A broad-spectrum condensate demulsifier and a preparation method thereof

Abstract

The present application provides a kind of broad-spectrum condensate demulsifier and its preparation method.The demulsifier of the present application is composed of the following components: firstly, a mixture HW of three structures formed by esterification cross-linking of inorganic acid polyhydroxy alkyl quaternary amine and polyoxypropylene polyoxyethylene ether with novel structure using diisocyanate;secondly, propoxylated hydrazine ether NW using a compound with hydrazine structure as a starter agent, and according to the mass ratio, HW:NW=2-10:3-7.The condensate demulsifier of the present application can be used for paraffin-based, intermediate-based and naphthenic-based condensate oils, as well as condensate oils containing different chemical agents obtained by different processes, and has the characteristics of low temperature, rapid, deep demulsification and low oil content in water, which is a broad-spectrum condensate demulsifier worthy of promotion.

Description

Technical Field

[0001] This invention relates to the field of oilfield chemical formulation technology, and in particular to a broad-spectrum condensate demulsifier and its preparation method. Background Technology

[0002] Condensate oil is the liquid phase component condensed from condensate gas fields or associated gas in oil fields, also known as natural gasoline. Its main components are a mixture of C5 to C11+ hydrocarbons, containing small amounts of hydrocarbons larger than C8, as well as impurities such as sulfur dioxide, thiophenes, thiols, thioethers, and polysulfides. Condensate oil is classified into three types: paraffinic, intermediate, and naphthenic. In actual high-temperature, high-pressure condensate gas reservoirs, the hydrocarbon fluid is in a saturated gaseous state with a high condensate water content. This condensate water is produced along with the condensate oil during extraction. Simultaneously, due to different extraction methods, such as depletion-type secondary drainage, foam drainage, circulating gas injection, high-temperature deep well drainage gas production, acid fracturing, and other production and drainage processes, the condensate oil forms emulsified condensate oil under dynamic driving. Because of the complex composition of emulsified condensate oil, traditional conventional demulsifiers are difficult to effectively demulsify, requiring specialized research and extensive screening and compounding work for different types and components, which brings considerable difficulties to practical applications.

[0003] Patent CN103937539A discloses a condensate demulsifier, composed of various conventional polyethers and sulfonates, which is effective for demulsifying certain types of condensate oils, but not very effective for paraffinic condensate oils. Patent CN103980933A discloses a condensate demulsifier, composed of polyoxyethylene ether, polyethylene polyamine ether, sodium chloride, and citric acid, which can rapidly demulsify condensate oil after acid fusing, but its demulsification effect on emulsified condensate oil obtained from the foam drainage process is not ideal. Patent CN104498080A discloses a condensate demulsifier, composed of crosslinked block polyether, comb-type silica-containing demulsifier, and betaine fluorocarbon surfactant, which can effectively demulsify emulsified condensate oil obtained from the foam drainage process, but its demulsification effect on condensate oil after acid fusing is not ideal. Patent CN106947517A discloses an oil-soluble demulsifier for condensate oil, which is obtained by compounding conventional demulsifiers. It can effectively demulsify emulsified condensate oil obtained from foam drainage processes, but its demulsification effect on naphthenic condensate oil is not ideal, and its oil solubility is not environmentally friendly. Patent CN107459999A discloses a condensate oil demulsifier, which is compounded by cationic polyether demulsifiers, water purification and oil removal agents, allyl chloride, and gemini quaternary ammonium salt surfactants. It can effectively demulsify emulsified condensate oil obtained from foam drainage processes, but the dosage is 700-10000 ppm, resulting in high costs. Patent CN108165302A discloses a condensate oil demulsifier, which is obtained by compounding phenolic resin polyether after trans-butenedioic acid esterification with the neutralization product of methanesulfonic acid and monoethanolamine, but its low-temperature demulsification effect is not ideal. Summary of the Invention

[0004] The purpose of this invention is to provide a broad-spectrum condensate demulsifier and its preparation method to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a broad-spectrum condensate demulsifier and its preparation method, comprising a mixture of HW and hydrazine ether NW, wherein the mass ratio of HW : NW = 2~10 : 3~7;

[0006] Wherein, the mixture HW is a mixture of three structures containing the following structural formulas I, II and III, formed by crosslinking inorganic acid polyhydroxyalkyl quaternary ammonium and polyoxypropylene polyoxyethylene ether through esterification of diisocyanate;

[0007] The hydrazine ether NW is a compound with the following structural formula IV, obtained by propoxylation reaction using a compound having a hydrazine structure as an initiator.

[0008] Among them, structural formulas I, II, III and IV are:

[0009] Formula I

[0010]

[0011] Formula II

[0012]

[0013] Formula III

[0014]

[0015] Formula IV

[0016] .

