pump 1; the primary water injection d is converged with the preheated mixed oil in a pipeline through a pump 3, then sequentially enters a mixer 4 and a mixing valve 5, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the primary oil-water emulsion e enters an electric desalting tank 6 again for primary electric desalting treatment, and primary cut water g and primary dehydrated oil f are separated under the action of an electric field and a gravitational field; and (4) discharging the primary cut water g out of the system, and performing subsequent secondary demetallization treatment on the primary demetallized oil f. The secondary water injection h is converged with the primary dewatering oil f in a pipeline through a pump 7, then sequentially enters a mixer 8 and a mixing valve 9, and the oil phase and the water phase are fully mixed to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10 for secondary electric desalting treatment, and secondary cut water k and secondary dehydrated oil j are separated under the action of an electric field and a gravitational field; the secondary cut-off water k is either directly discharged or, as shown in fig. 2, is merged with the fresh water injection as primary water injection d.
The present invention will be described in detail below by way of examples.
In the following examples:
the metal removal rate is (metal element content of the mixed oil-average metal element content of the dehydrated oil)/metal element content of the mixed oil is 100%, and the average metal element content of the dehydrated oil refers to the metal element content of the upper layer and the metal element content of the lower layer of the oil sample which are respectively measured, and the average metal element content of the upper layer and the average metal element content of the lower layer of the oil sample are calculated.
The polyoxyethylene nonyl phenyl ether is NP-4 from chemical industry Co., Ltd in Guangzhou, and the polymerization degree of the structure of the polyoxyethylene ether is 4.
The octyl phenol polyoxyethylene ether is OP-6 purchased from the company of Schchen Tai Lanxing science and technology, and the structural polymerization degree of the polyoxyethylene ether is 6.
The polyoxyethylene lauryl ether is purchased from Brij L4 of Shanghai Aladdin Biotechnology, Inc., and has a structural polymerization degree of 4.
Demulsifier # 1 was BSA108 (an alkyl phenol resin block polyether demulsifier) available from shozu corporation.
The properties of the clear tank oil and the crude oil are shown in table 1.
TABLE 1
Note:*most of the iron element in the clear tank oil exists in the form of solid particles of sulfur-iron compound.
Demetallizing agent preparations 1 to 20
This preparation example is intended to illustrate the demetallizing agent and the composition thereof of the present invention.
The cosolvent and the cocatalyst component (the amount and the type of each component are shown in table 2) are stirred and mixed until the cocatalyst component is dissolved, then the bactericidal component, the organic carboxylic acid component and the wetting modification component (the amount and the type of each component are shown in table 2) are introduced, stirred for a certain time at a specified stirring speed (the stirring condition is shown in table 2), and uniformly mixed to obtain the demetallization agent.
Preparation of demetallizing agent comparative example 1
According to the method described in preparation example 3 of the demetallizing agent, except that the co-catalyst component was not used, and the content of the organic carboxylic acid component was adjusted, as shown in Table 2, specifically, to obtain the demetallizing agent DA 1.
Preparation of demetallizing agent comparative example 2
According to the method described in preparation example 3 of the demetallizing agent, except that the organic carboxylic acid component was not used and the content of the co-catalyst component was adjusted, as shown in Table 2, the demetallizing agent DA2 was obtained.
Demetallizing agent preparation comparative example 3
According to the method described in preparation example 3 of the demetallizing agent, except that n-octanol was replaced with nonylphenol polyoxyethylene ether in equal parts by weight, as shown in Table 2, a demetallizing agent DA3 was obtained.
Demetallizing agent preparation comparative example 4
According to the method described in preparation example 3 of the demetallizing agent, except that nonylphenol polyoxyethylene ether was replaced with n-octanol in equal parts by weight, as shown in Table 2, a demetallizing agent DA4 was obtained.
Preparation of demetallizing agent comparative example 5
According to the method described in preparation example 3 of the demetallizing agent, except that n-octanol was replaced by an equal part by weight of ethanol, as shown in Table 2, the demetallizing agent DA5 was obtained.
TABLE 2
Example 1
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A1 and the demulsifier No. 1 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.54 wt%, and the content of the demulsifier is 0.03 wt%.
