NL2030766B1

NL2030766B1 - Broad-spectrum polyether crude oil demulsifier and preparation method thereof

Info

Publication number: NL2030766B1
Application number: NL2030766A
Authority: NL
Inventors: Wang Lili; Wang Zi'ang; Ma Mengyao; Wang Hongguo
Original assignee: Fushun Taimiao Chemical Tech Co Ltd
Priority date: 2022-01-28
Filing date: 2022-01-28
Publication date: 2023-08-08

Abstract

The present disclosure relates to a broad—spectrum polyether crude oil demulsifier and a preparation method thereof. The tea polyphenol amine type phenolic resin is used as the initiator, and the epoxy ethane and epoxy propane diblock polyether demulsifier using the tea polyphenol amine type phenolic resin as the initiator is obtained through ring opening polymerization of epoxy propane and epoxy ethane at the temperature of lower than 130°C and the pressure of lower than 0.25 MPa. The prepared demulsifier has a good demulsification effect on oil field produced liquid. The raw materials used in the initiator of the present disclosure are natural non—toxic food antioxidant—tea polyphenols, which have the advantages of easy availability of raw materials, environmental protection, good biodegradability, multiple active groups, and good demulsification and dehydration effect of the synthesized demulsifier; have the characteristics of low dosage, low demulsification temperature, environmental protection and pollution—free, and strong broad spectrum.

Description

P2994 /NLpd

BROAD-SPECTRUM POLYETHER CRUDE OIL DEMULSIFIER AND PREPARATION

METHOD THEREOF

TECHNICAL FIELD

The present disclosure relates to a block polyether demulsi- fier using tea polyphenol amine type phenolic resin as an initia- tor and a preparation method thereof.

BACKGROUND ART

With the continuous development and application of oil pro- duction technology, crude oil emulsions have become more and more stable, which has increased the water content of produced fluids of oilfield year by year, increased the difficulty of crude oil demulsification and dehydration, enhanced the equipment load in the storage, transportation, and refining processes and increased the fuel consumption during the heating process. Therefore, demul- sifiers, as surfactants that quickly and efficiently remove the water content of crude oil, are one of the indispensable chemical reagents for oilfields and refineries nowadays.

In China, the technical route for the development of non- ionic demulsifiers can be summarized as "changing initiator, es- terfying the terminal functional groups, adding new frameworks in the structure of the demulsifier, crosslinking, buiding-up differ- ent demulsifiers”. Of which, changing initiator is mainly to modi- fy the initiator, design and synthesize an initiator with high ac- tivity and good demulsification characteristics. Because the mate- rial composition of crude oil is extremely complex and has a poly- cyclic chemical structure, the choice of an initiator is very im- portant for the synthesis of demulsifiers. Therefore, the initia- tor not only needs to contain active hydrogen, but also needs to have a phenol nucleus or bisphenol nucleus structure.

Studies at home and abroad have shown that tea polyphenols contain a large amount of catechins, which have strong activity when reacting with formaldehyde. Tea polyphenols are natural prod- ucts with a wide range of sources and good biodegradability, and have remarkable safety performance and are convenient for trans- portation compared with the conventional petroleum alkylphenol as an initiator raw material.

The novel crude oil demulsifier conceived and prepared in the present disclosure is based on the above theory. The catechins contained in tea polyphencls have strong reactivity with formalde- hyde. A new type of phenolic amine-aldehyde resin initiator is de- signed and synthesized, and a novel block polyether demulsifier is obtained.

SUMMARY

In order to overcome the defects of the prior art, the pre- sent disclosure discloses a broad-spectrum polyether crude oil de- mulsifier and a preparation method thereof, and aims to provide a crude oil demulsifier with strong broad spectrum and good demulsi- fication performance.