[0017] Preferred structures: I, II, III, and IV:

[0018] x is an integer from 1 to 11;

[0019] y is an integer from 1 to 11;

[0020] f is an integer between 20 and 30;

[0021] g is an integer between 10 and 25;

[0022] n is 0, 1, 2, or 3;

[0023] n1, n2, and n3 are integers from 1 to 12, and n1 + n2 + n3 = 15;

[0024] R is selected from tolyl, dicyclohexylmethane, isophorone, dimer acid, or diphenylmethane;

[0025] R0 is selected from methylbenzothiazolyl, chloropyridinyl, pyridinyl, pyrimidinyl, cyanoethyl, tert-butoxy, dimethylpyrimidinyl, methyl formate, ethyl formate, tert-butyl formate, or benzyl formate.

[0026] R1 is selected from inorganic acid polyhydroxyethyl quaternary ammonium, inorganic acid polyhydroxypropyl quaternary ammonium, inorganic acid polyhydroxybutyl quaternary ammonium or inorganic acid polycis-hydroxybutyl quaternary ammonium;

[0027] R3 is selected from polymerized ethylene oxide, polymerized propylene oxide, polymerized butyl oxide, or cis-polymerized butyl oxide;

[0028] R2⁻ is selected from Cl⁻, I⁻, Br⁻, HSO3⁻ or H2PO4⁻.

[0029] Preferably, the polyhydroxyalkyl quaternary ammonium cationic portion of the inorganic acid polyhydroxyalkyl quaternary ammonium has the following structural formula V, VI, VII or VIII:

[0030] Formula V Formula VI

[0031]

[0032] Formula VII

[0033]

[0034] Where m is an integer from 2 to 5.

[0035] Preferably, the initiator used to synthesize the polyoxypropylene polyoxyethylene ether has the following structural formula IX:

[0036] Formula IX

[0037] .

[0038] Preferably, the initiator used to synthesize the hydrazine ether NW has the following structural formula X:

[0039] Formula X

[0040] .

[0041] Preferably, it includes: S1. Synthesizing inorganic acid polyhydroxyalkyl quaternary ammonium:

[0042] Prepare a tertiary amine deionized water solution with a mass fraction of 40-60%, add an ionic liquid catalyst accounting for 0.1-0.3% of its total mass, and mix thoroughly.

[0043] Based on a molar ratio of tertiary amine to alkyl epoxide of 1:2 to 5, the deionized aqueous solution of tertiary amine and alkyl epoxide are simultaneously fed into a tubular reactor using metering pumps. The material residence time in the reactor is set to 50 to 150 seconds, the reaction temperature to -10 to 20°C, and the reaction pressure to 0.8 to 1.5 MPa to obtain hydroxyalkyl quaternary amine hydroxide.

[0044] The hydroxyalkyl quaternary ammonium hydroxide and the inorganic acid were mixed at a molar ratio of 1:1 at room temperature and then the solvent was removed under a vacuum of ≤-0.097 MPa and a temperature of 100-105℃ to obtain powdered inorganic acid hydroxyalkyl quaternary ammonium.

[0045] S2. Synthetic polyoxypropylene polyoxyethylene ether:

[0046] According to the molar ratio of initiator of structural formula IX, propylene oxide and ethylene oxide 1:20~30:10~15, add 0.3% of the total mass of the three basic catalysts to the initiator of structural formula IX at room temperature;

[0047] Heat to 90-100℃, dehydrate under vacuum for 30 minutes, and maintain the final temperature at 120-125℃ with a vacuum degree ≤-0.097MPa;

[0048] Under vacuum conditions, the temperature is gradually increased to 130–155°C, and a specified amount of propylene oxide is introduced within this range, while the reaction pressure is controlled at 0.2–0.45 MPa.

[0049] After the propylene oxide is fed in, aging is carried out at a temperature of 140-150℃.

[0050] After aging is complete, the system pressure is adjusted to ≤-0.02 MPa, and the specified amount of ethylene oxide is introduced. The reaction temperature is 125~140℃, and the reaction pressure is 0.15~0.35 MPa.

[0051] After the ethylene oxide is fed in, it is aged at a temperature of 130-140℃.

[0052] After aging is complete, the pressure is controlled at ≤-0.02 MPa to obtain polyoxypropylene polyoxyethylene ether;

[0053] S3. Preparation of mixture HW:

[0054] Based on the mass ratio of powdered inorganic acid hydroxyalkyl quaternary ammonium to polyoxypropylene polyoxyethylene ether, a solution with a mass fraction of 50-80% is prepared using a mixed solvent.

[0055] Heat the solution to 75–80°C, and add dropwise a diisocyanate solution with a mass fraction of 25–40% prepared in advance with a mixed solvent. The mass of the added diisocyanate accounts for 2–5% of the total mass of the powdered inorganic acid hydroxyalkyl quaternary ammonium and polyoxypropylene polyoxyethylene ether.

[0056] After the addition is complete, keep warm at 75-80℃ for 1 hour to obtain mixture HW.

