A crude oil defoamer and its synthesis method and application

Abstract

The present invention belongs to the technical field of oil production, and specifically relates to a crude oil defoamer and its synthesis method and application. The synthesis method is as follows: add cyanuric chloride, methanol, propylamino tris (trimethylsiloxy) silane in a four-necked flask, stir, maintain pH6-7, and react for 20-30min; add 1-amino-3,6,9,12,15,18-hexaoxahene-11-decane-21-acid, stir, maintain pH7-8, and react for 60-90min; add 12-aminododecanoic acid, heat to 60-70°C while stirring, maintain pH7-8, and react for 60-90min; vacuum distillation obtains a viscous solid, adds deionized water, heats to 50-60°C, stirs for 20-30min, cools to below 20°C, stands for 24-32h, and separates the oil phase, i.e., the product. The defoamer of the present invention has a good defoaming effect, and the crude oil defoaming rate reaches more than 95%.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum exploitation, and in particular relates to a crude oil defoamer and a synthesis method and application thereof. Background Art

[0002] Foam fluids have been widely used in foam flooding, profile control and water plugging, fracturing and acidizing, etc. In particular, foam flooding provides a new way to improve crude oil recovery. However, during the oil and gas transportation process, when the crude oil is separated into gas and liquid in the separator, the gas dissolved in the crude oil will escape due to the pressure reduction. At this time, the crude oil containing natural or artificial surfactants will produce a lot of foam. Some foams will exist stably in the crude oil for a long time without bursting. At this time, these stable foams will absorb tiny impurity solids, causing blockage. A large amount of foam will also cause cavitation in the pump, causing many harms to crude oil gathering and transportation.

[0003] During the extraction and processing of crude oil, the increase in temperature and the decrease in pressure will destroy the gas-liquid balance of crude oil, causing the light hydrocarbons dissolved in the crude oil to escape as gas; however, due to factors such as oil phase viscosity, space, and flow, it is difficult for light hydrocarbon gas to escape smoothly from the surface of crude oil. It will form bubbles inside the oil phase, causing the volume of crude oil to expand and generate foam. On the one hand, crude oil foam will cause fluctuations in the entire production process; on the other hand, it will affect the operation of the gas phase system, posing a threat to personal and equipment safety.

[0004] In order to eliminate or reduce foam, defoaming agents are generally added in actual operations, and some surfactants are added to the system, thereby reducing the concentration of surfactants in the liquid film and promoting the bursting of foam. High-efficiency defoaming agents using pressure method are particularly important.

[0005] CN102284198A discloses a water-soluble polyether-modified organosilicon defoamer. The preparation method of the polyether-modified organosilicon defoamer comprises the following steps: firstly, adding terminal allyl polyoxyalkylene ether into a container and stirring to remove water; then, adding solvent and low hydrogen silicone oil into the above solution and stirring; then, adding a catalyst and stirring in N 2and stirring and heating reaction under reflux condensation conditions; after the reaction is completed, the solvent and low-boiling substances are removed to obtain a water-soluble polyether-modified silicone. The invention also provides a compounding method for the water-soluble polyether-modified silicone defoamer obtained by the above-mentioned preparation method. The defoamer solves the problems that polysiloxanes are poorly soluble in water, have poor high temperature resistance, poor strong alkali resistance, and that the defoaming speed and anti-foaming time of polyether defoamers are not ideal. The compounding method of the water-soluble polyether-modified silicone defoamer solves the problems that dimethyl silicone oil-type defoamers are incompletely emulsified, demulsified during use, are not resistant to high temperatures, and have poor anti-foaming ability. The focus of the invention is the defoaming of the aqueous phase system. In the preparation process of these defoamer emulsions, a certain amount of emulsifiers are added for emulsification. The presence of these emulsifiers will more or less solubilize part of the silicone oil, thereby reducing the anti-foaming performance of the defoamer.

[0006] CN115228148B discloses a composite defoamer for oil fields and a preparation method thereof, belonging to the field of chemical defoaming technology, comprising the following steps: step 1, preparing modified polysiloxane; step 2: preparing modified silicon dioxide; step 3: adding isophthaloyl chloride and metaphenylenediamine for polymerization reaction to obtain aramid polymer solution; step 4, uniformly mixing modified polysiloxane, modified silicon dioxide, and meta-aramid polymer solution to obtain a silane complex; step 5, uniformly mixing the silane complex with acrylate to prepare a composite agent; step 6, uniformly mixing the composite agent with carbon nanotubes to obtain a composite defoamer for oil fields. The composite defoamer for oil fields prepared by the inventive method is easy to disperse in crude oil and has high defoaming efficiency. The addition of meta-aramid can form a layered and branched structure, increase the number of crosslinks between modified polysiloxane and modified silicon dioxide, and improve the stability of antifoaming. However, the complete defoaming time of the invention requires more than 15 minutes, and the defoaming ability needs to be further improved in actual production. Summary of the invention

[0007] The present invention aims to provide a crude oil defoamer and its synthesis method and application in view of the above-mentioned deficiencies in the prior art. The defoamer of the present invention has good defoaming effect, and the crude oil defoaming rate reaches more than 95%.

[0008] One of the purposes of the present invention is to provide a method for synthesizing a crude oil defoamer, the method comprising the following steps:

[0009] (1) Add cyanuric chloride, methanol and propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 20-30 minutes;

[0010] (2) Add 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60-90 minutes;

[0011] (3) Add 12-aminododecanoic acid, heat to 60-70°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60-90 minutes;

[0012] (4) Vacuum distillation is performed to obtain a viscous solid, deionized water is added, and the mixture is heated to 50-60°C, rapidly stirred for 20-30 minutes, cooled to below 20°C, and allowed to stand for 24-32 hours to separate the oil phase and obtain the defoaming agent product.

