LU501295B1 - Method for preparing modified multi-branched polyether demulsifier - Google Patents

Abstract

The present invention relates to a method for synthesizing and modifying a multi-branched polyether demulsifier. The method includes: (1) mixing, heating and dissolving 2,2-bis(4-hydroxyphenyl) propane and triethylene tetramine, then performing a thermal insulation reaction in a formaldehyde solution, adding xylene for backflow dehydration, then heating to evaporate the xylene and enabling remaining substances to react to generate an initiator; (2) using potassium hydroxide as a catalyst, putting the initiator into a high-temperature high-pressure reaction kettle, sealing and vacuumizing the reaction kettle, and adding propylene oxide, so as to enable a polyether reaction in the reaction kettle to generate an intermediate product 1; (3) with potassium hydroxide as a catalyst, putting the intermediate product 1 into the high-temperature high-pressure reaction kettle, sealing and vacuumizing the reaction kettle, and introducing ethylene oxide, so as to enable a polyether reaction in the reaction kettle to generate a multi-branched polyether B; and (4) with potassium hydroxide as a catalyst, heating the multi-branched polyether B in a water bath, and slowly and dropwise adding epoxy chloropropane for modification to generate the multi-branched polyether demulsifier. The present invention has the beneficial effects of safety, environmental friendliness, a satisfactory surface tension reduction efficiency and effect, excellent hydrophilcity, wettability and permeability, rapid approach to an oil-water interface, a high dehydration rate, a reduced usage amount, a desirable demulsification effect, a high demulsification rate as well as an improved crude oil production efficiency.

Description

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LU501295

METHOD FOR PREPARING MODIFIED MULTI-BRANCHED POLYETHER

DEMULSIFIER

TECHNICAL FIELD

[01] The present invention particularly relates to a method for preparing a novel modified multi-branched polyether demulsifier and belongs to the technical field of oil field chemicals.

BACKGROUND ART

[02] Petroleum, as the significant energy and basic chemical raw material, is a significant strategic material in China. In the process of oil production, the implementation of various enhanced oil recovery methods such as water flood recovery, heavy oil thermal recovery, alkaline flooding, polymer flooding and surfactant flooding poses greater difficulties in demulsification of a crude oil emulsion and a growing demand for the demulsifier. Therefore, it is of great importance to demulsify the crude oil emulsion.

[03] The demulsification methods can include a physico-mechanical method and a physico-chemical method, of which the physico-mechanical method includes electric sedimentation, filtration, ultrasound and the like, while the physico-chemical method is mainly to change the interfacial property of the emulsion for demulsification. Currently, the polyether demulsifiers are widely applied in oil fields in China. Different polyether demulsifiers are obtained through different initiators, propylene oxide and the ethylene oxide with different adduct numbers and ratios and different modifiers. The multi-branched polyether demulsifier plays a greater part in reducing the surface tension of the oil-water interface compared with the common linear polyether demulsifier and a denser micelle formed by the multi-branched polyether. Therefore, the multi-branched polyether demulsifier features a better crude oil demulsification effect.

SUMMARY

[04] Objective of the Invention

[05] An objective of the present invention is to provide a novel modified multi-branched polyether demulsifier, featuring an excellent demulsification effect, a high dehydration rate, a smaller usage amount, a higher crude oil production efficiency, high hydrophilcity, wettability and permeability, rapid approach to an oil-water interface, a satisfactory surface tension reduction efficiency and effect as well as a contribution to the demulsification effect. A preparation method thereof features simplicity, a convenient configuration, a high speed, a high efficiency and a low cost.

[06] Summary of the Invention

[07] An objective of the present invention is to provide a novel modified multi-branched polyether demulsifier, featuring excellent hydrophilcity, wettability and permeability, a smaller usage amount, a desirable demulsification effect as well as a high demulsification rate.

