CN113416576A - Compound demulsifier and application thereof - Google Patents
Compound demulsifier and application thereof Download PDFInfo
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- CN113416576A CN113416576A CN202110745219.4A CN202110745219A CN113416576A CN 113416576 A CN113416576 A CN 113416576A CN 202110745219 A CN202110745219 A CN 202110745219A CN 113416576 A CN113416576 A CN 113416576A
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- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Abstract
The invention provides a compound demulsifier and application thereof, wherein the demulsifier is prepared from a demulsifier X-75 and a demulsifier L-4 according to a mass ratio of 1-3: 1-3; the demulsifier X-75 is a five-membered copolymerized polyether demulsifier, and mainly solves the problem of dehydration amount; the demulsifier L-4 is a demulsifier modified by phenolic amine aldehyde resin block polyether, and mainly solves the problems of dehydration and wall hanging. The compound demulsifier provided by the invention has the advantages of small using amount, low dehydration temperature, high dehydration rate, clear dehydrated water, quick oil-water separation in the demulsification process and uniform oil-water interface, can quickly and efficiently solve the problem that a certain amount of single/mixed oil well shaft maintenance agent and a certain amount of single/mixed well-entering operation flowback residual liquid interfere the normal dehydration of crude oil at low temperature, cannot generate secondary pollution to the crude oil, and cannot introduce new impurities. The present invention can solve or partially solve similar problems in most oilfield production.
Description
Technical Field
The invention belongs to the field of oilfield application chemistry and environmental protection, and particularly relates to a compound demulsifier and application thereof.
Background
Crude oil water is a common phenomenon in oil and gas field development. At present, electrochemical methods and thermochemical methods are mainly used in crude oil dehydration processes in oil fields. Generally, high aqueous crude emulsions that are easily dehydrated are treated chemically, and low aqueous emulsions that are difficult to dehydrate are treated electrochemically. The most common process is chemical demulsification followed by electric de-emulsification with the assistance of chemical demulsification.
However, as the development of oil fields in China enters the middle and later stages, in order to ensure the normal production and stable yield increase of the oil fields, various production measures are adopted in each large oil field, and a large amount of oil extraction chemical agents are used in the production. Such as to maintain normal production from an oil well, wellbore servicing agents such as: a part of the shaft maintainer inevitably enters an oil-water treatment system along with the produced liquid of crude oil; in order to increase and stabilize yield, operations such as acidification, fracturing, sand prevention and the like can be carried out frequently, and a large amount of acidification plugging removal liquid, emulsion fracturing liquid, sand carrying liquid and the like are used in the operation process. The measures play an important role in stabilizing yield and increasing yield, but after the operation is finished, part of flowback residual liquid inevitably enters an oil-water treatment system along with produced liquid.
Production practices and researches of a plurality of domestic oil fields show that crude oil emulsions containing oil extraction aids or operation flowback residual liquid directly enter a gathering and transportation system to generate impact on the dehydration of the crude oil emulsions, so that normal dehydration is influenced; moreover, the accuracy of the evaluation on the yield increasing effect of the measure well can be influenced if the emulsion containing the oil extraction auxiliary agent or the operation flowback residual liquid does not enter a gathering and transportation system; in addition, the method can not measure oil and water, and a large amount of crude oil is wasted without counting the yield, thereby influencing the verification of the measure yield; finally, even if the emulsion containing the oil extraction auxiliary agent or the operation flowback residual liquid is independently treated, the emulsion is difficult to be treated to the standard of commodity oil, thereby influencing the selling price and the economic benefit of the oil field. Therefore, the oil extraction auxiliary agent and the operation flowback residual liquid inevitably affect the stable yield and the yield increase of the oil field. Therefore, enough attention must be paid to and solved for the problem that produced fluid containing oil extraction aids and operation flowback residual liquid affects demulsification and dehydration of a gathering system, and guarantee can be provided for oilfield development.
For this reason, specialists and technicians have made some specific research work. For example, research in the model oscillation of university of Zhejiang indicates that H + in the acidized flowback fluid activates naphthenic acid in the heavy oil, increases the amount of the emulsifier, increases the strength of an emulsion membrane, and makes demulsification of crude oil produced fluid difficult. Panyi of Jiangsu oil field and the like are researched aiming at the demulsification and dehydration problems of crude oil produced by oil wells corresponding to real 35 polymer flooding HPAMs, 400mg/L of compound demulsifier RDH-54 is added, when the concentration of HPAM in produced liquid is less than 200mg/L, the demulsification rate reaches over 90 percent, and the demulsification requirement of the produced liquid under certain polymer concentration is basically met. The Sanguo research of China university of mining discovers that the polymer has obvious inhibition effect on the demulsification of 31 demulsifiers, and the water layer after dehydration has high oil content and is quite stable; the influence of low-solid-phase polymer drilling fluid, boron crosslinked guar fracturing fluid gel breaking fluid, alkaline earth acid spent acid, paraffin remover, bactericide, scale inhibitor, polyaluminium/polymeric iron composite flocculant, polymer HPAM, weak gel, NaOH, hydrochloric acid and the like on the dehydration effect of a specific demulsifier YT-100 is researched by Zhangong and the like of Xian Ouden Petroleum engineering technology Co.
