CN103086472B - High-temperature sewage treatment reverse demulsifier of ultra-heavy oil - Google Patents

Abstract

A kind of anti-phase demulsifier for ultra-heavy oil high-temperature sewage treatment of the present invention first uses glycerol and epichlorohydrin as raw materials, boron trifluoride ether solution as initiator to prepare chlorinated polyether, and chlorinated polyether Ether and trimethylamine aqueous solution are prepared in a high-pressure reactor to prepare cationic polyether; then methanol is used as a solvent, boron trifluoride ether is used as an initiator, and ethylenediamine, methyl acrylate, etc. are repeatedly and alternately carried out Michael addition reaction and amidation reaction , to prepare 3.0 generation dendrimer polyamide-amine; then polyethylene glycol and polypropylene glycol are used as raw materials, potassium hydroxide powder is used as catalyst, and polypropylene glycol is added after polyethylene glycol reacts for a period of time to obtain nonionic polyether ; Finally, the 3.0 generation polyamide-amine is used as the cross-linking agent, and the cationic polyether is compounded with the non-ionic polyether to obtain a modified composite type - polyamide-amine-polyether type super heavy oil high temperature sewage treatment reverse demulsifier.

Description

A reverse phase demulsifier for ultra-heavy oil high temperature sewage treatment

technical field

The invention relates to the technical field of petrochemical treatment agents, and the provided inverse demulsifier is especially suitable for the treatment of ultra-heavy oil high-temperature sewage.

Background technique

The important feature of super heavy oil that is different from other types of petroleum resources is that it has high asphaltene and colloid content, resulting in high viscosity and high density. Super heavy oil is mostly exploited by steam thermal recovery, and the high temperature produced fluid has the following characteristics: (1) Ultra-heavy oil has a high density. Due to the high content of colloids and asphaltene, the density difference between crude oil and water is small. The average density of heavy oil is 900kg/m ³ , and the density of ultra-heavy oil is above 990kg/m ³ (2) The super-heavy oil production fluid has more impurities, the oil content and suspended solids content are as high as 10000 mg/L or more, and contains petroleum, suspended solids, dispersed oil and slick oil, emulsified oil and chemical agents, etc. (3) Due to the natural emulsifying properties of colloid and asphalt, it is difficult to increase the coagulation of oil droplets, which increases the difficulty in demulsification of super-heavy oil production fluid, and the emulsification is serious; (4) has a large viscosity, especially It is more obvious when the water temperature is low; (5) the water temperature is high, in order to reduce the crude oil viscosity in the development process, the temperature is often raised to above 90°C; (6) the super heavy oil production fluid contains a large amount of cations (Na ⁺ , Ca ²⁺ , etc.) and anions (Cl ^- , SO ₄ ^2-, etc.), which will affect the buffer capacity, salt content and scaling tendency of heavy oil produced fluid; During the process, a large amount of chemical agents such as demulsifiers used will remain in the sewage, making the emulsion formed by the sewage extremely stable, and it is one of the most difficult oil production wastewater to treat.

Patent disclosure for inverse demulsifiers: the U.S. has announced a quaternary ammonium salt inverse demulsifier (US387017); the U.S. has announced an allyl inverse demulsifier (US4614593); Amine polymer compound demulsifier developed by crude oil (EP0331323A2); China announced a reverse phase demulsifier and its preparation method (CN102559246A), which is cationic polyamide-amine, polyepichlorohydrin quaternary ammonium salt, polyacrylamide Oxyethyltrimethylammonium chloride and water are mixed to obtain the reverse phase demulsifier. China has announced a kind of preparation method (CN101357992) of high-efficiency reverse phase demulsifier of star-shaped polyquaternium ammonium salt. Using polyamide-amine as cross-linking agent, the star-shaped polyquaternium reverse phase demulsifier was finally prepared. China has also announced a kind of high-efficiency inverse demulsifier for heavy oil sewage treatment (CN1966138), using propylene glycol as an initiator, under the action of a catalyst, carrying out propoxylation reaction, and then carrying out addition polymerization with ethylene oxide, Using nonylphenol as an initiator, under the action of a catalyst, it reacts with ethylene oxide to generate nonylphenol ethoxylate, and then conducts addition polymerization with propylene oxide to generate alkylphenol polyoxyethylene ether; The mixture of propylene glycol polyether and alkylphenol polyoxyethylene ether is esterified with acrylic acid under acidic conditions, and undergoes free radical polymerization under the action of an initiator to form an esterified product; then esterified with maleic acid and partially blocked , Generate acrylic modified polymer demulsifier.