[0057] Preferably, the method includes the following steps: mixing the mixture HW obtained by the method of claim 5 with the hydrazine ether NW obtained by the method of claim 6 at room temperature according to a mass ratio of HW : NW = 2-10 : 3-7, and stirring until homogeneous to obtain the broad-spectrum condensate demulsifier.

[0058] The technical effects and advantages of this invention are as follows:

[0059] The demulsifier prepared by this invention is a mixture of three structures formed by esterification and crosslinking of inorganic acid polyhydroxyalkyl quaternary ammonium with novel polyoxypropylene polyoxyethylene ether using diisocyanate, and then mixed with a novel propoxylated hydrazine ether in a certain proportion. In terms of structure, it expands the molecular surface activity and can form monolayers or multilayers at solid-liquid and liquid-liquid interfaces, thereby changing the properties of the oil-water interface. It optimizes the shortcomings of traditional condensate oil demulsifiers, which cannot simultaneously perform wettability, adsorption, permeability, coagulation and displacement. Therefore, this condensate oil demulsifier has the characteristics of wide applicability, low temperature, high efficiency, fast demulsification speed, and low oil content in treated wastewater. It greatly improves the defects of existing products, such as poor adaptability, unsatisfactory demulsification effect, low condensate oil recovery rate, especially the defects of no demulsification or insufficient demulsification in winter. It is a new type of condensate oil demulsifier worthy of promotion. Detailed Implementation

[0060] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0061] This invention provides a broad-spectrum condensate oil demulsifier and its preparation method:

[0062] Preparation of chlorinated polyhydroxyethyltrimethylamine: A 45% deionized trimethylamine aqueous solution was prepared, and 0.15% of the total mass of the deionized trimethylamine aqueous solution was added to an ionic liquid catalyst, N-octylpyridine bromide, and stirred until homogeneous. The trimethylamine and ethylene oxide were simultaneously pumped into a tubular reactor using a metering pump at a molar ratio of 1:3. The residence time of the materials in the tubular reactor was controlled to be 80–85 seconds. The reaction temperature was controlled to be -10 to -5℃, and the reaction pressure was controlled to be 0.8–0.9 MPa, yielding liquid hydroxyethyltrimethylamine hydroxide. The liquid hydroxyethyltrimethylamine hydroxide and hydrochloric acid were then mixed homogeneously at room temperature, and the solvent was extracted under vacuum ≤ -0.097 MPa at 100–105℃ to obtain powdered chlorinated polyhydroxyethyltrimethylamine.

[0063] Preparation of 2-octyl-1-dodecyl alcohol ether from polyoxypropylene and polyoxyethylene: The molar ratio of 2-octyl-1-dodecyl alcohol: propylene oxide: ethylene oxide = 1:25:11 was used. At room temperature, 0.3% sodium hydroxide catalyst (based on the total mass of 2-octyl-1-dodecyl alcohol, propylene oxide, and ethylene oxide) was added. The temperature was raised to 90–100°C, and vacuum dehydration was initiated for 30 minutes. The final temperature was controlled at 120–125°C, and the vacuum was controlled at ≤-0.097 MPa. Under vacuum, the 2-octyl-1-dodecyl alcohol initiator was gradually heated to 135–140°C, and dehydration was initiated within this temperature range. A specified amount of propylene oxide is introduced, and the reaction pressure is controlled at 0.25–0.35 MPa. After the propylene oxide is completely introduced, aging begins, with the aging temperature controlled at 140–150 °C. After aging, the pressure is controlled at ≤-0.02 MPa. Then, a specified amount of ethylene oxide is introduced, with the reaction temperature controlled at 125–130 °C and the reaction pressure controlled at 0.15–0.25 MPa. After the ethylene oxide is completely introduced, aging begins, with the aging temperature controlled at 130–140 °C. After aging, the pressure is controlled at ≤-0.02 MPa, yielding polyoxypropylene polyoxyethylene 2-octyl-1-dodecyl alcohol ether.

[0064] A mixture H formed by esterification and crosslinking of chlorinated polyhydroxyethyltrimethylamine and polyoxypropylene polyoxyethylene 2-octyl-1-dodecyl ether W1 Preparation: Chlorinated polyhydroxyethyltrimethylamine:polyoxypropylene polyoxyethylene 2-octyl-1-dodecyl ether = 5:16 by mass. Using this total mass as a base, a 65% solution was prepared with a mixed solvent (dimethylformamide:tetrahydrofuran = 1:1.5 by mass). The solution was heated and controlled at 75–80°C. A 30% toluene diisocyanate solution prepared with the mixed solvent was then added dropwise. The added toluene diisocyanate solute accounted for 2% of the total mass of the powdered inorganic acid hydroxyalkyl quaternary ammonium and polyoxypropylene polyoxyethylene ether. After the addition was complete, the mixture was kept at 75–80°C for 1 hour to obtain mixture H.W1。