The present disclosure is realized by the following technical means:

A method for preparing a broad-spectrum polyether crude oil demulsifier comprises the following steps: (1) mixing tea polyphenol and organic amine in a certain proportion, stirring for 30 min at room temperature in a nitrogen environment, heating to 70°C, continuously stirring until the tea polyphenol is completely dissolved, continuously stirring for 30 min, adding dropwise a formaldehyde solution at a speed of 1 drop/s by using a pressure-equalizing dropping funnel, and contin- uously stirring for 3 h at a constant temperature of 70°C after adding dropwise, to obtain a reaction product; (2) in order to remove the residual formaldehyde and organic amine and byproduct water in the reaction, performing distillation under reduced pressure on the obtained product for 5 h under a vacuum condition to remove excessive formaldehyde and organic amine and reaction byproduct water, to obtain a target product, namely, reddish brown viscous liquid, a tea polyphenol amine type phenolic resin initiator; (3) adding the product prepared in the step (2) and a cata- lyst into a high-temperature high-pressure reaction kettle, seal-

ing the reaction kettle, and performing purging and replacement by using dry nitrogen; (4) performing purging and replacement by using dry nitrogen in the step (3), vacuumizing, and repeating for at least twice; (5) starting stirring, heating to the reaction temperature, adding epoxypropane, controlling the temperature and pressure in the kettle, and reacting completely until the pressure in the ket- tle is normal pressure; (6) adding ethylene oxide, controlling the temperature and pressure in the kettle, and reacting completely until the pressure in the kettle is normal pressure; and (7) finally, continuously reacting for 60-90 min when the temperature in the kettle is 120°C, cooling after the reaction ends, cooling, opening the kettle, and discharging, to obtain the reaction product, namely the tea polyphenol amine type diblock polyether demulsifier.

The organic amine in the step (1) can be any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine.

The catalyst in the step (3) is potassium hydroxide, the us- ing amount of the catalyst is 0.1-0.3% of the sum of the mass of reaction raw materials, and the reaction raw materials are epoxy- propane added in the step (5) and ethylene oxide added in the step (6).

The mass ratio of the tea polyphenol amine type phenolic res- in initiator to the epoxypropane added in the step (5) is 1: (25- 400).

The reaction temperature is controlled to be 120-130°C, and the reaction pressure is controlled to be 0-0.25 MPa.

The mass ratio of the tea polyphenol amine type phenolic res- in initiator to the ethylene oxide added in the step (6) is 1: (25-400).

An ethylene oxide and epoxypropane block polyether demulsifi- er is prepared by adopting the preparation method.

The added organic amine is diethylenetriamine, and the struc- tural formula of the obtained novel tea polyphenol amine type di- block polyether demulsifier is as follows:

R %, 0 (Ck Ie, Cat LH

R P

HEH OCHO | 7) ln KEE

R | Rs {Ry waarin geldt dat, & ~— HOH OH “ey IH 3 HOC0, Cron

Ry = sw op 0

HEC HOD pl CHa

HEHE CRONE ji ee CR CH ACEC

HOCH, DCH OO ™ {CHOC HH where, m and n respectively represent the number of moles of an epoxypropane block and an ethylene oxide block of a molecular chain block.

The synthetic route of the diblock polyether demulsifier is as follows:

CHINO HOH KETEN NH,

NHL HUH NEO EEN HOR, en B 5

RON VOEL NEC Í i

AI

+ RH OH Ra

R CF Ry (0 840 0H

XK prs

HEH 040, H Og LAR \ 4 DHE (Era

LCS

B | OR:3 7

UB3

Hoch BEE ha fC Hg Dy waarin geldt dat, | OEE ko NEMO NCA CHN EE

ETE PTA RI SERS IG We HCHO hp (Up H gy,

The present disclosure has the following advantages and bene- ficial effects:

The tea polyphenol amine type phenolic resin is used as the 5 initiator, and the epoxy ethane and epoxy propane diblock polyeth- er demulsifier using the tea polyphenol amine type phenolic resin as the initiator is obtained through ring opening polymerization of epoxy propane and epoxy ethane at the temperature of lower than 130°C and the pressure of lower than 0.25 MPa. The prepared demul- sifier has a good demulsification effect on oil field produced liquid.