The reason that the well bore maintenance agent commonly used in the oil field breaks the emulsion and dehydrates the original emulsion of the oil field is very complicated and is not completely explained at present, and the inventor analyzes the possible reason: the main component of the maintenance agent corrosion inhibitor added into the shaft is a compound of octadecyl dimethyl benzyl ammonium chloride and imidazoline, wherein the component is tenThe ammonium chloride is an ammonium chloride with both cationic and anionic surfactants, and as corrosion inhibitor, it has the action of inhibiting corrosion mainly by filming, and imidazoline is strongly alkaline, stable in acidic and alkaline medium, and can be compatible with anionic, cationic and nonionic surfactants. After the demulsifier is added into a shaft, the thickness and the stability of an oil-water interface film can be increased, and on the other hand, the demulsifier can react with the demulsifier, so that the dehydration efficiency of the demulsifier is reduced. The main component of the desulfurizer is triazine amine compounds, wherein the sulfur capacity of the n-butylamine and di-n-butylamine triazine based desulfurizer is lower. Triazinylcyclohexylamines having high sulfur capacity but reacting with H2S reaction generates sediment, and the produced sediment can cause thickening of an oil-water interface film, increase of strength and influence of dehydration. Wherein the main component of the non-solid phase well killing fluid is CaCl2After entering the crude oil emulsion, the ions in the water are balanced, and CaCO may be generated3、CaSO4And CaS and the like, which cause difficulty in demulsification and dehydration.
The mixed multiple wellbore maintenance agents have stronger demulsification effect inhibition effect on crude oil, the reasons are related to the performance of a single agent, even the agents are incompatible, if the solid-free well killing fluid is mixed with a desulfurizing agent, a small amount of precipitate can be generated, and the precipitate can cause thickening of an oil-water interface film, increase of strength and influence on dehydration. This additive effect exacerbates the adverse effects of these agents on dehydration. As shown in fig. 1, dehydration using different demulsifiers was performed for a crude oil emulsion to which 20% (V/V) of a mixed wellbore servicing agent (devulcanizing agent + corrosion inhibitor + no solid phase + hot wash additive + viscosity reducer) was added. FIG. 2 is a dehydration of a crude oil emulsion with 20% (V/V) of a mixed wellbore servicing agent (devulcanizing agent + corrosion inhibitor + no solid phase + hot wash agent + viscosity reducer + bio-enzyme) with different demulsifiers.
Because the oil field operation is of various types and even cross simultaneous operation, the types and components of the operation flowback residual liquid are complex, the influence on dehydration is more serious when the residual liquid enters the crude oil produced liquid, but the influence causes and mechanisms are unclear and are mostly conjectured. For example, the main component of the multi-heat washing agent is sodium nonylphenolsulfonate, which has high temperature resistance and salt resistance, and is also a surfactant, but the hot washing flowback residual liquid contains aggregates of mechanical impurities such as water, oil, paraffin, colloid, asphalt, sand, suspended matters and the like, and some of the substances can be adsorbed on an oil-water interface, so that the interfacial tension is reduced, the thickness and the strength of an oil-water interfacial film are increased, the interfacial stability is increased, the film forming capability is enhanced, and the emulsion stability is increased. Therefore, the membrane breaking dehydration is difficult, and the oil content in the dehydrated water is higher.
The acidification of the flowback residual liquid makes the crude oil demulsification and dehydration more difficult. The main manifestations are slow dehydration speed, unclear water color, lengthened transition zone and floccule under water. The reason for this is probably that in the course of acidification, some acidified sludge containing asphaltenes and colloids as main components may be generated after the crude oil is contacted with the acid solution, which makes the oil-water interface film more stable and makes the emulsion more difficult to dehydrate. It is also possible that the acid activates naphthenic acids in the crude oil, resulting in enhanced emulsification and difficulty in dehydration.
The main component of the fracturing fluid and the filling filtrate in the fracturing operation is guar gum, the main component of the sand control fluid is epoxy resin, besides, the working fluids also contain additives such as cross-linking agent, regulator, stabilizer, anti-swelling agent, cleanup additive and the like, the components of the oil-water well are complex before entering the well, and after the operation is finished, the components of the oil-water well are more complex when the oil-water well returns to the ground from the well bottom, not only oil and salt but also a large amount of mud and sand and other mechanical solid impurities exist, after the residual liquid is discharged back into the system, the surface viscosity is increased because polymers such as guar gum, epoxy resin and the like in the residual liquid form a mixed film on an interface, the strength of the interface film is improved, the interface tension is effectively reduced, the crude oil is more stable, and because of a large amount of entrained silt, salt and the like, the oil-water interfacial tension of the crude oil emulsion in the system is reduced, the stability of the emulsion is increased, and the difficulty of demulsification and dehydration is increased. FIG. 3 shows the dehydration condition of crude oil emulsion containing 10% (V/V) (hot washing, high pressure filling filtration, emulsion fracturing fluid, composite fiber sand fixation and prevention, acidized flowback fluid) mixed flowback residual liquid by using different demulsifiers.
The inventor carries out research on the influence of various working fluids, flowback fluid residual liquid and main components thereof such as various acids, polymers, colloids, asphaltenes and the like on crude oil demulsification and dehydration. However, because of the large differences of reservoir characteristics, produced fluid properties, wellbore maintenance, operation measure types and the like of each oil field, a demulsifier capable of resisting dehydration interference of a certain amount of single/mixed wellbore maintainer, a certain amount of single/mixed well-entering operation flowback residual liquid, a certain amount of single/mixed wellbore maintainer and well-entering operation flowback residual liquid on the produced fluid at the same time is not researched in the early stage.
Disclosure of Invention
The invention provides a compound demulsifier and application thereof, aiming at the demulsification problems of high mechanical strength and the like of crude oil produced liquid containing a shaft maintainer/operation flowback residual liquid, such as low oil-water interfacial tension, stable interfacial film, film thickness and solid particle substances on the film, the demulsifier is used for dehydrating crude oil and can resist the interference of the shaft maintainer of an oil well and the flowback residual liquid in underground operation.
The technical scheme of the invention is that the compound demulsifier is prepared from demulsifier X-75 and demulsifier L-4 according to a mass ratio of 1-3: 1-3; wherein the demulsifier X-75 is a five-membered copolymerized polyether demulsifier; and the demulsifier L-4 is a demulsifier modified by phenolic aldehyde resin block polyether.