At present, there are many kinds of inverse demulsifiers, which are highly targeted, mainly including inorganic polymer compounds and organic cationic polymers. However, when applied to the inverse demulsification of super heavy oil production fluid, the effect is not good. Ideal, with the increasingly complex water quality of ultra-heavy oil high-temperature sewage, the high-temperature sewage has changed from the W/O type at the initial stage of development to the O/W type or W/O/W type. The oil-water emulsification stability is extremely strong, and the traditional reverse phase Demulsifiers have been difficult to meet the requirements, so the development of super heavy oil high-temperature production fluid inverse demulsifiers with high temperature resistance and excellent performance is particularly urgent.

In the present invention, polyamide-amine, polyether and non-ionic polymer are copolymerized to obtain a new type of modified inverse demulsifier, which belongs to water-soluble polymer and has excellent breaking effect on oil-in-water emulsion of ultra-heavy oil and high-temperature sewage. Emulsion effect, also has the properties of electrical neutralization, adsorption, bridging, etc. Adding 10-30ppm can effectively remove oil, suspended solids and other pollutants in high oily sewage.

Contents of the invention

The object of the present invention is to provide a high-efficiency reverse phase demulsifier for super-heavy oil high-temperature sewage treatment, which can efficiently treat super-heavy oil high-temperature sewage, has the beneficial effects of fast oil-water separation speed, improved product universality and economic benefits of the product.

The purpose of the present invention is achieved in this way: a kind of reverse phase demulsifier for super heavy oil high temperature sewage treatment, the obtained modified composite reverse phase demulsifier uses cationic polyether and nonionic polyether as raw materials, and uses 3.0G dendritic polyether Amide-amine is a crosslinking agent, and the implementation steps are as follows:

Wherein the synthesis of cationic polyether:

Add 0.020-0.030mol of glycerol into a four-necked flask equipped with a stirrer, condenser, and thermometer, then add 2.10-2.17g of boron trifluoride ether, control the temperature at 45-55°C under stirring, and then slowly drop Add 38-42g of epichlorohydrin, dropwise for 4-6min, after the dropwise addition is complete, raise the temperature to 75°C, and react for 5-7h to obtain a brown viscous hydroxy-terminated chloropolyether; add 90-110g of hydroxy-terminated chlorine Substitute polyether and 182-202g trimethylamine aqueous solution, put in a clean reaction kettle, pass nitrogen to remove the air, control the temperature at 70-80°C, react for 4-6h, continue to heat up to 120-130°C, react for 6-8h, Obtain brown water-soluble cationic polyether; Wherein the mass fraction ratio of epichlorohydrin, glycerol, trimethylamine is 40-60:1:40-60, the consumption of initiator boron trifluoride ether solution is ring 1% of oxychloropropane;

The synthesis of 3.0G PAMAM:

1) Synthesis of 0.5G polyamide-amine: under the protection of nitrogen, add 30.6g of ethylenediamine and 96.2g of methanol into a four-necked flask equipped with a stirring bar, a thermometer and a condenser, and cool to 0°C with an ice-water bath Finally, slowly add 174.0g of methyl acrylate dropwise, stir and control the temperature at 22-27°C, and continue the reaction for 22-26h. The obtained light yellow liquid is distilled under reduced pressure at 45°C to obtain light yellow 0.5G polyamide - amine products;

2) Synthesis of 1.0G polyamide-amine: dissolve 270g of 1.0G polyamide-amine with 120g of methanol, add it to a four-neck flask, cool it to 0°C in an ice-water bath, slowly add ethylenediamine dropwise, and control the temperature for 23 -28°C, dropwise time 1-1.5h, continue to react for 24h after the dropwise addition, the obtained light yellow liquid is subjected to vacuum distillation at 70°C to obtain a light yellow 1.0G polyamide-amine product;