[08] A process for synthetizing a novel modified multi-branched polyether demulsifier includes:

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LU501295

[09] (1) putting 1 part of 2,2-bis(4-hydroxyphenyl) propane and 2-3 parts of triethylene tetramine into a four-necked flask, heating to 45-55°C to completely dissolve same, slowly and dropwise adding a formaldehyde solution at 35-55°C, then adding 1.7-2.3 parts of xylene, heating to 100-110°C for backflow dehydration and finally heating to 185-195°C after 1.5-2.5 h to evaporate the xylene, to generate an initiator;

[10] (2) putting the initiator and potassium hydroxide into a high-temperature high-pressure reaction kettle, sealing and vacuumizing the reaction kettle with a vacuum pump for 4-6 min to a negative pressure, introducing propylene oxide, heating to 105°C-115°C and controlling a pressure gauge reading to be 0.19-0.21 MPa, to generate an intermediate product 1;

[11] (3) putting the intermediate product 1 and 0.13-0.81 parts of potassium hydroxide into the high-temperature high-pressure reaction kettle, sealing the high-temperature high-pressure reaction kettle, opening a feeding valve, slowly introducing ethylene oxide, adding all ethylene oxide, then closing the feeding valve, reducing a pressure in the reaction kettle to be negative and ending a reaction, to obtain a multi-branched polyether B; and

[12] (4) putting 10 parts of multi-branched polyether B into a three-necked flask, stirring, performing water bath heating to 50-60°C, adding 0.11-0.13 parts of potassium hydroxide, then continuously performing water bath heating to 60-80°C, slowly and dropwise adding 0.2-0.24 parts of epoxy chloropropane for about 2-3 h, finally performing water bath heating to 80-90°C and maintaining a temperature for 8 h, to prepare the multi-branched polyether demulsifier.

[13] According to the solution described above, a mass part of the 2,2-bis(4-hydroxyphenyl) propane to the triethylene tetramine to the formaldehyde solution in step (1) is 1:2:0.4-1:3:0.6, specifically 1:2.5:0.5.

[14] According to the solution described above, a heating and dissolving temperature of the 2,2-bis(4-hydroxyphenyl) propane and the triethylene tetramine in step (1) is 45-55°C, specifically 50°C.

[15] According to the solution described above, in an initiator generation reaction in step (1), a concentration of the formaldehyde solution is 37-40% and a thermal insulation time after formaldehyde is added is 35-45 min, specifically 30 min.

[16] According to the solution described above, in step (1), an addition amount of the xylene is half of the total amount of a material, a backflow dehydration temperature is 100-110°C, and a backflow dehydration time is 2 h.

[17] According to the solution described above, a reaction temperature of a mixed solution of the 2,2-bis(4-hydroxyphenyl) propane and the triethylene tetramine and the formaldehyde solution in step (1) is 185-195°C, specifically 190°C, and a reaction time is 1-2 h, specifically 1 h.

[18] According to the solution described above, in steps (2)-(3), 69-359 parts of propylene oxide are added,18.9-180 parts of ethylene oxide are added, reaction temperatures are both 110°C after heating and an opening of the feeding valve 1s adjusted during the reaction to maintain the pressure gauge reading of the high-pressure reaction kettle to fall within 0.2+0.01 MPa.

[19] According to the solution described above, in steps (2)-(3), a catalyst for a

BL-5384

LU501295 polyether reaction is the potassium hydroxide, of which usage amounts are 0.2% and 0.15% of total parts for the first time and second time respectively.

[20] According to the solution described above, in steps (2)-(3), nitrogen gas 1s used to replace gas in the kettle, a vacuumizing time is 4-6 min and a gauge pressure of the reaction kettle is -0.09 MPa.

[21] According to the solution described above, a catalyst for a modification reaction in step (4) is the potassium hydroxide, of which a usage amount is 0.11-0.13 parts, specifically 0.12 parts.

[22] According to the solution described above, step (4) particularly includes: heating to 50-60°C in a water bath for the first time, adding the potassium hydroxide, and then stirring for 15-25 min; heating to 60-80°C in the water bath for the second time; and heating to 80-90°C in the water bath for the third time and maintaining the temperature for 8 h.

[23] According to the solution described above, in step (4), the epoxy chloropropane has a usage amount of 0.2-0.24 part, specifically 0.2 part and may be dropwise added with a separation funnel for 2-3 h.