In the preferred scheme, the demulsifier is prepared from demulsifier X-75 and demulsifier L-4 according to the mass ratio of 1: 1.
Further, when the demulsifier X-75 is prepared, firstly, the bisphenol A phenolic amine resin diblock polyether demulsifier is prepared, wherein the mass ratio of Propylene Oxide (PO) to Ethylene Oxide (EO) is 1:1-3: 1; and then esterifying the bisphenol A phenolic amine resin diblock polyether demulsifier with acrylic acid, and copolymerizing with methyl methacrylate, styrene, methacrylic acid and acrylic acid by adopting an emulsion method to synthesize the five-membered copolymerized polyether demulsifier.
Further, the mass ratio of the demulsifier after esterification to the methyl methacrylate to the styrene to the methacrylic acid to the acrylic acid is 6-7: 0.5-1: 1.5-2: 0.5-1: 0.5 to 1.
Furthermore, the demulsifier L-4 is a modified ultra-high molecular demulsifier which is obtained by using phenolic aldehyde resin polyoxypropylene polyoxyethylene block polyether as a framework and crosslinking and chain extending epoxy chloropropane, and has the molecular weight of 80-280 ten thousand.
During the specific preparation of the demulsifier L-4, epoxy chloropropane with the mass fraction of 8-10% is dripped into phenolic amine aldehyde resin polyoxypropylene polyoxyethylene block polyether at the temperature of 40-100 ℃, and the demulsifier L-4 is obtained after the addition and the reaction for 8-12 h.
The invention also relates to a method for preparing the compound demulsifier, which comprises the steps of respectively taking demulsifier driers X-75 and L-4 according to the proportion, dissolving the demulsifier X-75 by using methanol and the demulsifier L-4 by using dimethylbenzene at normal temperature, and finally uniformly mixing the demulsifier driers X-75 and L-4.
The invention also relates to application of the compound demulsifier in crude oil dehydration. The crude oil is dehydrated, and the interference of a well shaft maintenance agent and/or a flowback residual liquid in well entering operation exists.
Further, the anti-oil well shaft maintenance agent is a single-component or mixed-component shaft maintenance agent; the well-entry operation flowback residual liquid is single-component or mixed-component flowback residual liquid for well-entry operation.
When the demulsifier is specifically applied, the demulsification temperature is 40-50 ℃, the dehydration time is 45-75min, and the addition amount of the demulsifier is 10-60 mg/L.
The invention has the following beneficial effects:
in the compound demulsifier provided by the invention, the demulsifier X-75 is a five-membered co-polyether demulsifier, and mainly solves the problem of dehydration amount; the demulsifier L-4 is a demulsifier modified by phenolic amine aldehyde resin block polyether, and mainly solves the problems of dehydration and wall hanging. The demulsifier molecules compounded by the two can be adsorbed on an oil-water interfacial film to partially replace film-forming substances, a PEO chain segment in each polyether branched chain extends into a water phase, a PPO chain segment connected with the PEO chain segment extends into the water phase at a small part and is partially distributed on the oil-water interfacial film close to an oil phase, and the demulsifier molecules participate in forming a loose mixed interfacial film, so that the strength of the interfacial film is reduced, the influence of an oil production agent and operation flowback residual liquid on emulsion is eliminated, and oil and water are more easily separated.
When the ratio of propylene oxide/ethylene oxide (PO/EO) in the demulsifier X-75 is controlled to be fixed at 1:1-3:1, the demulsifier has good low-temperature demulsification performance. The demulsifier L-4 is a modified ultra-high molecular copolymer which is obtained by using phenolic amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework and crosslinking and chain extending epoxy chloropropane under certain conditions, has good wettability to an oil-water interface, good dispersibility in an oil-water two-phase, quick demulsification, clear dehydration and no wall hanging, and is an excellent mixed low-temperature demulsifier.
The compound demulsifier of the invention has stable property at normal temperature, can be stored for a long time, and has simple formula components and low cost. Has the advantages of small dosage (10mg/L-60mg/L), high dehydration speed (less than or equal to 75min) at low temperature (40-50 ℃), clear dehydrated water and the like. It has strong specificity. Can solve the problem of disturbing the demulsification and dehydration of crude oil produced liquid under similar production conditions, and has good economic benefit and environmental benefit.
Drawings
As shown in fig. 1, dehydration using different demulsifiers was performed for a crude oil emulsion to which 20% (V/V) of a mixed wellbore servicing agent (devulcanizing agent + corrosion inhibitor + no solid phase + hot wash additive + viscosity reducer) was added.
FIG. 2 is a dehydration of a crude oil emulsion with 20% (V/V) of a mixed wellbore servicing agent (devulcanizing agent + corrosion inhibitor + no solid phase + hot wash agent + viscosity reducer + bio-enzyme) with different demulsifiers.
FIG. 3 shows the dehydration condition of crude oil emulsion containing 10% (V/V) (hot washing, high pressure filling filtration, emulsion fracturing fluid, composite fiber sand fixation and prevention, acidized flowback fluid) mixed flowback residual liquid by using different demulsifiers.