(2) By adopting the system and the process shown in the figure 1, the clear tank oil is mixed into the crude oil according to the mass ratio of 1:100 to form mixed oil, and the mixed oil enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 80 ℃; the water is injected and is converged with the preheated mixed oil at the flow rate of 250g/h through a pump 3, then the mixed oil sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 50kPa, and oil and water are fully mixed to form oil-water emulsion; the oil-water emulsion enters an electric desalting tank 6, and electric desalting treatment is carried out at the temperature of 120 ℃, the electric field intensity of 1000V/cm and the pressure of 0.5MPa (the retention time is 30 min); under the action of an electric field and a gravity field, primary cut water and primary dehydrated oil are separated, the primary cut water is discharged out of the system from an outlet at the bottom of the electric desalting tank 6, and the primary dehydrated oil is directly discharged out of the system without secondary demetalization treatment.
The metal element contents of the upper and lower layers of the first-stage dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Example 2
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A2 and the demulsifier No. 2 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.5 weight percent, and the content of the demulsifier is 0.019 weight percent.
(2) By adopting the system and the flow shown in the figure 2, the clear tank oil b is mixed into the crude oil a according to the mass ratio of 5:100 to form mixed oil c, and the mixed oil c enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 80 ℃; the primary water injection d is converged with the preheated mixed oil at the flow rate of 400g/h through a pump 3, and then sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 50kPa, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the first-stage oil-water emulsion e enters an electric desalting tank 6, and first-stage electric desalting treatment is carried out at the temperature of 120 ℃, the electric field intensity of 1000V/cm and the pressure of 0.5MPa (the retention time is 25 min); and separating first-stage cut water g and first-stage dewatering oil f under the action of an electric field and a gravity field, discharging the first-stage cut water g from an outlet at the bottom of the electric desalting tank 6 to a system, and carrying out subsequent second-stage demetallization treatment on the first-stage dewatering oil f. Converging the secondary water injection h with the primary dehydrated oil f at the flow rate of 400g/h through a pump 7, then sequentially entering a mixer 8 and a mixing valve 9, wherein the pressure difference of the mixing valve is 50kPa, and fully mixing the oil phase and the water phase to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10, and secondary electric desalting treatment is carried out at the temperature of 120 ℃, the electric field intensity of 1000V/cm and the pressure of 0.5MPa (the retention time is 25 min); separating secondary cut water k and secondary dehydrated oil j under the action of an electric field and a gravity field; converging 60 wt% of secondary cut water k with fresh water injection to form primary water injection d, and discharging the rest of the secondary cut water k out of the system; and the secondary dewatering oil j is directly discharged out of the system.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Example 3
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A3 and the demulsifier No. 1 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.8 wt%, and the content of the demulsifier is 0.01 wt%.
(2) By adopting the system and the flow shown in the figure 2, the clear tank oil b is mixed into the crude oil a according to the mass ratio of 10:100 to form mixed oil c, and the mixed oil c enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 85 ℃; the primary water injection d is converged with the preheated mixed oil at the flow rate of 500g/h through a pump 3, and then sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 50kPa, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the first-stage oil-water emulsion e enters an electric desalting tank 6, and first-stage electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); and separating first-stage cut water g and first-stage dewatering oil f under the action of an electric field and a gravity field, discharging the first-stage cut water g from an outlet at the bottom of the electric desalting tank 6 to a system, and carrying out subsequent second-stage demetallization treatment on the first-stage dewatering oil f. Converging the secondary water injection h with the primary dehydrated oil f through a pump 7 at a flow rate of 500g/h, and then sequentially entering a mixer 8 and a mixing valve 9, wherein the pressure difference of the mixing valve is 42kPa, and fully mixing oil and water to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10, and secondary electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); separating secondary cut water k and secondary dehydrated oil j under the action of an electric field and a gravity field; converging 50 wt% of secondary cut water k with fresh water injection to form primary water injection d, and discharging the rest of the secondary cut water k out of the system; and the secondary dewatering oil j is directly discharged out of the system.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Example 4
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A4 and the demulsifier No. 1 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.92 wt%, and the content of the demulsifier is 0.02 wt%.
(2) By adopting the system and the flow shown in the figure 2, the clear tank oil b is mixed into the crude oil a according to the mass ratio of 15:100 to form mixed oil c, and the mixed oil c enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 85 ℃; the primary water injection d is converged with the preheated mixed oil at the flow rate of 500g/h through a pump 3, then sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 54kPa, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the first-stage oil-water emulsion e enters an electric desalting tank 6, and first-stage electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); and separating first-stage cut water g and first-stage dewatering oil f under the action of an electric field and a gravity field, discharging the first-stage cut water g from an outlet at the bottom of the electric desalting tank 6 to a system, and carrying out subsequent second-stage demetallization treatment on the first-stage dewatering oil f. Converging the secondary water injection h with the primary dehydrated oil f through a pump 7 at a flow rate of 500g/h, then sequentially entering a mixer 8 and a mixing valve 9, wherein the pressure difference of the mixing valve is 54kPa, and fully mixing oil and water to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10, and secondary electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); separating secondary cut water k and secondary dehydrated oil j under the action of an electric field and a gravity field; converging 50 wt% of secondary cut water k with fresh water injection to form primary water injection d, and discharging the rest of the secondary cut water k out of the system; and the secondary dewatering oil j is directly discharged out of the system.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Example 5
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A5 and the demulsifier No. 1 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.71 wt%, and the content of the demulsifier is 0.016 wt%.