[0065] 4,4-Methylbenzothiazole polyoxypropylene hydrazine ether N W1 Preparation: Following a molar ratio of 4-methyl-2-hydrazinobenzothiazole:propylene oxide = 1:8, 4-methyl-2-hydrazinobenzothiazole was first mixed with an equal mass of dimethylformamide and stirred until heated to 35–60°C. Then, an equal mass of propylene oxide was introduced, and the mixture was maintained at 35–60°C for 30–60 minutes. Next, 0.1% (by mass) of sodium hydride catalyst was added to the reaction solution, and the mixture was stirred while hydrogen was extracted under a vacuum ≤ -0.03 MPa for 30 minutes. Then, the remaining propylene oxide was introduced while controlling the reaction temperature at 110–120°C and the reaction pressure at 0.15–0.25 MPa. After the propylene oxide was completely introduced, the mixture was maintained at an aging temperature of 110–120°C for 30 minutes to obtain 4-methylbenzothiazole polyoxypropylene hydrazine ether N. W1。

[0066] Preparation of broad-spectrum condensate demulsifier: According to the mass ratio, H W1 :N W1 =6:4, H W1 and N W1 The broad-spectrum condensate demulsifier DNX-1 of this invention was obtained by mixing and stirring at room temperature according to the mass ratio.

[0067] The physicochemical properties of demulsifier DNX-1 are as follows:

[0068] 1. Appearance: Amber-colored, viscous, transparent liquid

[0069] 2. RSN=13.5

[0070] Preparation of sulfite-modified polyhydroxypropyltriethylamine: A 50% deionized triethylamine aqueous solution was prepared, and 0.18% (by mass) of the total mass of the deionized triethylamine aqueous solution was added to an ionic liquid N-hexylpyridine hexafluorophosphate catalyst and stirred until homogeneous. The triethylamine aqueous solution and propylene oxide were simultaneously pumped into a tubular reactor using a metering pump at a molar ratio of 1:4. The residence time of the materials in the tubular reactor was controlled to be 90–95 seconds, the reaction temperature was controlled to be -5–0℃, and the reaction pressure was controlled to be 0.85–0.95 MPa, yielding liquid hydroxypropyltriethylamine hydroxide. The liquid hydroxypropyltriethylamine hydroxide and sulfurous acid were then mixed homogeneously at room temperature, and the solvent was extracted under vacuum ≤-0.097 MPa at 100–105℃ to obtain powdered sulfite-modified polyhydroxypropyltriethylamine.

[0071] Preparation of 2-hexyl-1-decyl alcohol ether from polyoxypropylene and polyoxyethylene: According to the molar ratio of 2-hexyl-1-decyl alcohol: propylene oxide: ethylene oxide = 1:26:12, 0.3% sodium hydroxide catalyst (based on the total mass of 2-hexyl-1-decyl alcohol, propylene oxide, and ethylene oxide) was added to 2-hexyl-1-decyl alcohol at room temperature. The temperature was raised to 90–100°C, and vacuum dehydration was initiated for 30 minutes. The final temperature was controlled at 120–125°C, and the vacuum was controlled at ≤-0.097 MPa. Under vacuum, the temperature of 2-hexyl-1-decyl alcohol was gradually raised to 135–140°C, and maintained within this temperature range. A specified amount of propylene oxide is introduced into the reactor, and the reaction pressure is controlled at 0.25–0.35 MPa. After the propylene oxide is completely introduced, aging begins, with the aging temperature controlled at 140–150 °C. After aging, the pressure is controlled at ≤-0.02 MPa. Then, a specified amount of ethylene oxide is introduced, with the reaction temperature controlled at 125–130 °C and the reaction pressure controlled at 0.15–0.25 MPa. After the ethylene oxide is completely introduced, aging begins, with the aging temperature controlled at 130–140 °C. After aging, the pressure is controlled at ≤-0.02 MPa, yielding polyoxypropylene-ethylene 2-hexyl-1-decyl alcohol ether.

[0072] A mixture H formed by esterification and crosslinking of sulfite-treated polyhydroxypropyl quaternary ammonium with polyoxypropylene and polyoxyethylene 2-hexyl-1-decyl alcohol ether W2 Preparation: A 55% solution was prepared using a mixed solvent (dimethylformamide:tetrahydrofuran = 1:1.8) based on the total mass of the mixture, with a mass ratio of 6:17 (sulfite-treated polyhydroxypropyltriethylamine:polyoxypropylene / polyoxyethylene 2-hexyl-1-decyl alcohol ether). The solution was heated to 75–80°C, and a 32% solution of diphenylmethane diisocyanate (prepared with the mixed solvent) was added dropwise. The added solute, diphenylmethane diisocyanate, accounted for 3% of the total mass of the sulfite-treated polyhydroxypropyltriethylamine and polyoxypropylene / polyoxyethylene 2-hexyl-1-decyl alcohol ether. After the addition was complete, the mixture was kept at 75–80°C for 1 hour to obtain mixture H. W2。