FIG. 4 is a graph of the dewatering effect of 5 complex demulsifiers from examples 1-5 on the addition of a single wellbore servicing agent crude oil emulsion. Wherein, fig. 4-1 is a number 1-9 tube from left to right: the demulsifiers in the embodiments 1-5 are sequentially added into a blank (without adding a corrosion inhibitor and a demulsifier), 2 demulsifiers with a corrosion inhibitor, 3 demulsifiers with L-4, 4 demulsifiers with X-75 and 5-9, wherein the adding amount of the corrosion inhibitor in the crude oil emulsion is 10 mg/L; FIG. 4-2 is tube No. 1-9 from left to right: the demulsifiers of the embodiments 1-5 are sequentially added into a blank (non-pressurized well fluid and demulsifier), 2 pressurized well fluids, 3 demulsifier L-4, 4 demulsifier X-75 and 5-9, wherein the addition amount of the non-solid-phase well fluid in the crude oil emulsion is 1% (V/V); fig. 4-3, from left to right, are tubes No. 1-9: the demulsifiers of examples 1-5 were added sequentially in a blank (no desulfurizer, demulsifier), 2 desulfurizers, 3 demulsifiers L-4, 4 demulsifiers X-75, 5-9, and the amount of desulfurizers added in the crude oil emulsion was 10% (V/V).
FIG. 5 is a graph showing the dehydration effect of 5 kinds of the complex demulsifiers obtained in examples 1 to 5 on crude oil emulsion to which a single-operation flowback residual liquid is added. Wherein, fig. 5-1 is a number 1-9 tube from left to right: blank (heating washing-back liquid, without demulsifier), 2 not heating washing-back liquid, without demulsifier, 3 with demulsifier L-4, 4 with demulsifier X-75, 5-9 and adding the demulsifiers of the embodiments 1-5 in turn, wherein the adding amount of the hot washing-back liquid in the crude oil emulsion is 20% (V/V); FIG. 5-2 is tube No. 1-9 from left to right: blank (adding the strain-free return fluid, not adding the demulsifier), 2 not adding the strain-free return fluid, not adding the demulsifier, 3 adding the demulsifier L-4, 4 adding the demulsifier X-75, 5-9 and sequentially adding the demulsifiers in the embodiments 1-5), wherein the adding amount of the high-pressure filling strain-free return fluid in the crude oil emulsion is 20% (V/V); fig. 5-3, from left to right, are tubes No. 1-9: blank (adding the emulsion fracturing flowback fluid, not adding the demulsifier), 2 adding no the emulsion fracturing flowback fluid, not adding the demulsifier, 3 adding the demulsifier L-4, 4 adding the demulsifier X-75, 5-9 and sequentially adding the demulsifiers in the embodiments 1-5), wherein the adding amount of the emulsion fracturing flowback fluid in the crude oil emulsion is 20% (V/V); fig. 5-4, from left to right, is: blank (adding acidized fracturing flowback fluid, not adding demulsifier), 1 adding demulsifier L-4, 2 adding demulsifier X-75, 3-7 and adding the demulsifiers of examples 1-5 in turn, wherein the adding amount of the acidized flowback fluid in the crude oil emulsion is 10% (V/V).
FIG. 6 is a diagram showing the demulsification effect of the crude oil emulsion with different amounts of the flowback raffinate in example 3, wherein the amounts of the mixed flowback raffinate added from left to right are 1%, 1.6%, 2%, 4%, 5% and 20% in sequence. Wherein FIG. 6-1 shows the effect of dehydration by adding a single demulsifier X-75; FIG. 6-2 shows the effect of dehydration with the addition of a single demulsifier L-4; FIG. 6-3 shows the dehydration effect of adding a compounded demulsifier (YZL-08).
Fig. 7 shows the demulsification effect of the original emulsion of the mixed wellbore servicing fluid and the mixed flowback raffinate (adjusted to pH 7) by using the compound demulsifier provided in example 3, wherein the left side shows the effect of adding the mixed wellbore servicing fluid, and the right side shows the effect of adding the mixed flowback raffinate.
FIG. 8 shows the demulsifying effect of the compounded demulsifier provided in example 4 on a crude oil emulsion of mixed liquor (5 flowback raffinates mixed with 6 wellbore servicing agents), wherein a blank is formed by adding 10% (V/V) of the mixed liquor (5 flowback raffinates mixed with 6 wellbore servicing agents) and no demulsifier is added; adding 10% (V/V) mixed liquor (5 flowback residual liquors are mixed with 6 wellbore maintenance agents) into 1 pipe, and adding 60mg/L single demulsifier L-4; 2, adding 10% (V/V) mixed liquor (5 flowback residual liquors are mixed with 6 wellbore maintenance agents) into a pipe, and adding 60mg/L of single demulsifier X-75; and 3 pipes are added with 10 percent (V/V) of mixed liquor (5 flowback residual liquors are mixed with 6 wellbore maintenance agents), and 60mg/L of compound demulsifier is added.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The specific synthetic method of the demulsifier X-75 comprises the following steps: 100g of bisphenol A and 120g of polyethylene polyamine (average molecular weight 275) are added into a 1000mL three-neck flask, and the mixture is stirred for 1h at a constant temperature of 50 ℃ so that the bisphenol A is completely dissolved in the polyamine liquid; 138mL of a formaldehyde solution (40%) was slowly added dropwise to the solution using a dropping funnel, followed by warming to 120 ℃ and reacting at a constant temperature for 2 hours. After the reaction is finished, evaporating excessive formaldehyde and water, and performing vacuum drying to obtain reddish brown viscous liquid, namely the bisphenol A phenolic amine resin. Putting a certain amount of bisphenol A phenolic amine resin and a catalyst potassium hydroxide into a dry and clean stainless steel high-pressure reaction kettle, vacuumizing to-0.1 MPa, replacing with high-purity nitrogen for several times, and continuously vacuumizing to 100 ℃. When the temperature is close to 120 ℃, the propylene oxide is slowly, continuously and slightly introduced, and the pressure of the reaction kettle is lower than 0.4 MPa. After the reaction is finished, the ethylene oxide is slowly, continuously and slightly introduced in the same way, and the pressure is controlled to be lower than 0.2MPa and the temperature is controlled to be lower than 120 ℃ due to the high EO activity. And obtaining the block polyether demulsifier after the reaction is completed. Bisphenol A phenol amine diblock polyether demulsifiers with different PO/EO polymerization ratios are respectively prepared. And (3) reacting the bisphenol A phenolic amine diblock polyether demulsifier with acrylic acid at 80 ℃ for 12 hours to obtain the esterified bisphenol A phenolic amine diblock polyether demulsifier. And (2) mixing a certain amount of esterified demulsifier, methyl methacrylate and styrene, adding into a constant pressure funnel, adding a certain amount of methacrylic acid and acrylic acid into another constant pressure funnel, respectively weighing potassium persulfate and sodium dodecyl sulfate according to 1.25% and 8% of the total amount of monomers, dissolving with 45mL of distilled water, adding into a three-neck flask, placing into a constant temperature water bath at 80 ℃, dropwise adding the solution in the constant pressure funnel while stirring to finish the dropwise adding within 2h, and continuing to react for 30 min. Then the temperature is reduced to 60 ℃, triethanolamine and anhydrous sodium sulfite are respectively weighed according to 0.5 percent and 0.75 percent of the total amount of the monomers, dissolved in 15mL of distilled water and added dropwise into a three-neck flask for reaction for 1 h. Wherein the mass ratio of the demulsifier after esterification to the methyl methacrylate to the styrene to the methacrylic acid to the acrylic acid is 6-7: 0.5-1: 1.5-2: 0.5-1: 0.5 to 1.