CH3 { ) | { ) H

HO | OH HoN V\ NS VA

[24] CH3 +4 À Na —— — +4H—C—H

NWN VW

CH

H2N N 3 N NH,

HO 1 OH

CH3

H H

NWN VW

HaN N N NH»

N HN NH N

„NN M,

HO C OH bh,

N HN NH N KOH

, AW MAM, + ml Po) + n(po) LES

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LU501295

To]

R N N N N R

VAN cr VWVVY

N N | N N 1 15 | ll 151 re 151

WWW WWW j 1 j 1

R R R R

R= —fC:H50 4—ÉC:H,0}—H where

KOH Hz

R + \/ \ — ——{CaHeO Jf CHO JC IV

O CI O

25] A novel modified multi-branched polyether demulsifier is characterized in that it has a general structural formula as follows:

R FR: R R \ R ! R R | R §

R : R \ ! R { R

R ; R R | R

ResRes en Frs AN eu À eee, Les EL NE ee Te MR

Se” ST Nr ar M7 © ey CH 3 Ft { MT No” ad Sp se 1

Ry Re Te Ra À bs à Re ZN VE AED TER „AN a oe at MRR “hy N° Se EU Sn” vo H,C D Su” Le no N° Le, i

R R | R R

R R R | R {

R, | BR, 3 i R, i H,

Ry R, Ry R, where { i À E nn x

R=—{—CyHy 0 C,H403—

R,= sess <>

Hs X 8

D 8

[26] Effect of the Invention

[27] Compared with conventional surfactants or other polyether demulsifiers in the prior art, the novel modified multi-branched polyether demulsifier of the present invention has the following beneficial effects of excellent demulsification, a high dehydration rate, reduced usage amount, improved crude oil production efficiency, excellent hydrophilcity, wettability and permeability, rapid approach to an oil-water interface, satisfactory surface tension reduction efficiency and effect, contribution to the demulsification effect as well as superior effect compared with a traditional demulsifier.

A preparation method thereof features simplicity, a convenient configuration, a high

BL-5384

LU501295 speed, a high efficiency and a low cost. Moreover, the multi-branched polyether demulsifier features a high surface activity, high stability, etc, and thereby has an excellent research prospect in the field of demulsification. 5 BRIEF DESCRIPTION OF THE DRAWINGS

[28] FIG 1 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 1-4 of the present invention;

[29] FIG 2 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 5-8 of the present invention;

[30] FIG 3 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 9-12 of the present invention;

[31] FIG 4 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 13-16 of the present invention;

[32] FIG 5 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 17-20 of the present invention; and

[33] FIG 6 is a picture of demulsification effects, on crude oil in a certain oil field, of samples 21-24 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[34] The following examples are provided to further explain the objective, the technical solution and specific contents of the present invention. The scope of use of the present invention is not affected by the examples, and the specific implementations may be determined according to the technical solution and specific use conditions of the present invention.

[39] Example 1

[36] 20 g of 2,2-bis(4-hydroxyphenyl) propane and 50 g of triethylene tetramine were put into a four-necked flask, water bath heating was performed to 50°C during stirring to completely dissolve same and then a temperature was maintained for 15 min.

Then 10 g of formaldehyde solution was slowly and dropwise added and a thermal insulation reaction was performed for 30 min after addition. 40 g of xylene was added and heating was performed to 105°C for backflow dehydration. Heating was gradually performed to 190°C after 2 h, so that transparency of reactants and the xylene was gradually increased and the xylene was completely evaporated at 190°C. Finally, a reaction was ended after 1 h. A deep red viscous liquid was obtained as an initiator 1.

[37] 4 g of initiator 1 and 3.7 g of potassium hydroxide were added into a high-temperature high-pressure reaction kettle and the reaction kettle was sealed. Prior to heating, nitrogen gas was used for purging and replacing air and then the reaction kettle was vacuumized with a vacuum pump. Heating was started after 5 min and stopped when a temperature was increased to 110°C. A feeding valve was opened, 556 g of propylene oxide was introduced, a pressure was controlled to fall within 0.2+0.01

MPa and the temperature was controlled to be unchanged. A reaction was continuously performed for 25 min after all materials in the kettle completely reacted and a pressure dropped, so that a pressure was reduced to -0.09 MPa. Finally a temperature was reduced and the kettle was opened for discharging to obtain an intermediate product 1.

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[38] After the reaction, the intermediate product 1 and 185 g of potassium hydroxide were added into the high-temperature high-pressure reaction kettle and the reaction kettle was sealed. Prior to heating, nitrogen gas was used for purging and replacing air and then the reaction kettle was vacuumized with the vacuum pump.