3) Inverted phase demulsifier: use the above 1.0G polyamide-amine to continue Michael addition reaction to obtain 1.5G polyamide-amine, and then perform amidation reaction to obtain 2.0G polyamide-amine, followed by Michael addition reaction Addition reaction and amidation reaction, that is, polyamide-amine of corresponding generation is obtained;

The synthesis of nonionic polyether:

Add 90-110g of potassium hydroxide powder and 900-1100ml of dichloromethane into the three-necked flask, mix and stir at room temperature, then add 230-270g of 600-polyethylene glycol dropwise, and add them at 1.0h, 2.0h, and 3.0h respectively 4-6g of potassium hydroxide powder, in which 20g of polypropylene glycol is added in the middle of the potassium hydroxide powder, and the crude product is obtained after continuing the reaction for 20 hours. After the methylene chloride is volatilized, dissolve it with 400-500ml of heated toluene and let it stand Finally, take potassium hydroxide to precipitate, and then dissolve once with 400-500ml of heated toluene to obtain polyoxyethylene oxypropylene;

Among them, the synthesis of modified compound reverse phase demulsifier: in the aqueous solution with a total weight of 800-1200g, add cationic polyether 100-250g, 3.0 generation dendritic polyamide-amine 150-400g, nonionic polyether 50g -100g; Stir at 35-45°C for 2-3 hours to obtain a modified composite reverse demulsifier, which is a reverse demulsifier for super heavy oil high temperature sewage treatment.

The reverse phase demulsifier is used to treat ultra-heavy oil high-temperature sewage, and its oil content is reduced from 6250 mg/L to below 10 mg/L.

Function and mechanism of the present invention: the synthesis mechanism of multi-segment cationic polyether-glycerol chlorinated polyether: using glycerol as the initiator, boron trifluoride ether solution as the initiator, triggering epichlorohydrin to proceed Cationic ring-opening polymerization to generate hydroxy-terminated chloropolyether; the active chlorine atoms in the hydroxy-terminated chloropolyether undergo amine alkylation reaction with trimethylamine to generate a positively charged polycationic polyether. Synthetic mechanism of polyamide-amine: Alternate Michael addition and amidation reaction to obtain 1.5 generation, 2.0 generation, 2.5 generation, 3.0 generation PAMAM.

The method for the inverse demulsifier prepared by the present invention includes the synthesis of cationic polyether, the synthesis of 3.0 generation polyamide-amine, the synthesis of nonionic polyether, polyamide-amine-polyether type-modified compound type reverse phase The synthesis of demulsifier has simple technical route, mild reaction conditions, fast dehydration speed, high demulsification efficiency, and excellent practical effect in production. The new product provided reduces production cost and also sets a demonstration for enterprises to save energy and reduce consumption. Demonstrate technological progress.

Detailed ways

The present invention is further described in conjunction with embodiment.

Example

1) Synthesis of cationic polyether:

Add 0.025mol of glycerol as a starting agent in a four-necked flask equipped with a stirrer, a condenser, and a thermometer, then add 2.13g (about 1%) boron trifluoride ether solution, and control it under stirring conditions. temperature at 50°C, slowly add epichlorohydrin dropwise for 5 minutes, and then raise the temperature to 75°C for 6 hours to obtain a brown viscous hydroxyl-terminated chloropolyether; mix 100g of hydroxyl-terminated chloropolyether with 191.3g Trimethylamine aqueous solution (equivalent of amino group and chlorine atom) is placed in a clean reaction kettle, nitrogen is passed through to remove the air, the temperature is controlled at 75°C, and the reaction is for 5 hours, and the temperature is continued to rise to 125°C, and the reaction is for 7 hours to obtain a brown water-soluble cationic polymer. Ether; Wherein the mass fraction ratio of epichlorohydrin, glycerol, trimethylamine is 40:1:40 or 60:1:60, epichlorohydrin and trimethylamine equivalent, take boron trifluoride ether solution as Initiator, its consumption is 1% of epichlorohydrin.