Example 1:
a compound demulsifier adopts demulsifier X-75 and demulsifier L-4 according to the mass ratio of 1:1, preparing; the demulsifier X-75 is a pentabasic copolymerized polyether demulsifier, and the mass ratio of the demulsifier after esterification to the methyl methacrylate, the styrene, the methacrylic acid and the acrylic acid is 7: 0.5: 1.5: 0.5: 0.5. and the demulsifier L-4 is a demulsifier modified by phenolic aldehyde resin block polyether. The demulsifier L-4 takes phenolic aldehyde amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework, 10 percent of epoxy chloropropane is dripped into the phenolic aldehyde resin polyoxypropylene polyoxyethylene block polyether at the temperature of 80 ℃, and the modified ultrahigh molecular demulsifier L-4 (with the molecular weight of 260 ten thousand) is obtained after the addition of the epoxy chloropropane is reacted for 10 hours.
The preparation method of the compound demulsifier comprises the following steps: respectively taking synthetic demulsifier driers X-75 and L-4 with the same mass, respectively dissolving the demulsifier driers with the same volume of methanol and dimethylbenzene at normal temperature, and then uniformly mixing the two agents according to the ratio of 1: 1.
Example 2:
a compound demulsifier adopts demulsifier X-75 and demulsifier L-4 according to the mass ratio of 2:1, preparing; in the demulsifier X-75, the mass ratio of the demulsifier after esterification, methyl methacrylate, styrene, methacrylic acid and acrylic acid is 6: 1: 2: 0.5: 0.5. the demulsifier L-4 takes phenolic aldehyde amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework, 8 percent of epoxy chloropropane is dripped into the phenolic aldehyde resin polyoxypropylene polyoxyethylene block polyether at the temperature of 70 ℃, and the modified ultrahigh molecular demulsifier L-4 (with the molecular weight of 200 ten thousand) is obtained after the addition of the epoxy chloropropane is reacted for 12 hours.
The preparation method of the compound demulsifier comprises the following steps: taking the synthesized demulsifier dry agents X-75 and L-4 according to the mass ratio of 2:1, respectively dissolving the demulsifier dry agents X-75 and L-4 with methanol and xylene which have the same volume at normal temperature, and then uniformly mixing according to the ratio of 1:1 (V/V).
Example 3:
a compound demulsifier adopts demulsifier X-75 and demulsifier L-4 according to the mass ratio of 3:1, preparing; the demulsifier X-75 is a pentabasic copolymerized polyether demulsifier, and the mass ratio of the demulsifier after esterification to the methyl methacrylate, the styrene, the methacrylic acid and the acrylic acid is 6: 1: 1.5: 1: 0.5; the demulsifier L-4 is a modified demulsifier of phenolic amine resin block polyether, and is prepared by taking phenolic amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework, dropwise adding 9% of epoxy chloropropane into the phenolic amine resin polyoxypropylene polyoxyethylene block polyether at 60 ℃, and reacting for 10h after the addition is finished to obtain the modified ultrahigh molecular demulsifier L-4 (with the molecular weight of 160 ten thousand).
The preparation method of the compound demulsifier comprises the following steps: taking the synthesized demulsifier dry agent X-75 and L-4 according to the mass ratio of 3:1, respectively dissolving with methanol and xylene which have the same volume at normal temperature, and then uniformly mixing the two according to the ratio of 1:1 (V/V).
Example 4:
a compound demulsifier adopts demulsifier X-75 and demulsifier L-4 according to the mass ratio of 1:2, preparing; wherein the demulsifier X-75 is a five-membered copolymerized polyether demulsifier; and the demulsifier L-4 is a demulsifier modified by phenolic aldehyde resin block polyether. In the five-membered copolymer polyether demulsifier X-75, the mass ratio of the demulsifier after esterification, methyl methacrylate, styrene, methacrylic acid and acrylic acid is 7: 0.5: 1:1: 0.5. the demulsifier L-4 takes phenolic aldehyde amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework, 10 percent of epoxy chloropropane is dripped into the phenolic aldehyde resin polyoxypropylene polyoxyethylene block polyether at the temperature of 75 ℃, and the modified ultrahigh molecular demulsifier L-4 (with the molecular weight of 190 ten thousand) is obtained after the addition of the epoxy chloropropane is reacted for 12 hours.