Heating was started after 5 min and stopped when a temperature was increased to 110°C.

The feeding valve was opened, 370g of ethylene oxide was introduced, a pressure was controlled to fall within 0.2+0.01 MPa and the temperature was controlled to be unchanged. À reaction was continuously performed for 25 min after all materials in the kettle completely reacted and a pressure dropped, so that a pressure was reduced to -0.09 MPa. Finally, a temperature was reduced and the kettle was opened for discharging, so as to obtain a multi-branched polyether A.

[39] 80 g of multi-branched polyether A was put into a three-necked flask, stirred and heated to 55°C in a water bath. 3 g of 40% potassium hydroxide was added and stirred for 20 min. Then water bath heating was continuously performed to 70°C, and 2 g of epoxy chloropropane was slowly and dropwise added for 2.5 h. Finally water bath heating was performed to 85°C and a temperature was maintained for 8 h, to prepare the modified multi-branched polyether demulsifier 1.

[40] As described in Example 1, different mult-branched polyethers A were obtained by modifying mass parts of the propylene oxide and the ethylene oxide introduced, and then modified to prepare different modified multi-branched polyether demulsifiers 2-24.

[41] Example 2 Evaluation on modified multi-branched polyether demulsifier

[42] With crude oil produced liquids in a certain oil field as treatment objects, dehydration effects of different modified multi-branched polyether demulsifiers were evaluated. Experimental results were shown in the table below:

Dosing . Presence . 15 30 145 160 [75 [90 1135 . ns in {nn in min min_'"8"8 min [min [min [min [min min [min

Pas ppp 2-69 (2:1)

Ne bhp pe 2-69 (2.7:1) nn

Aqueous solution

Bm Lh bh espe

Aqueous solution em CA 0

Aqueous solution oan Iw #6 6e papes eee rp pi 2-99 (2.7:1)

Aqueous solution pan 0 5 psp poke poe

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LU501295

Aqueous solution 100 4 4 45 5 55 7.5 11 se (3.7:1) oo 6 6 as 6 sspsm

Aqueous solution 00 3 3 135 45 45 55 16.5 2-159 (2:1) CT

Aqueous solution 10 100 2.5 3 3 35 4 4 5 no fe (2.7:1) oo esp 3 88 hs

Aqueous solution jo (3:1) oo 35854 5 79 fe je

Aqueous solution 12 100 4 5.5 165 [15 12 [17 Ye 12 pe (3.7:1) oo 6 ps pshsp ha 17 je

Aqueous solution 13 100 05 (1.5 115 2 13 20 (2:1) oo | | pspshse ||]

Aqueous solution 14 [pe (2.7:1) oo hsp 2 psps

Aqueous solution 15 100 05 |1 1 1 1 15 20 (3:1) oo esp hhh 16 [Mucous = solution 0 05/1 2 25383 8 Yes 2-199 (3.7:1) ; ;

Aqueous solution 17 100 1 1 2 2.5 25 17 je (2:1) oo | ph ep | |] 18 [Mucous = solution 0 052 252 [5p Yes 2-259 (2.7:1) 19 Aqueous solution 100 1 ısbsbsh 2-259 (3:1) nf

Aqueous solution 20 100 0.5 105 1 1.5 po fe (3.7:1) oo | pspsh | hs}

Aqueous solution Turbi 21 100 1.5 1.5 2 2 25 13 21 9 59 (2:1) oo hs hsp 2 psp 1 1 UT 22 Aqueous solution), 00 0s It 15 b Yes 2-359 (2.7:1)

Aqueous solution 23 100 1 1 1 1 1 1.5 2s 59 (3:1) oo hhh hs) LE

Aqueous solution 24 100 0.5 0.5 1 1 1.5 1.5 ps 0 59 (3.7:1) oo pss h psps

[43] Inventive step

[44] Currently, the most similar synthesis technology: (modification and demulsification research on bisphenol A phenol amine resin polyether) Quantitative bisphenol A and tetraethylenepentamine with a molar amount 4 times that of the bisphenol A were evenly mixed and dissolved at 50°C. Then, a formaldehyde solution with the same molar amount as the tetraethylenepentamine was slowly and dropwise added and a temperature was continuously maintained for 2 h after dropwise adding. A certain amount of xylene was added into a flask and a water separator was installed, so as to completely remove water generated from a reaction. A temperature was increased

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LU501295 for backflow, and to take away all the water. Vacuumizing treatment was performed to remove residual xylene, to obtain (bisphenol A) BPA phenol amine resin.