Tea polyphenol is used as a raw material for preparing the initiator for the first time. The tea polyphenol is a mixture and contains 70-80% of flavanol compounds using catechins as major in- gredients. Compared with the traditional petroleum alkylphenol used as the raw material, the tea polyphenol is a natural product, and has rich sources, low price and high safety and has the ad- vantages of non-toxicity, green and environment-friendly, and good biodegradability; and a polyhydroxy structure is used, so a prod- uct with a plurality of active groups can be synthesized, and a plurality of branched chains are contained in molecules.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Example 1 59.086 g of tea polyphenol and 108.329 g of diethylenetri- amine were weighed by using a 250 mL four-neck flask and were stirred for 30 min at room temperature in a nitrogen environment; after the temperature was increased to 70°C, stirring was continu- ously carried out until the tea polyphenol was completely dis- solved; stirring was continued for 30 min, then 18.919 g of for- maldehyde solution was added dropwise by using a pressure- equalizing dropping funnel at a speed of 1 drop/s; and after add- ing dropwise, stirring was continuously carried out for 3 h at constant temperature in the nitrogen environment. The operation was repeated for multiple times to obtain a sufficient amount of product.

Distillation under reduced pressure was carried out on the obtained product for 5 h under the vacuum conditions of 150°C and 1.33 kPa to remove excessive formaldehyde, diethylenetriamine and reaction byproduct water, so as to obtain reddish brown viscous liquid, a tea polyphenol amine type phenclic resin initiator. 100 g of the initiator prepared in the Example 1 and 24 g of potassium hydroxide were added into a high-temperature high- pressure reaction kettle, and the reaction kettle was sealed.

Purging and replacement were carried out with nitrogen before heating, vacuumizing was carried out with a vacuum pump, and the operation was repeated twice; then stirring and heating were started, heating was stopped when the temperature was raised to 120°C; a feed valve was opened, 4,900 g of propylene oxide was add- ed dropwise; the reaction temperature was controlled to be not higher than 130°C and the pressure to be 0.25 MPa or below; after the materials were completely reacted and the pressure returned, reacting was carried out for 30 min again, and the pressure was reduced to normal pressure; then heating was carried out to reach 120°C, 3,800 g of ethylene oxide was added, and the reaction tem- perature was controlled to be not higher than 130°C and the pres- sure to be 0.25 MPa or below; and after the materials were com- pletely reacted and the pressure returned, the reacting was car-

ried out for 30 min again, and then the pressure was reduced to normal pressure. Cooling was carried out, the kettle was opened for discharging, to obtain the ethylene oxide and propylene oxide diblock polyether demulsifier taking the tea polyphenol amine type phenolic resin as the initiator.

Tarim crude oil (the water content of 44.7%), Karamay crude oil (the water content of 58.1%), Liaohe crude oil (the water con- tent of 62.9%) and Daqing crude oil (the water content of 91.3%) were subjected to demulsification dehydration evaluation, and the adaptability and the universality of the broad-spectrum polyether crude oil demulsifier were investigated. When the amount of the demulsifier was 40 mg/L and the temperature was 50°C, the dehydra- tion rate of the ethylene oxide and propylene oxide block polyeth- er demulsifier taking the tea polyphenol amine type phenolic resin as the initiator after demulsification for 2 h was shown in a ta- ble 1. A crude oil dehydration test was carried out according to

SY 5281-2000 “Bottle test method for the demulsifica- tion performance of crude oil demulsifiers”.