The preparation method of the compound demulsifier comprises the following steps: taking the synthesized demulsifier dry agents X-75 and L-4 according to the mass ratio of 1:2, respectively dissolving the demulsifier dry agents and the L-4 with methanol and xylene which have the same volume at normal temperature, and then uniformly mixing the demulsifier dry agents and the dimethyl ether according to the mass ratio of 1:1 (V/V).
Example 5:
a compound demulsifier adopts demulsifier X-75 and demulsifier L-4 according to the mass ratio of 1:3, preparing; wherein the demulsifier X-75 is a five-membered copolymerized polyether demulsifier; and the demulsifier L-4 is a demulsifier modified by phenolic aldehyde resin block polyether. In the five-membered copolymer polyether demulsifier X-75, the mass ratio of the demulsifier after esterification, methyl methacrylate, styrene, methacrylic acid and acrylic acid is 6.5: 0.5: 1.5: 1: 0.5. the demulsifier L-4 takes phenolic aldehyde amine resin polyoxyethylene polyoxypropylene ether block polyether as a framework, 10 percent of epoxy chloropropane is dripped into the phenolic aldehyde resin polyoxypropylene polyoxyethylene block polyether at 85 ℃, and the modified ultrahigh molecular demulsifier L-4 (with the molecular weight of 180 ten thousand) is obtained after the addition of the epoxy chloropropane is reacted for 10 hours.
The preparation method of the compound demulsifier comprises the following steps: taking the synthesized demulsifier dry agents X-75 and L-4 according to the mass ratio of 1:3, respectively dissolving the demulsifier dry agents and the L-4 with methanol and xylene which have the same volume at normal temperature, and then uniformly mixing the demulsifier dry agents and the dimethyl ether according to the mass ratio of 1:1 (V/V).
Application case 1:
5 kinds of compound demulsifiers (YZL-08) obtained in examples 1 to 5 are adopted to carry out dehydration treatment on crude oil produced liquid of an oil production plant facing a plate: the demulsification temperature is 43 ℃, the dehydration time is 75min, and when the addition is 10mg/L, the crude oil production fluid can meet the requirements that the dehydration rate is more than or equal to 90 percent and the water phase cleanliness is not less than 1 grade (oil content is less than 100mg/L)
Application case 2:
respectively adding a certain amount of single wellbore maintenance agent into the crude oil produced liquid according to actual production: 10mg/L of corrosion inhibitor, 10 percent (V/V) of desulfurizer and 1 percent (V/V) of solid-free well control fluid. The 5 compound demulsifiers obtained in the examples 1 to 5 can resist the interference of the single wellbore maintainer on demulsification and dehydration of crude oil produced fluid, and can meet the requirements of dehydration rate of more than or equal to 90% and water phase cleanliness of not less than 1-level (oil content of less than 100 mg/L). ,
the dehydration effect of the 5 kinds of compound demulsifiers (YZL-08) obtained in the embodiments 1 to 5 on the crude oil emulsion added with the single wellbore servicing agent is shown in figure 4, and compared with the dehydration condition before compounding under the same condition (the dehydration condition is demulsification temperature of 43 ℃, dehydration time of 75min and demulsifier addition of 10mg/L), the compound demulsifier has obvious synergistic effect and can improve the dehydration amount, and the 5 kinds of compound demulsifiers have certain capacity of resisting the single wellbore servicing agent.
Application case 3:
respectively adding a certain amount of single flowback residual liquid into the crude oil produced liquid according to actual production: 20% (V/V) of hot washing flowback liquid, 20% (V/V) of high-pressure filling hanging filtration flowback liquid, 20% (V/V) of emulsion fracturing flowback liquid and 10% (V/V) of acidification flowback liquid. The compound demulsifier can resist the interference of single flowback residual liquid on demulsification and dehydration of crude oil emulsion, and can meet the requirements of that the dehydration rate is greater than or equal to 90% and the water phase cleanliness is not less than 1 grade (oil content is less than 100 mg/L).
The dehydration effect of the 5 kinds of compound demulsifiers (YZL-08) obtained in the examples 1 to 5 on the crude oil emulsion with the single-operation flowback residual liquid is shown in fig. 5, and the compound demulsifier has a remarkable synergistic effect and can improve the dehydration amount compared with the dehydration condition before compounding under the same conditions (the dehydration conditions are demulsification temperature of 43 ℃, dehydration time of 75min, demulsifier addition amount of 10mg/L and the like), and the 5 kinds of compound demulsifiers have certain capacity of resisting the single-operation flowback residual liquid.
Application case 4:
according to the actual production, 1% -20% of mixed wellbore maintenance agents (each wellbore maintenance agent is mixed according to the use concentration and the equal volume ratio) are respectively added into crude oil produced liquid, and the mixed wellbore maintenance agents are respectively: corrosion inhibitor + desulfurizer (1:1), corrosion inhibitor + solid-free kill fluid + desulfurizer (1:1:1), corrosion inhibitor + solid-free kill fluid + desulfurizer + hot-wash additive (1:1:1:1), corrosion inhibitor + solid-free kill fluid + desulfurizer + hot-wash additive + viscosity reducer (1:1:1:1:1), corrosion inhibitor + solid-free kill fluid + desulfurizer + hot-wash additive + viscosity reducer + bio-enzyme cleaner (1:1:1:1: 1)). Compared with the dehydration condition before compounding under the same conditions (at the demulsification temperature of 50 ℃, the dehydration time of 75min, the demulsifier addition amount of 60mg/L and the like) by adopting the compound demulsifier (YZL-08) obtained in the embodiment 3, the compound demulsifier YZL-08 can resist the interference of the mixed shaft maintainer on the demulsification and dehydration of the crude oil produced liquid, and can meet the requirements that the dehydration rate is more than or equal to 90 percent and the water phase cleanliness is not lower than grade 1 (oil content is less than 100 mg/L). And under the same conditions (at the demulsification temperature of 50 ℃, the dehydration time of 75min, the addition of the demulsifier of 60mg/L and the like), the single demulsifiers X-75 and L-4 can not resist the interference of the mixed wellbore maintainer on the demulsification and dehydration of the crude oil produced fluid, and can not meet the requirements of that the dehydration rate is more than or equal to 90 percent and the water phase cleanliness is not lower than 1 level (oil content is less than 100 mg/L). The compound demulsifier has obvious synergistic effect and can improve the dehydration amount, and the compound demulsifier has certain capability of resisting the interference of the mixed shaft maintainer on dehydration.