[0073] 4,4,6-Dimethylpyrimidine polyoxypropylene hydrazine ether N W2Preparation: Following a molar ratio of 2-hydrazino-4,6-dimethylpyrimidine to propylene oxide = 1:9, 2-hydrazino-4,6-dimethylpyrimidine was first mixed with an equal mass of dimethylformamide and stirred until heated to 35–60°C. Then, an equal mass of propylene oxide was introduced, and the mixture was maintained at 35–60°C for 30–60 minutes. Next, 0.1% (by mass) of sodium hydride catalyst was added to the reaction solution, and the mixture was stirred while hydrogen was extracted under a vacuum ≤ -0.03 MPa for 30 minutes. Then, the remaining propylene oxide was introduced while controlling the reaction temperature at 110–120°C and the reaction pressure at 0.15–0.25 MPa. After the propylene oxide was completely introduced, the mixture was maintained at an aging temperature of 110–120°C for 30 minutes to obtain 4,6-dimethylpyrimidine polyoxypropylene hydrazine ether N. W2。

[0074] Preparation of broad-spectrum condensate demulsifier: According to the mass ratio, H W2 :N W2 =6:5, H W2 and N W2 The broad-spectrum condensate demulsifier DNX-2 of this invention was obtained by mixing and stirring at room temperature according to the mass ratio.

[0075] The physicochemical properties of demulsifier DNX-2 are as follows:

[0076] 1. Appearance: Amber-colored, viscous, transparent liquid

[0077] 2. RSN=11.6

[0078] Preparation of dihydrophosphorylated polyhydroxybutyltripropylamine: A 52% deionized tripropylamine aqueous solution was prepared, and 0.21% of the total mass of the deionized tripropylamine aqueous solution was added to an ionic liquid N-hexylpyridine tetrafluoroborate catalyst and stirred until homogeneous. The tripropylamine and cis-2,3-epoxybutane were simultaneously pumped into a tubular reactor using a metering pump at a molar ratio of 1:3. The residence time of the materials in the tubular reactor was controlled to be 95–100 seconds, the reaction temperature was controlled to be 0–5℃, and the reaction pressure was controlled to be 0.95–1 MPa, yielding liquid hydroxybutyltripropylamine hydroxide. The liquid hydroxybutyltripropylamine hydroxide and dihydrophosphoric acid were then mixed homogeneously at room temperature, and the solvent was extracted under vacuum ≤-0.097 MPa and at a temperature of 100–105℃ to obtain powdered dihydrophosphorylated polyhydroxybutyltripropylamine.

[0079] Preparation of 2-pentyl-1-nonanol ether from polyoxypropylene and polyoxyethylene: At room temperature, 0.3% (by mass of the total mass of 2-pentyl-1-nonanol, propylene oxide, and ethylene oxide) of an alkaline catalyst was added to 2-pentyl-1-nonanol in a molar ratio of 1:27:13. The temperature was raised to 90–100°C, and vacuum dehydration was initiated for 30 minutes. The final temperature was controlled at 120–125°C, and the vacuum was controlled at ≤-0.097 MPa. Under vacuum, the IX-structure initiator was gradually heated to 135–140°C, and dehydration was initiated within this temperature range. A specified amount of propylene oxide is introduced, and the reaction pressure is controlled at 0.25–0.35 MPa. After the propylene oxide is completely introduced, aging begins, with the aging temperature controlled at 140–150°C. After aging, the pressure is controlled at ≤-0.02 MPa. Then, a specified amount of ethylene oxide is introduced, with the reaction temperature controlled at 125–130°C and the reaction pressure controlled at 0.15–0.25 MPa. After the ethylene oxide is completely introduced, aging begins, with the aging temperature controlled at 130–140°C. After aging, the pressure is controlled at ≤-0.02 MPa, yielding polyoxypropylene polyoxyethylene 2-pentyl-1-nonyl alcohol ether.

[0080] H is a mixture formed by crosslinking dihydrophosphorylated polyhydroxybutyltripropylamine with polyoxypropylene and polyoxyethylene 2-pentyl-1-nonyl alcohol ether. W3 Preparation: A 60% solution was prepared using a mixed solvent (dimethylformamide:tetrahydrofuran = 1:2) based on the mass ratio of dihydrophosphorylated polyhydroxybutyltripropylamine to polyoxypropylene / polyoxyethylene 2-pentyl-1-nonyl alcohol ether (6:15). The solution was heated to 75–80°C, and a 34% solution of dimer acid diisocyanate (prepared with the mixed solvent) was added dropwise. The added mass of dimer acid diisocyanate accounted for 3% of the total mass of the powdered dihydrophosphorylated polyhydroxybutyltripropylamine and polyoxypropylene / polyoxyethylene 2-pentyl-1-nonyl alcohol ether. After the addition was complete, the mixture was kept at 75–80°C for 1 hour to obtain mixture H. W3。