2) Synthesis of 3.0GPAMAM

(1) Synthesis of 0.5G polyamide-amine: under the protection of nitrogen, add 30.6g of ethylenediamine and 96.2g of methanol to a four-necked flask with a stirring bar, a thermometer, and a condenser, and cool it to 0 with an ice-water bath. ℃, slowly add methyl acrylate dropwise, stir and control the temperature at 25°C, and continue the reaction for 24h after the addition time is 1h. The obtained light yellow liquid is distilled under reduced pressure at 45°C to obtain 0.5G of polyamide-amine Pale yellow product.

(2) Synthesis of 1.0G polyamide-amine: Dissolve and separate 1.0G polyamide-amine with methanol, add it into a four-neck flask, cool it to 0°C in an ice-water bath, slowly add ethylenediamine dropwise, and control the temperature under stirring 25°C, dropwise for 1-1.5h and continue to react for 24h, the obtained light yellow liquid was subjected to vacuum distillation at 70°C to obtain 1.0G of a light yellow product of polyamidoamine.

The inverse demulsifier (3) uses the 1.0G polyamide-amine obtained above to continue the Michael addition reaction to obtain 1.5G polyamide-amine, and then undergoes amidation reaction to obtain 2.0G polyamide-amine, followed by Michael addition reaction and amidation reaction are carried out to obtain polyamide-amine of corresponding generation.

3) Synthesis of nonionic polyether

Add 100g of potassium hydroxide powder and 1000ml of dichloromethane into a three-necked flask, mix and stir at room temperature, then add 250g of polyethylene glycol-600 dropwise, and add 5g of potassium hydroxide powder at 1.0h, 2.0h, and 3.0h respectively , and drop 20g of polypropylene glycol at 2.0h, and continue to react for 20h to obtain a crude product. After dichloromethane volatilizes, dissolve it with 400-500ml of hot toluene, let it stand to remove unreacted potassium hydroxide precipitation, and then use 400-500ml of hot toluene was used to dissolve the precipitate once to obtain the product of polyethylene oxide and propylene oxide.

4) Synthesis of modified composite inverse demulsifier

Mix cationic polyether with non-ionic polyether, 3.0G polyamidoamine is crosslinking agent, in the aqueous solution with total weight of 1000g, cationic polyether is 100 or 250g, 3.0 generation dendritic polyamidoamine is 150 or 400g, non-ionic polyether 50 or 100g; stir at 40°C for 2 hours to obtain the final product modified composite reverse demulsifier, that is, super heavy oil high temperature sewage treatment reverse demulsifier.

The reverse-phase demulsifier of the present invention is a synthetic agent, which can reduce the oil content of ultra-heavy oil high-temperature sewage from 6249.3 mg/L to 10 mg at 85 ° C, pH: 7.0 or 8.0, and an addition of 30 mg/L /L below, the evaluation results are shown in the table below:

The anti-phase demulsifier described in the present invention has strong charge affinity, enough to balance the negative charge formed by the emulsifier; has strong surface activity, can destroy the interfacial energy of the emulsion, and the oil removal rate is greater than 98%; The inverse demulsifier has no stratification, no agglomeration, no mechanical impurities, good water solubility, fast oil-water separation, and low oil content in water.

The invention obtains a modified composite reverse-phase demulsifier, that is, the product of the reverse-phase demulsifier for super-heavy oil high-temperature sewage treatment meets the enterprise standard.

The manufacturer of the glycerin used in the present invention is Shanghai Jinrui Chemical Products Co., Ltd.; the manufacturer of boron trifluoride ether is Sinopharm Group Chemical Reagent Co., Ltd.; the manufacturer of epichlorohydrin is Qilu Petrochemical Company; The ether is self-made; the manufacturer of trimethylamine is Changzhou Jufeng Chemical Co., Ltd.; the manufacturer of potassium hydroxide powder is Jinan Jinhao Chemical Co., Ltd.; the manufacturer of polypropylene glycol is Jiangsu Haian Petrochemical Factory.