Example 2 59.086 g of tea polyphenol and 108.329 g of diethylenetri- amine were weighed by using a 250 mL four-neck flask and were stirred for 30 min at room temperature in a nitrogen environment; after the temperature was increased to 70°C, stirring was continu- ously carried out until the tea polyphenol was completely dis- solved; stirring was continued for 30 min, then 18.919 g of for- maldehyde solution was added dropwise by using a pressure- equalizing dropping funnel at a speed of 1 drop/s; and after add- ing dropwise, stirring was continuously carried out for 3 h at constant temperature in the nitrogen environment. The operation was repeated for multiple times to obtain a sufficient amount of product.

Distillation under reduced pressure was carried out on the obtained product for 5 h under the vacuum conditions of 150°C and 1.33 kPa to remove excessive formaldehyde, diethylenetriamine and reaction byproduct water, so as to obtain reddish brown viscous liquid, a tea polyphenol amine type phenolic resin initiator.

100 g of the initiator prepared in the Example 2 and 10 g of potassium hydroxide were added into a high-temperature high- pressure reaction kettle, and the reaction kettle was sealed.

Purging and replacement were carried out with nitrogen before heating, vacuumizing was carried out with a vacuum pump, and the operation was repeated twice; then stirring and heating were started, heating was stopped when the temperature was raised to 130°C; a feed valve was opened, 2,500 g of propylene oxide was add- ed dropwise; the reaction temperature was controlled to be not higher than 130°C and the pressure to be 0.25 MPa or below; after the materials were completely reacted and the pressure returned, reacting was carried out for 30 min again, and the pressure was reduced to normal pressure; then heating was carried out to reach 120°C, 2,500 g of ethylene oxide was added, and the reaction tem- perature was controlled to be not higher than 130°C and the pres- sure to be 0.25 MPa or below; and after the materials were com- pletely reacted and the pressure returned, the reacting was car- ried out for 30 min again, and then the pressure was reduced to normal pressure. Cooling was carried out, the kettle was opened for discharging, to obtain the ethylene oxide and propylene oxide diblock polyether demulsifier taking the tea polyphenol amine type phenolic resin as the initiator.

Example 3 59.086 g of tea polyphenol and 108.329 g of diethylenetri- amine were weighed by using a 250 mL four-neck flask and were stirred for 30 min at room temperature in a nitrogen environment; after the temperature was increased to 70°C, stirring was continu- ously carried out until the tea polyphenol was completely dis- solved; stirring was continued for 30 min, then 18.919 g of for- maldehyde solution was added dropwise by using a pressure- equalizing dropping funnel at a speed of 1 drop/s; and after add- ing dropwise, stirring was continuously carried out for 3 h at constant temperature in the nitrogen environment. The operation was repeated for multiple times to obtain a sufficient amount of product.

Distillation under reduced pressure was carried out on the obtained product for 5 h under the vacuum conditions of 150°C and 1.33 kPa to remove excessive formaldehyde, diethylenetriamine and reaction byproduct water, so as to obtain reddish brown viscous liquid, a tea polyphenol amine type phenolic resin initiator. 100 g of the initiator prepared in the Example 3 and 160 g of potassium hydroxide were added into a high-temperature high- pressure reaction kettle, and the reaction kettle was sealed.

Purging and replacement were carried out with nitrogen before heating, vacuumizing was carried out with a vacuum pump, and the operation was repeated twice; then stirring and heating were started, heating was stopped when the temperature was raised to 120°C; a feed valve was opened, 40,000 g of propylene oxide was added dropwise; the reaction temperature was controlled to be not higher than 130°C and the pressure to be 0.25 MPa or below; after the materials were completely reacted and the pressure returned, reacting was carried out for 30 min again, and the pressure was reduced to normal pressure; then heating was carried out to reach 120°C, 40,000 g of ethylene oxide was added, and the reaction tem- perature was controlled to be not higher than 130°C and the pres- sure to be 0 MPa or below; and after the materials were completely reacted and the pressure returned, the reacting was carried out for 30 min again, and then the pressure was reduced to normal pressure. Cooling was carried out, the kettle was opened for dis- charging, to obtain the ethylene oxide and propylene oxide diblock polyether demulsifier taking the tea polyphenol amine type phenol- ic resin as the initiator.