[0081] Methyl formate hydrazide N W3Preparation: Following a molar ratio of methyl hydrazine formate to propylene oxide of 1:10, methyl hydrazine formate was first mixed with an equal mass of dimethylformamide and stirred until heated to 35–60°C. Then, an equal mass of propylene oxide was introduced, and the mixture was maintained at 35–60°C for 30–60 minutes. Next, 0.1% (by mass) of sodium hydride catalyst was added to the reaction solution, and the mixture was stirred while hydrogen was extracted under a vacuum ≤ -0.03 MPa for 30 minutes. Then, the remaining propylene oxide was introduced while controlling the reaction temperature at 110–120°C and the reaction pressure at 0.15–0.25 MPa. After the propylene oxide was completely introduced, the mixture was maintained at an aging temperature of 110–120°C for 30 minutes to obtain methyl formate hydrazine ether N. W3。

[0082] Preparation of broad-spectrum condensate demulsifier: According to the mass ratio, H W3 :N W3 =7:4, H W and N W The broad-spectrum condensate demulsifier DNX-3 of this invention was obtained by mixing and stirring at room temperature according to the mass ratio.

[0083] The physicochemical properties of demulsifier DNX-3 are as follows:

[0084] 1. Appearance: Amber-colored, viscous, transparent liquid

[0085] 2. RSN=10.8

[0086] Preparation of dihydrophosphorylated polyhydroxybutyltriethylamine: A 55% deionized triethylamine aqueous solution was prepared, and 0.25% of the total mass of the deionized triethylamine aqueous solution was added to an ionic liquid N-hexylpyridine bis(trifluoromethanesulfonyl)imide salt catalyst and stirred until homogeneous. The triethylamine and cis-2,3-epoxybutane were simultaneously pumped into a tubular reactor using a metering pump at a molar ratio of 1:5. The residence time of the materials in the tubular reactor was controlled to be 90–95 seconds, the reaction temperature was controlled to be -5–0℃, and the reaction pressure was controlled to be 0.85–0.95 MPa, yielding liquid polyhydroxybutyltriethylamine hydroxide. The polyhydroxybutyltriethylamine hydroxide and dihydrophosphoric acid were then mixed homogeneously at room temperature at a molar ratio of 1:1. The solvent was extracted under vacuum ≤-0.097 MPa and at a temperature of 100–105℃ to obtain powdered polyhydroxybutyltriethylamine dihydrophosphorylated.

[0087] Preparation of 2-butyl-1-octanol ether from polyoxypropylene and polyoxyethylene: According to the molar ratio of 2-butyl-1-octanol: propylene oxide: ethylene oxide = 1:26:13, 0.3% (by mass) of an alkaline catalyst (based on the total mass of 2-butyl-1-octanol, propylene oxide, and ethylene oxide) was added to 2-butyl-1-octanol at room temperature. The temperature was raised to 90–100°C, and vacuum dehydration was initiated for 30 minutes. The final temperature was controlled at 120–125°C, and the vacuum was controlled at ≤-0.097 MPa. Under vacuum, the IX-structure initiator was gradually heated to 135–140°C, and dehydration was initiated within this temperature range. A specified amount of propylene oxide is introduced, and the reaction pressure is controlled at 0.25–0.35 MPa. After the propylene oxide is completely introduced, aging begins, with the aging temperature controlled at 140–150°C. After aging, the pressure is controlled at ≤-0.02 MPa. Then, a specified amount of ethylene oxide is introduced, with the reaction temperature controlled at 125–130°C and the reaction pressure controlled at 0.15–0.25 MPa. After the ethylene oxide is completely introduced, aging begins, with the aging temperature controlled at 130–140°C. After aging, the pressure is controlled at ≤-0.02 MPa, yielding polyoxypropylene polyoxyethylene ether 2-butyl-1-octanol ether.

[0088] H is a mixture formed by crosslinking dihydrophosphorylated polyhydroxybutyltriethylamine with oxypropylene polyoxyethylene ether 2-butyl-1-octanol ether via esterification. W4 Preparation: A 65% solution was prepared using a mixed solvent (dimethylformamide:tetrahydrofuran = 1:1.5) based on a mass ratio of 5:17 (dihydrophosphorylated polyhydroxybutyltriethylamine:oxypropylene polyoxyethylene ether 2-butyl-1-octanol ether). The solution was heated to 75–80°C, and a 30% isophorone diisocyanate solution prepared with the mixed solvent was added dropwise. The added isophorone diisocyanate solute accounted for 4% of the total mass of the dihydrophosphorylated polyhydroxybutyltriethylamine and the oxypropylene polyoxyethylene ether 2-butyl-1-octanol ether. After the addition was complete, the mixture was kept at 75–80°C for 1 hour to obtain mixture H. W4。