Application case 5:
1-20% (V/V) of mixed flowback raffinate (various flowback raffinates are mixed according to the equal volume ratio) is respectively added into the crude oil produced liquid, and the mixed flowback raffinate is respectively: hot washing return liquid + high pressure filling hanging filter return liquid (1:1), hot washing return liquid + high pressure filling hanging filter return liquid + emulsion fracturing fluid return liquid (1:1:1), hot washing return liquid + high pressure filling hanging filter return liquid (guar gum sand-carrying liquid) + emulsion fracturing fluid return liquid + composite fiber sand consolidation agent sand prevention return liquid (1:1:1:1), hot washing return liquid + high pressure filling hanging filter return liquid (guar gum sand-carrying liquid) + emulsion fracturing fluid return liquid + composite fiber sand consolidation agent sand prevention return liquid + acidizing deblocking liquid (1:1:1: 1). The compound demulsifier YZL-08 can resist the interference of the mixed flowback residual liquid on the demulsification and dehydration of crude oil produced liquid, and can meet the requirements of dehydration rate more than or equal to 90 percent and water phase cleanliness not lower than level 1 (oil content less than 100mg/L) for the produced liquid of an adjacent-tray oil production plant except weak wall built-up
Specifically, 1-20% (V/V) of mixed flowback raffinate [ hot washing flowback liquid + high-pressure filling hanging filtration flowback liquid (guar gum sand-carrying liquid) + emulsion fracturing fluid flowback liquid + composite fiber sand consolidation agent sand control flowback liquid + acidification deblocking liquid (mixed in an equal volume of 1:1:1:1:1 ] are added to the crude oil emulsion according to the volume ratio, and the compound demulsifier (YZL-08) obtained in example 3 is used to perform a dehydration effect experiment, and the results are shown in table 1 and fig. 6.
TABLE 1 demulsification and dehydration effect of original emulsion by adding different amounts of mixed flowback residual liquid
As can be seen from table 1 and fig. 6, in comparison with the dehydration condition before the combination under the same conditions (at the demulsification temperature of 43 ℃, the dehydration time of 75min, the demulsifier addition of 60mg/L, etc.), the combination demulsifier (YZL-08) has a good dehydration effect on crude oil emulsion added with different amounts of mixed flowback residual liquid, which indicates that the combination demulsifier has a significant synergistic effect, can improve the dehydration amount, and has a certain capability of resisting the interference of the mixed flowback residual liquid with dehydration.
Application case 6:
taking mixed flowback residual liquid (LPP2-504 well hot washing flowback liquid, LPP2-X172 well high-pressure filling hanging filtration flowback liquid, LNXI70-X068 well emulsion fracturing fluid flowback liquid, LPP80-X10C well composite fiber sand consolidation agent sand control flowback liquid and acidification unblocking stock solution) (mixing the components in equal volume according to the ratio of 1:1:1:1:1), adjusting the pH of the mixed liquid to be neutral by NaOH, and adding the mixed liquid into crude oil according to the ratio of 10% (V/V); meanwhile, mixed wellbore maintenance agents (a corrosion inhibitor, a thick oil viscosity reducer, a desulfurizer, a hot washing additive, a solid-free kill fluid and a biological enzyme cleaning agent) are also taken (mixed according to the volume ratio of 1:1:1:1:1), the pH value is about 8.0, the pH value is not adjusted, and the mixed wellbore maintenance agents are added into the crude oil according to the volume ratio of 10% (V/V); crude oil emulsion is prepared according to SY/T5281-2000 method for detecting service performance of crude oil demulsifier, and the compound demulsifier (YZL-08) obtained in example 3 is adopted to carry out dehydration effect experiment. The results are shown in table 2 and fig. 7.
TABLE 2 demulsification Effect study of demulsifiers
Wherein the dosage of the demulsifier is 60mg/L, the demulsification temperature is 43 ℃, and the dehydration time is 75 min.
Application case 7:
taking 5 mixed flowback residual liquids (LPP2-504 well hot washing flowback liquid, LPP2-X172 well high-pressure filling hanging filtration flowback liquid, LNXI70-X068 well emulsion fracturing fluid flowback liquid, LPP80-X10C well composite fiber sand consolidation agent sand control flowback liquid and acidification unblocking stock solution) (mixing according to the volume ratio of 1:1:1:1:1), taking 5 mixed wellbore maintenance agents (corrosion inhibitor, thick oil viscosity reducer, desulfurizer, hot washing additive, non-solid phase well pressing liquid and biological enzyme cleaning agent) (mixing according to the volume ratio of 1:1:1:1:1, mixing according to the volume ratio of 1:1, and adding the mixed liquid of the two into crude oil according to the volume ratio of 10% (V/V); crude oil emulsion is prepared according to SY/T5281-2000 method for detecting service performance of crude oil demulsifier, and the compound demulsifier (YZL-08) obtained in example 4 is adopted to carry out dehydration effect experiment. The results are shown in table 3 and fig. 8.