(2) By adopting the system and the flow shown in the figure 2, the clear tank oil b is mixed into the crude oil a according to the mass ratio of 20:100 to form mixed oil c, and the mixed oil c enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 85 ℃; the primary water injection d is converged with the preheated mixed oil at the flow rate of 500g/h through a pump 3, then sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 54kPa, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the first-stage oil-water emulsion e enters an electric desalting tank 6, and first-stage electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); and separating first-stage cut water g and first-stage dewatering oil f under the action of an electric field and a gravity field, discharging the first-stage cut water g from an outlet at the bottom of the electric desalting tank 6 to a system, and carrying out subsequent second-stage demetallization treatment on the first-stage dewatering oil f. Converging the secondary water injection h with the primary dehydrated oil f through a pump 7 at a flow rate of 500g/h, then sequentially entering a mixer 8 and a mixing valve 9, wherein the pressure difference of the mixing valve is 54kPa, and fully mixing oil and water to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10, and secondary electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); separating secondary cut water k and secondary dehydrated oil j under the action of an electric field and a gravity field; converging 45 wt% of secondary cut water k with fresh water injection to form primary water injection d, and discharging the rest of the secondary cut water k out of the system; and the secondary dewatering oil j is directly discharged out of the system.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Example 6
This example illustrates the treatment of the clear tank oil according to the invention.
(1) And adding the demetallization agent A6 and the demulsifier No. 1 into water, and uniformly mixing to obtain water injection containing the demetallization agent and the demulsifier, wherein the content of the demetallization agent is 0.6 wt%, and the content of the demulsifier is 0.023 wt%.
(2) By adopting the system and the flow shown in the figure 2, the clear tank oil b is mixed into the crude oil a according to the mass ratio of 25:100 to form mixed oil c, and the mixed oil c enters a heater 2 through a pump 1 at the flow rate of 5000g/h and is preheated to 85 ℃; the primary water injection d is converged with the preheated mixed oil at the flow rate of 500g/h through a pump 3, then sequentially enters a mixer 4 and a mixing valve 5, the pressure difference of the mixing valve is 54kPa, and the oil phase and the water phase are fully mixed to form a primary oil-water emulsion e; the first-stage oil-water emulsion e enters an electric desalting tank 6, and first-stage electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); and separating first-stage cut water g and first-stage dewatering oil f under the action of an electric field and a gravity field, discharging the first-stage cut water g from an outlet at the bottom of the electric desalting tank 6 to a system, and carrying out subsequent second-stage demetallization treatment on the first-stage dewatering oil f. Converging the secondary water injection h with the primary dehydrated oil f through a pump 7 at a flow rate of 500g/h, then sequentially entering a mixer 8 and a mixing valve 9, wherein the pressure difference of the mixing valve is 54kPa, and fully mixing oil and water to form a secondary oil-water emulsion i; the secondary oil-water emulsion i enters an electric desalting tank 10, and secondary electric desalting treatment is carried out at the temperature of 125 ℃, the electric field intensity of 1000V/cm and the pressure of 0.6MPa (the retention time is 25 min); separating secondary cut water k and secondary dehydrated oil j under the action of an electric field and a gravity field; converging the secondary cut water k with the weight percent of 40% with fresh water injection to be used as primary water injection d, and discharging the rest secondary cut water k out of the system; and the secondary dewatering oil j is directly discharged out of the system.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content and the metal removal rate were calculated, and the results are shown in table 3.
Examples 7 to 20
This example illustrates the treatment of the clear tank oil according to the invention.
According to the method described in the embodiment 3, except that, when the water injection is prepared in the step (1), the demetallizing agent A7-A20 is respectively adopted to replace A3, so that after the subsequent electric desalting treatment, the corresponding secondary cut water and secondary dehydrated oil are obtained through separation.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content was calculated, and the metal removal rate finally obtained by calculation is shown in table 3.