Claims (2)

1. a super Heavy Oil High Temperature sewage disposal reverse-phase emulsifier, is characterized in that: implement step by step:

1) cation polyether is synthetic:

In the four-hole boiling flask that agitator, prolong, thermometer are housed, add the glycerol of 0.025mol as initiator, then add 2.13 g boron trifluoride diethyl etherate liquid, under agitation condition, temperature control is 50 ℃, slowly drip epoxy chloropropane, time for adding 5min, after be warming up to 75 ℃ reaction 6h, obtain the thick terminal hydroxy group chloro polyethers of brown; By 100g terminal hydroxy group chloro polyethers and 191.3 g trimethylamine aqueous solutions ,be placed in clean reactor, pass into nitrogen excluding air, 75 ℃ of temperature controls, reaction 5h, continues to be warmed up to 125 ℃, and reaction 7h, obtains the water miscible cation polyether of brown; Wherein the ratio of quality and the number of copies of epoxy chloropropane, glycerol, Trimethylamine 99 is 40:1:40 or 60:1:60, and the quality such as epoxy chloropropane and Trimethylamine 99 be take boron trifluoride diethyl etherate liquid as initiator, and its consumption is epoxy chloropropane 1%;

2) 3.0GPAMAM's is synthetic:

(1) 0.5G polyamide-amide is synthetic: under the protection of nitrogen, in the four-hole boiling flask with stirring rod, thermometer, prolong, add quadrol 30.6g, methyl alcohol 96.2g, with ice-water bath, be cooled to 0 ℃, slowly drip methyl acrylate, stir 25 ℃ of lower temperature controls, the complete continuation reaction of time for adding 1h 24h, the weak yellow liquid obtaining, under 45 ℃ of conditions, carry out underpressure distillation, obtain the light yellow product of 0.5G polyamide-amide;

(2) 1.0G polyamide-amide is synthetic: the 0.5G polyamide-amide of separating with dissolve with methanol, join in four-hole boiling flask, ice-water bath is cooled to 0 ℃, slowly drip quadrol, stir 25 ℃ of lower temperature controls, time for adding 1-1.5h continues reaction 24h, the weak yellow liquid obtaining, under 70 ℃ of conditions, carry out underpressure distillation, obtain the light yellow product of 1.0G polyamide-amide;

(3) with 1.0G polyamide-amide obtained above, proceed Michael addition reaction, obtain 1.5G polyamide-amide, then carry out amidate action, obtain 2.0G polyamide-amide, carry out successively Michael addition reaction and amidate action, obtain the polyamide-amide of corresponding algebraically;

3) nonionic polyoxyalkylene is synthetic:

In there-necked flask, add 100g potassium hydroxide powder and 1000mL methylene dichloride, mix and blend under room temperature, then drip 250g polyoxyethylene glycol-600, the potassium hydroxide powder that adds respectively 5g while being 1.0h, 2.0h, 3.0h, and when 2.0h, drip 20g polypropylene glycol, continue to obtain crude product after reaction 20h, after methylene dichloride is evaporated completely, with hot toluene 400-500mL, dissolve, the standing unreacted potassium hydroxide precipitation of removing, the toluene 400-500mL dissolution precipitation of reusable heat once, obtains the product of polyoxyethylene propylene oxide;

4) modified composite reverse-phase emulsifier is synthetic:

Cation polyether is mixed with nonionic polyoxyalkylene, and 3.0G polyamide-amide is linking agent, and in the aqueous solution that is 1000g in gross weight, cation polyether is that 100-250g, 3.0G polyamide-amide are 150-400g, and nonionic polyoxyalkylene is 50-100g; At 40 ℃, stir 2h, obtain final product modified composite reverse-phase emulsifier, must surpass Heavy Oil High Temperature sewage disposal reverse-phase emulsifier.

2. according to reverse-phase emulsifier described in claim 1, it is characterized in that: adopt the super Heavy Oil High Temperature sewage of this product treatment, its oleaginousness drops to below 10mg/L from 6250mg/L.