As shown in Table 1, when the amount of the demulsifier was 40 mg/L and the temperature was 50°C, the dehydration rates of the series of demulsifier were all 853 or more, the interface was neat, and the dehydrated water was clear, which showed that the series of demulsifiers had good demulsification performance and had the advantages of less use amount, low temperature and wide application range. No. 0 was a blank test without adding the de- mulsifier, and No. 1 to No. 8 were a series of novel demulsifiers with different masses of propylene oxide and ethylene oxide.

Table 1 Dehydration rate of block polyether demulsifier with different EO and PO ratios

Demulsifier

No.

Dehydration 1 2 3 4 5 7 rate /%

Type of crude oil

Tarim crude | 0 85.1 | 87.9 | 88.2 (87.4 {85.8 [86.2 185.9 | 87.5 a

Karamay 85.3 {86.7 | 87.1 | 87.9 1 88.3 | 90.4 1 90.1 | 89.7 men

Liaohe 87.9 91.4 1 92.7 | 95.1 | 94.5 | 93.3 1 92.6 | 91.3

Ed

Daging 0.4}190.3 | 92.8 | 93.2 | 95.0 | 96.7 | 96.3 1 95.9 | 94.7

EE

Claims

CONCLUSIONS

A process for preparing a polyether-based broad-spectrum crude oil demulsifier comprising the following steps: (1) mixing tea polyphenol and organic amine in a certain ratio, stirring for 30 minutes at room temperature in a nitrogen environment, heating to 70 °C, stirring continuously until the tea polyphenol is completely dissolved, stirring continuously for 30 minutes, adding a formaldehyde solution dropwise at a rate of 1 drop/ sec. using a pressure equalizing dropping funnel, and stirring continuously at a constant temperature of 70°C for 3 hours after adding dropwise, to obtain a reaction product; (2) to remove the residual formaldehyde and organic amine and the by-product water in the reaction, conducting distillation under reduced pressure on the obtained product for 5 hours under vacuum conditions to remove excess formaldehyde and organic amine and remove by-product water in the reaction, to obtain a target product, which is a red-brown viscous liquid, a tea polyphenolamine type phenolic resin initiator; (3) adding the product prepared in step (2) and a catalyst to a high-temperature high-pressure reaction kettle, sealing the reaction kettle, and performing purification and replacement using dry nitrogen ; (4) performing purge and replacement using dry nitrogen in step (3), drawing a vacuum and repeating at least two times; (5) starting stirring, heating up to the reaction temperature, adding propylene oxide, controlling the temperature and pressure in the kettle, and reacting completely until the pressure in the kettle is normal pressure; (6) adding ethylene oxide, controlling the temperature and pressure in the kettle, and allowing it to react completely until the pressure in the kettle is normal pressure; and (7) finally, continuously reacting for 60 ~ 90 minutes when the temperature in the kettle is 120 °C, cooling after the reaction is over, cooling, opening the kettle and discharging, to obtain the reaction product, know the demulsifier of a tea polyphenolamine type diblock polyether.

A broad-spectrum polyether-based crude oil demulsifier manufactured in accordance with the method of claim 1, wherein a block polyether demulsifier based on ethylene oxide and propylene oxide is prepared by applying the method.

A broad-spectrum polyether-based crude oil demulsifier according to claim 2, wherein the added organic amine is diethylenetriamine, and the structural formula of the resulting new demulsifier of a tea polyphenolamines type diblock polyether is as follows : R OREL] FCF ONC HON Ou” pr P= {CHO (HOH Bo ORy OR where, Ry — HOH QH : : — {IN Be BL qa noe, (TO By — —0—0R 8 BOHOL CHO) £ CATE CHE, H Poe “UH | CHT EANOH OHH BCO CH DICH CHO m and n represent the number of moles of an epoxy propane block and an ethylene oxide block of a molecular chain block, respectively.