Comparative examples 1 to 5
According to the method described in the embodiment 3, except that, when the water injection is prepared in the step (1), demetallizing agents DA1-DA5 are respectively adopted to replace A3, so that after the subsequent electric desalting treatment, corresponding secondary cut water and secondary dehydrated oil are obtained through separation.
The metal element contents of the upper and lower layers of the secondary dehydrated oil were measured, and the average metal element content was calculated, and the metal removal rate finally obtained by calculation is shown in table 3.
TABLE 3
The data in table 3 show that the demetallizing agent containing the composition of the present invention can effectively remove metal impurities in the clear tank oil by the coordination of the components in the composition in the treatment of the clear tank oil in combination with the operation of the treatment method of the present invention, for example, metal elements such as iron, calcium, sodium, potassium, magnesium, aluminum, etc. can be effectively removed, and particularly, the demetallizing agent containing the composition preferred by the present invention can make the removal rate of various metals in the clear tank oil reach more than 90%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (36)
1. The demetallizing agent composition for demetallizing the clear tank oil is characterized by comprising a sterilization component, a cocatalyst component, an organic carboxylic acid component and a wetting modification component;
wherein the bactericidal component is one or more of oilfield bactericides;
the cocatalyst component is one or more of carboxylic acid ammonium salt; the ammonium carboxylate is one or more of ammonium acetate, ammonium propionate, ammonium oxalate, ammonium malonate, ammonium malate, ammonium succinate and ammonium citrate;
the wetting modification component is a combination of polyoxyethylene ether surfactant and saturated straight-chain alcohol with more than 6 carbon atoms;
based on 100 parts by weight of the sterilization component, the content of the promoter component is 10-150 parts by weight, the content of the organic carboxylic acid component is 20-100 parts by weight, and the content of the wetting modification component is 0.1-20 parts by weight.
2. The composition as set forth in claim 1, wherein the co-catalyst component is contained in an amount of 20 to 120 parts by weight, the organic carboxylic acid component is contained in an amount of 25 to 80 parts by weight, and the wettability-modifying component is contained in an amount of 0.5 to 15 parts by weight, based on 100 parts by weight of the germicidal component.
3. The composition as set forth in claim 2, wherein the co-catalyst component is contained in an amount of 22 to 100 parts by weight, the organic carboxylic acid component is contained in an amount of 30 to 75 parts by weight, and the wettability-modifying component is contained in an amount of 0.5 to 10 parts by weight, based on 100 parts by weight of the germicidal component.
4. The composition according to any one of claims 1 to 3, wherein the oilfield bactericide is one or more of a quaternary phosphonium salt bactericide, an organic guanidine bactericide, a quaternary ammonium salt bactericide, and an isothiazolinone bactericide.
5. The composition of claim 4 wherein the oilfield biocide is one or more of tetrakis hydroxymethyl phosphonium sulfate, dodecylguanidine acetate, dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium bromide, cetylpyridinium chloride, dicococoal dimethyl ammonium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one, and 2-methyl-4-isothiazolin-3-one.
6. The composition of claim 5 wherein the oilfield biocide is tetrakis hydroxymethyl phosphonium sulfate.
7. The composition of any of claims 1-3 and 5-6, wherein the ammonium carboxylate salt is a combination of ammonium oxalate and ammonium citrate.
8. The composition according to claim 7, wherein the weight ratio of ammonium oxalate to ammonium citrate is 1: 0.5-10.
9. The composition according to claim 8, wherein the weight ratio of ammonium oxalate to ammonium citrate is 1: 1-5.
10. The composition of any of claims 1-3, 5-6, and 8-9, wherein the organic carboxylic acid component is a combination of a di-organic carboxylic acid that is one or more of oxalic acid, malonic acid, malic acid, and succinic acid and a tri-organic carboxylic acid that is one or more of citric acid, 1, 2-ethanedioic acid, 1,2, 3-propanetricarboxylic acid, and trimesic acid.
11. The composition of claim 10, wherein the weight ratio of the di-and tri-organic carboxylic acids is 1: 0.5-10.
12. The composition of claim 11, wherein the weight ratio of the di-and tri-organic carboxylic acids is 1: 1-4.
13. The composition according to any one of claims 1 to 3, 5 to 6, 8 to 9 and 11 to 12, wherein the weight ratio of the polyoxyethylene ether-based surfactant to the saturated linear alcohol in the wettability modifying component is 1: 0.5-10.
14. The composition according to claim 13, wherein the weight ratio of the polyoxyethylene ether-based surfactant to the saturated linear alcohol in the wettability modifying component is 1: 1-3.