TABLE 3 demulsification Effect study of demulsifiers
Wherein the dosage of the demulsifier is 60mg/L, the demulsification temperature is 43 ℃, and the dehydration time is 75 min.
As can be seen from table 3 and fig. 8, under the same conditions (temperature, time, demulsifier addition, etc.) compared with the dehydration condition before the combination, under the same conditions, for demulsification of crude oil emulsion to which 10% of mixed flowback residual liquid and mixed wellbore servicing agent are added, the single X-75 dehydration rate is 86.56%, severe wall hanging is achieved, the single L-4 dehydration rate is 48.42%, no wall hanging is achieved, and the demulsifier (YZL-08) combined with the two demulsifiers has a good dehydration rate of 92% for crude oil emulsion to which 10% (V/V) mixed liquid (mixed flowback residual liquid and mixed wellbore servicing agent) is added, and no wall hanging is achieved, indicating that the combination demulsifier has a significant synergistic effect, can improve the dehydration amount, and has a certain capability of resisting interference of the mixed flowback residual liquid and wellbore servicing agent in dehydration.
Claims (10)
1. The compound demulsifier is characterized by being prepared from a demulsifier X-75 and a demulsifier L-4 according to a mass ratio of 1-3: 1-3; wherein the demulsifier X-75 is a five-membered copolymerized polyether demulsifier; and the demulsifier L-4 is a demulsifier modified by phenolic aldehyde resin block polyether.
2. The compound demulsifier of claim 1, wherein: the demulsifier is prepared from a demulsifier X-75 and a demulsifier L-4 according to a mass ratio of 1: 1.
3. The compound demulsifier of claim 1, wherein: when the demulsifier X-75 is prepared, firstly preparing a bisphenol A phenolic amine resin diblock polyether demulsifier, wherein the mass ratio of propylene oxide to ethylene oxide is 1:1-3: 1; and then esterifying the bisphenol A phenolic amine resin diblock polyether demulsifier with acrylic acid, and copolymerizing with methyl methacrylate, styrene, methacrylic acid and acrylic acid by adopting an emulsion method to synthesize the five-membered copolymerized polyether demulsifier.
4. The compounded demulsifier of claim 3, wherein: wherein the mass ratio of the demulsifier after esterification to the methyl methacrylate to the styrene to the methacrylic acid to the acrylic acid is 6-7: 0.5-1: 1.5-2: 0.5-1: 0.5 to 1.
5. The compound demulsifier of claim 1, wherein: the demulsifier L-4 is a modified ultra-high molecular demulsifier which is obtained by using phenolic amine aldehyde resin polyoxypropylene polyoxyethylene block polyether as a framework and crosslinking and chain extending epoxy chloropropane, and has the molecular weight of 80-280 ten thousand.
6. The compound demulsifier of claim 5, which is characterized in that: during the specific preparation of the demulsifier L-4, epoxy chloropropane with the mass fraction of 8-10% is dripped into phenolic amine aldehyde resin polyoxypropylene polyoxyethylene block polyether at the temperature of 40-100 ℃, and the demulsifier L-4 is obtained after the addition and the reaction for 8-12 h.
7. The method for preparing the compound demulsifier of any one of claims 1-6, which is characterized by comprising the following steps: taking dry demulsifiers X-75 and L-4 according to the proportion, dissolving the demulsifier X-75 with methanol and the demulsifier L-4 with dimethylbenzene at normal temperature, and finally mixing the two uniformly to obtain the demulsifier.
8. The application of the compound demulsifier of any one of claims 1 to 6 in the dehydration of crude oil, wherein the interference of a well shaft maintenance agent and/or a flowback residual liquid in well entering operation exists during the dehydration of crude oil.
9. Use according to claim 8, characterized in that: the anti-oil well shaft maintenance agent is a single-component or mixed-component shaft maintenance agent; the well-entry operation flowback residual liquid is single-component or mixed-component flowback residual liquid for well-entry operation.
10. Use according to claims 8 to 9, characterized in that: when the demulsifier is used, the demulsification temperature is 40-50 ℃, the dehydration time is 45-75min, and the addition amount of the demulsifier is 10-60 mg/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023667A (en) * | 2022-12-28 | 2023-04-28 | 荆州市东泽化工科技有限公司 | Demulsifier and preparation method and application thereof |
| CN116144394A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Demulsifier for inferior crude oil and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100582A (en) * | 1989-12-28 | 1992-03-31 | Nalco Chemical Company | Water soluble polymer as water-in-oil demulsifier |
| CN1427018A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | High stability corboxylic latex |
| CN102746470A (en) * | 2011-04-19 | 2012-10-24 | 克拉玛依奥克化学有限公司 | Preparation method of efficient deemulsifier for naphthenic extra heavy oil and product thereof |
-
2021
- 2021-06-30 CN CN202110745219.4A patent/CN113416576B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100582A (en) * | 1989-12-28 | 1992-03-31 | Nalco Chemical Company | Water soluble polymer as water-in-oil demulsifier |
| CN1427018A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | High stability corboxylic latex |
| CN102746470A (en) * | 2011-04-19 | 2012-10-24 | 克拉玛依奥克化学有限公司 | Preparation method of efficient deemulsifier for naphthenic extra heavy oil and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴洪特等: "几种油田化学剂对原油破乳脱水的影响及破乳剂筛选", 《油田化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116144394A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Demulsifier for inferior crude oil and preparation method thereof |
| CN116023667A (en) * | 2022-12-28 | 2023-04-28 | 荆州市东泽化工科技有限公司 | Demulsifier and preparation method and application thereof |
| CN116023667B (en) * | 2022-12-28 | 2024-02-20 | 荆州市东泽化工科技有限公司 | Demulsifier and preparation method and application thereof |
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