[0089] benzyl formate hydrazine N W4Preparation: Following a molar ratio of benzyl hydrazinocarbamate to propylene oxide of 1:11, benzyl hydrazinocarbamate was first mixed with an equal mass of dimethylformamide and stirred until heated to 35–60°C. Then, an equal mass of propylene oxide was introduced, and the mixture was maintained at 35–60°C for 30–60 minutes. Next, 0.1% (by mass) of sodium hydride catalyst was added to the reaction solution, and the mixture was stirred while hydrogen was extracted under a vacuum ≤ -0.03 MPa for 30 minutes. Then, the remaining propylene oxide was introduced while controlling the reaction temperature at 110–120°C and the reaction pressure at 0.15–0.25 MPa. After the propylene oxide was completely introduced, the mixture was maintained at an aging temperature of 110–120°C for 30 minutes to obtain benzyl formate hydrazinocarbamate N. W4。

[0090] Preparation of broad-spectrum condensate demulsifier: According to the mass ratio, H W4 :N W4 =8:5, H W4 and N W4 The broad-spectrum condensate demulsifier DNX-4 of this invention was obtained by mixing and stirring at room temperature according to the mass ratio.

[0091] The physicochemical properties of demulsifier DNX-4 are as follows:

[0092] 1. Appearance: Amber-colored, viscous, transparent liquid

[0093] 2. RSN=9.9

[0094] All the above indicators meet the requirements of the People's Republic of China Petroleum and Natural Gas Industry Standard SY / T5280-2018 General Technical Conditions for the Use of Crude Oil Demulsifiers.

[0095] The following demulsification experiments were conducted to compare condensate oils obtained from different types and collection methods. The evaluation criteria adopted the People's Republic of China Petroleum and Natural Gas Industry Standard SY / T5280-2018 General Technical Conditions for Crude Oil Demulsifiers.

[0096] The water content of condensate oil was determined according to the People's Republic of China National Standard GB / T 8929-2006 Determination of Water Content in Crude Oil by Distillation Method.

[0097] The oil content in the condensate extract water was determined by spectrophotometry according to the People's Republic of China Petroleum and Natural Gas Industry Standard SY / T0530-2011, "Method for Determination of Oil Content in Oilfield Produced Water".

[0098] The experimental conditions and dosage concentrations were all based on the on-site process conditions and actual dosage concentrations, and were tested under comparable conditions.

[0099] Table 1 Comparative experimental data on dehydration and water purification using paraffin-based condensate oil demulsifiers.

[0100]

[0101] Table 2 Comparative Experimental Data of Dehydration and Water Purification Using Intermediate-Based Condensate Oil Demulsifier

[0102]

[0103] Table 3 Comparative experimental data on dehydration and water purification using naphthenic condensate oil demulsifiers

[0104]

[0105] Table 4 Comparative experimental data of condensate oil demulsifier dehydration and water purification obtained by acid fracturing

[0106]

[0107] Table 5 Comparative experimental data of condensate oil demulsifier dehydration and water purification obtained by acid fracturing

[0108]

[0109] Table 6 Comparative experimental data of obtaining condensate oil demulsifier dehydration and purification water using foam drainage

[0110]

[0111]

[0112] Table 7 Comparative experimental data of obtaining condensate oil demulsifier dehydration and purification water using foam drainage

[0113]

[0114] 1. The experimental data from Tables 1 to 3 clearly show that:

[0115] Under the same conditions, the condensate demulsifier of the present invention showed superior demulsification and water purification capabilities compared with the standard demulsifier for paraffinic, intermediate, and naphthenic condensate oils.

[0116] 2. The experimental data in Tables 4 and 6 clearly show that:

[0117] Under the same conditions, the condensate demulsifier of the present invention showed superior demulsification and water purification capabilities compared with the standard demulsifier for condensate obtained by acid fusing and foam drainage.

[0118] 3. The experimental data in Tables 5 and 7 clearly show that:

[0119] Under comparable conditions, the condensate demulsifier of the present invention exhibits superior demulsification and water purification capabilities at low temperatures for condensate oil obtained by acid fusing and foam drainage compared to the standard demulsifier.