[45] The BPA described above and potassium hydroxide (KOH) were sequentially added into a high-pressure reaction kettle, and the high-pressure reaction kettle was sealed, vacuumized to -0.1 MPa during heating and continuously vacuumized till a temperature reached 100°C. When the temperature was close to 120°C, propylene oxide (PO) was slowly, continuously and slightly introduced, with a pressure of the reaction kettle lower than 0.4 MPa. After feeding, the PO continuously reacted, a pressure was gradually reduced and a gauge pressure was reduced to -0.1 MPa, indicating a complete reaction, to prepare a BPA-PO lipophilic polyether.

[46] The BPA-PO lipophilic polyether described above and KOH were sequentially added into the high-pressure reaction kettle and ethylene oxide (EO) was slowly, continuously and slightly introduced in the same preparation mode. Due to a high activity of the EO, a pressure was controlled to be lower than 0.2 MPa and a temperature was controlled to be lower than 120°C. A pressure was reduced to -0.1 MPa, indicating a complete reaction, to prepare a BPA-PO-EO lipophilic polyether. The polyether was dissolved in dichloromethane and washed with water three times.

Anhydrous MgSO4 was added for drying and removing water. Finally, the dichloromethane was removed and then vacuum drying was performed to obtain a BPA block polyether product.

[47] A certain amount of isocyanate xylene solution was slowly and dropwise added into a three-necked flask with mechanical stirring at 55°C given that three added isocyanates was of the same molar amount. After dropwise adding, an isocyanate modified demulsifier solution with a concentration of 50% was obtained.

[48] Differences from the present invention:

[49] 1. The present invention utilized the triethylene tetramine to prepare the multi-branched polyether A, while the tetraethylenepentamine was used as a raw material to prepare the polyether described above.

[50] 2. The present invention used the epoxy chloropropane as an agent for modification, while the three isocyanates were used as agents in the modification experimental step described above.

[51] 3. The modified multi-branched polyether A demulsifier prepared by the present invention was hydrophilic, while the modified BPA-PO-EO block polyether product described above was lipophilic.

Claims (12)

BL-5384 LU501295 CLAIMS

1. À multi-branched polyether demulsifier, wherein a process for synthesizing and modifying same comprises: (1) putting 2,2-bis(4-hydroxyphenyl) propane and triethylene tetramine into a four-necked flask, heating to 45-55°C to completely dissolve same, maintaining a temperature for 35-45 min and then adding xylene for a reaction, to generate an initiator; putting the initiator and potassium hydroxide into a high-temperature high-pressure reaction kettle, sealing and vacuumizing the reaction kettle to a negative pressure, and introducing propylene oxide, to obtain an intermediate product 1; introducing ethylene oxide to obtain a multi-branched polyether B; and slowly and dropwise adding epoxy chloropropane to prepare the modified multi-branched polyether demulsifier.

2. The preparation method according to claim 1, wherein a mass part of three components is 1:2:0.4-1:3:0.6.

3. The preparation method according to claim 1, wherein a heating and dissolving temperature is 50°C.

4. The preparation method according to claim 1, wherein a thermal insulation time is 30 min.

5. The preparation method according to claim 1, wherein a backflow dehydration time is 2 h.

6. The preparation method according to claim 1, wherein a reaction temperature 1s 190°C and a reaction time 1s 1 h.

7. The preparation method according to claim 1, wherein a reaction temperature 1s 110°C.

8. The preparation method according to claim 1, wherein a catalyst for a polyether reaction is the potassium hydroxide.

9. The preparation method according to claim 1, wherein a vacuumizing time is 4-6 min and a gauge pressure is -0.09 MPa.

10. The preparation method according to claim 1, wherein a catalyst is the potassium hydroxide.

11. The preparation method according to claim 1, wherein temperatures are increased to 50-60°C°C, 60-80°C and 80-90°C for the first time, the second time and the third time, respectively.

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12. The preparation method according to claim 1, wherein 0.2 parts of epoxy chloropropane is used and an adding time is 2-3 h.