15. The composition of claim 13, wherein the polyoxyethylene ether surfactant is one or more of fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
16. The composition of claim 13, wherein the saturated, linear alcohol is one or more of C7-C14.
17. The composition of claim 16, wherein the saturated linear alcohol is one or more of n-heptanol, n-octanol, n-nonanol, n-decanol, n-dodecanol, and n-tetradecanol.
18. The composition of any one of claims 1-3, 5-6, 8-9, 11-12, and 14-17, wherein the composition further comprises a co-solvent that is a mixture of an alcoholic solvent and water.
19. The composition of claim 18, wherein the weight ratio of alcoholic solvent to water is 1: 0.5-10.
20. The composition of claim 19, wherein the weight ratio of alcoholic solvent to water is 1: 1-6.
21. The composition of claim 18, wherein the alcoholic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
22. The composition of claim 21, wherein the alcoholic solvent is ethanol.
23. The composition as set forth in claim 18, wherein the co-solvent is contained in an amount of 50 to 500 parts by weight, based on 100 parts by weight of the germicidal component.
24. The composition as set forth in claim 23, wherein the content of the co-solvent is 60 to 450 parts by weight based on 100 parts by weight of the germicidal component.
25. A demetallizing agent comprising the composition of any one of claims 1 to 24.
26. A method for processing clear tank oil, wherein the clear tank oil contains sulphur-iron compound particles, and the processing method comprises the following steps: mixing the clear tank oil, the crude oil, the demulsifier, the demetallization agent and water to obtain an oil-water emulsion; under the condition of electric desalting, carrying out electric desalting treatment on the oil-water emulsion to separate cut water and dehydrated oil;
wherein the demetallizing agent is the demetallizing agent of claim 25.
27. The method of claim 26, wherein the method comprises: mixing the clear tank oil, the crude oil and water to obtain an oil-water emulsion; wherein the water injection is an aqueous solution containing a demulsifier and a demetallization agent.
28. The method of claim 27, wherein the demulsifier is present in an amount of 0.01 to 0.2 wt% and the demetalling agent is present in an amount of 0.05 to 5 wt% of the water injection.
29. The method of claim 27, wherein the method comprises: mixing the clear tank oil and the crude oil to obtain mixed oil, and mixing the mixed oil with water to obtain the oil-water emulsion.
30. The method of claim 29, wherein the method further comprises: heating the mixed oil to 70-90 ℃, and then mixing with water injection.
31. The method of any one of claims 26 to 30, wherein the weight ratio of the clean-up oil to the blended crude oil is from 1 to 25: 100.
32. the method of claim 27, wherein the water injection is used in an amount of 5 to 10 parts by weight, based on 100 parts by weight of the combined weight of the pig oil and the crude oil.
33. The method of any one of claims 26-30 and 32, wherein the conditions of the electro-desalting process comprise: the temperature is 100-130 ℃, the electric field intensity is 700-1200V/cm, and the pressure is 0.3-0.8 MPa.
34. The method of claim 27, wherein the method comprises:
(1) mixing the clear tank oil, the crude oil and primary water injection to obtain primary oil-water emulsion;
(2) under the condition of first-stage electric desalting, carrying out first-stage electric desalting treatment on the first-stage oil-water emulsion to separate first-stage cut water and first-stage dehydrated oil;
(3) mixing the first-stage dehydrated oil and the second-stage injected water to obtain a second-stage oil-water emulsion;
(4) and under the condition of secondary electric desalting, carrying out secondary electric desalting treatment on the secondary oil-water emulsion to separate and obtain secondary cut water and secondary dehydrated oil.
35. The method of claim 34, wherein at least a portion of the secondary cut-off water is recycled as part of the primary water injection.
36. The method as claimed in any one of claims 26 to 30, 32 and 34 to 35, wherein the clear tank oil contains 200-2000Mg/kg of Fe element, 50-500Mg/kg of Ca element, 50-500Mg/kg of Na element, 5-20Mg/kg of K element, 10-50Mg/kg of Mg element and 20-100Mg/kg of Al element.
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| CN1760340A (en) * | 2004-10-13 | 2006-04-19 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid |
| CN102031142A (en) * | 2002-08-30 | 2011-04-27 | 贝克休斯公司 | Additives to enhance metal and amine removal in refinery desalting processes |
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| CN102031142A (en) * | 2002-08-30 | 2011-04-27 | 贝克休斯公司 | Additives to enhance metal and amine removal in refinery desalting processes |
| CN1760340A (en) * | 2004-10-13 | 2006-04-19 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid |
| CN102453496A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | De-emulsifier and demulsification method for hydrocarbon oil |
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