[0120] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A broad-spectrum condensate oil demulsifier, characterized in that: It consists of a mixture of HW and hydrazine ether NW, with a mass ratio of HW : NW = 2~10 : 3~7; Wherein, the mixture HW is a mixture of three structures containing the following structural formulas I, II and III, formed by crosslinking inorganic acid polyhydroxyalkyl quaternary ammonium and polyoxypropylene polyoxyethylene ether through esterification of diisocyanate; The hydrazine ether NW is a compound with the following structural formula IV, obtained by propoxylation reaction using a compound having a hydrazine structure as an initiator. Among them, structural formulas I, II, III and IV are: Formula I Formula II Formula III Formula IV 。 2. The broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: In structural formulas I, II, III, and IV: x is an integer from 1 to 11; y is an integer from 1 to 11; f is an integer between 20 and 30; g is an integer between 10 and 25; n is 0, 1, 2, or 3; n1, n2, and n3 are integers from 1 to 12, and n1 + n2 + n3 = 15; R is selected from tolyl, dicyclohexylmethane, isophorone, dimer acid, or diphenylmethane; R0 is selected from methylbenzothiazolyl, chloropyridinyl, pyridinyl, pyrimidinyl, cyanoethyl, tert-butoxy, dimethylpyrimidinyl, methyl formate, ethyl formate, tert-butyl formate, or benzyl formate. R1 is selected from inorganic acid polyhydroxyethyl quaternary ammonium, inorganic acid polyhydroxypropyl quaternary ammonium, inorganic acid polyhydroxybutyl quaternary ammonium or inorganic acid polycis-hydroxybutyl quaternary ammonium; R3 is selected from polymerized ethylene oxide, polymerized propylene oxide, polymerized butyl oxide, or cis-polymerized butyl oxide; R2⁻ is selected from Cl⁻, I⁻, Br⁻, HSO3⁻ or H2PO4⁻.

3. The broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: The polyhydroxyalkyl quaternary ammonium cationic moiety in the inorganic acid polyhydroxyalkyl quaternary ammonium has the following structural formula V, VI, VII or VIII: Formula V Formula VI Formula VII Where m is an integer from 2 to 5.

4. The broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: The initiator used to synthesize the polyoxypropylene polyoxyethylene ether has the following structural formula IX: Formula IX 。 5. The broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: The initiator used to synthesize the hydrazine ether NW has the following structural formula X: Formula X 。 6. The manufacturing process of a broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: include: S1. Synthesis of inorganic acid polyhydroxyalkyl quaternary ammonium: Prepare a tertiary amine deionized water solution with a mass fraction of 40-60%, add an ionic liquid catalyst accounting for 0.1-0.3% of its total mass, and mix thoroughly. Based on a molar ratio of tertiary amine to alkyl epoxide of 1:2 to 5, the deionized aqueous solution of tertiary amine and alkyl epoxide are simultaneously fed into a tubular reactor using metering pumps. The material residence time in the reactor is set to 50 to 150 seconds, the reaction temperature to -10 to 20°C, and the reaction pressure to 0.8 to 1.5 MPa to obtain hydroxyalkyl quaternary amine hydroxide. The hydroxyalkyl quaternary ammonium hydroxide and the inorganic acid were mixed at a molar ratio of 1:1 at room temperature and then the solvent was removed under a vacuum of ≤-0.097 MPa and a temperature of 100-105℃ to obtain powdered inorganic acid hydroxyalkyl quaternary ammonium. S2. Synthetic polyoxypropylene polyoxyethylene ether: According to the molar ratio of initiator of structural formula IX, propylene oxide and ethylene oxide 1:20~30:10~15, add 0.3% of the total mass of the three basic catalysts to the initiator of structural formula IX at room temperature; Heat to 90-100℃, vacuum dehydrate for 30 minutes, and finally maintain the temperature at 120-125℃ with a vacuum degree ≤-0.097 MPa; Under vacuum conditions, the temperature is gradually increased to 130–155°C, and a specified amount of propylene oxide is introduced within this range, while the reaction pressure is controlled at 0.2–0.45 MPa. After the propylene oxide is fed in, aging is carried out at a temperature of 140-150℃. After aging is complete, the system pressure is adjusted to ≤-0.02 MPa, and the specified amount of ethylene oxide is introduced. The reaction temperature is 125~140℃, and the reaction pressure is 0.15~0.35 MPa. After the ethylene oxide is fed in, it is aged at a temperature of 130-140℃. After aging is complete, the pressure is controlled at ≤-0.02 MPa to obtain polyoxypropylene polyoxyethylene ether; S3. Preparation of mixture HW: Based on the mass ratio of powdered inorganic acid hydroxyalkyl quaternary ammonium to polyoxypropylene polyoxyethylene ether, a solution with a mass fraction of 50-80% is prepared using a mixed solvent. Heat the solution to 75–80°C, and add dropwise a diisocyanate solution with a mass fraction of 25–40% prepared in advance with a mixed solvent. The mass of the added diisocyanate accounts for 2–5% of the total mass of the powdered inorganic acid hydroxyalkyl quaternary ammonium and polyoxypropylene polyoxyethylene ether. After the addition is complete, keep warm at 75-80℃ for 1 hour to obtain mixture HW.

7. The method for preparing a broad-spectrum condensate oil demulsifier according to claim 1, characterized in that: Includes the following steps: According to the mass ratio HW : NW = 2~10 : 3~7, the mixture HW obtained by the method of claim 5 and the hydrazine ether NW obtained by the method of claim 6 are mixed at room temperature and stirred evenly to obtain the broad-spectrum condensate demulsifier.

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