[0013] In the present invention, preferably, based on 1 mol part of cyanuric chloride, the amounts of propylaminotris(trimethylsiloxy)silane, 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid and 12-aminododecanoic acid are 0.8-1.2 mol parts, 0.8-1.2 mol parts and 0.9-1.3 mol parts respectively.

[0014] In the present invention, preferably, the mass ratio of methanol to cyanuric chloride in step (1) is 40-50:1.

[0015] In the present invention, preferably, the mass ratio of deionized water to cyanuric chloride in step (4) is 40-50:1.

[0016] The synthetic reaction equation of the crude oil defoamer of the present invention is as follows:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022] Another object of the present invention is to disclose a crude oil defoamer, the molecular structure of the defoamer is as follows:

[0023]

[0024] The third object of the present invention is to disclose the application of the above defoaming agent in oil production.

[0025] The crude oil defoamer of the present invention belongs to a silicon-containing surfactant, which has a small surface tension and can spread rapidly in a liquid. When spreading, a double-layer film is formed on the foam wall, which removes the surfactant of the crude oil in the foam, reduces the local surface tension of the foam, and causes the foam to burst. The siloxysilane, oxygen-hetero-long-chain fatty acid, and long-chain fatty acid in the molecular structure of the present invention are all typical defoaming groups, and the polyamine structure can also enhance the defoaming effect of the present invention. At the same time, the structure itself is multi-branched, which can also enhance the defoaming effect of the present invention. The crude oil defoamer of the present invention has a better defoaming effect, and the crude oil defoaming rate reaches more than 95%. DETAILED DESCRIPTION

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] The present invention will be further described below with reference to specific embodiments.

[0028] In the present invention, the devices or equipment used are all conventional devices or equipment known in the art and are commercially available.

[0029] In the following examples and comparative examples, unless otherwise specified, all reagents used were commercially available chemically pure reagents.

[0030] Example 1

[0031] (1) Add 20 mmol of cyanuric chloride, 169 g of methanol, and 16 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution. Continue the reaction for 20 min.

[0032] (2) Add 16 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60 min;

[0033] (3) Add 26 mmol of 12-aminododecanoic acid, heat to 60°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60 min;

[0034] (4) The viscous solid was obtained by vacuum distillation, 169 g of deionized water was added, and the mixture was heated to 50 °C, stirred rapidly for 20 min, cooled to below 20 °C, and allowed to stand for 24 h. The oil phase was separated to obtain the defoaming agent product.

[0035] Example 2

[0036] (1) Add 20 mmol of cyanuric chloride, 154 g of methanol, and 18 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 30 min;

[0037] (2) Add 21 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 90 min;

[0038] (3) Add 18 mmol of 12-aminododecanoic acid, heat to 60°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 70 min;

[0039] (4) The viscous solid was obtained by vacuum distillation, 164 g of deionized water was added, and the mixture was heated to 52 °C, stirred rapidly for 30 min, cooled to below 20 °C, and allowed to stand for 28 h. The oil phase was separated to obtain the defoaming agent product.

[0040] Example 3

[0041] (1) Add 20 mmol of cyanuric chloride, 183 g of methanol, and 19 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution. Continue the reaction for 25 min.

[0042] (2) Add 18 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 70 min;

[0043] (3) Add 22 mmol of 12-aminododecanoic acid, heat to 60°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 90 min;

[0044] (4) The viscous solid was obtained by vacuum distillation, 183 g of deionized water was added, and the mixture was heated to 50 °C, rapidly stirred for 25 min, cooled to below 20 °C, and allowed to stand for 32 h. The oil phase was separated to obtain the defoaming agent product.

[0045] Example 4

[0046] (1) Add 20 mmol of cyanuric chloride, 161 g of methanol, and 24 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution. Continue the reaction for 22 minutes.

[0047] (2) Add 18 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 80 min;

[0048] (3) Add 20 mmol of 12-aminododecanoic acid, heat to 66°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 80 min;

[0049] (4) The viscous solid was obtained by vacuum distillation, 161 g of deionized water was added, and the mixture was heated to 50°C, stirred rapidly for 22 min, cooled to below 20°C, and allowed to stand for 32 h. The oil phase was separated to obtain the defoaming agent product.

[0050] Example 5

[0051] (1) Add 20 mmol of cyanuric chloride, 152 g of methanol, and 22 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 30 min;

[0052] (2) Add 24 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 65 min;

[0053] (3) Add 18 mmol of 12-aminododecanoic acid, heat to 62°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60 min;

[0054] (4) The viscous solid was obtained by vacuum distillation, 182 g of deionized water was added, and the mixture was heated to 50 °C, stirred rapidly for 27 min, cooled to below 20 °C, and allowed to stand for 31 h. The oil phase was separated to obtain the defoaming agent product.

[0055] Example 6

[0056] (1) Add 20 mmol of cyanuric chloride, 149 g of methanol, and 21 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 22 minutes;

[0057] (2) Add 19 mmol 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain pH 7-8 with sodium hydroxide solution, and continue the reaction for 75 min;

[0058] (3) Add 20 mmol of 12-aminododecanoic acid, heat to 68°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 65 minutes;

[0059] (4) The viscous solid was obtained by vacuum distillation, 172 g of deionized water was added, and the mixture was heated to 55 °C, stirred rapidly for 26 min, cooled to below 20 °C, and allowed to stand for 32 h. The oil phase was separated to obtain the defoaming agent product.

[0060] Example 7

[0061] (1) Add 20 mmol of cyanuric chloride, 164 g of methanol, and 20 mmol of propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 27 minutes;

[0062] (2) Add 20 mmol of 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60 min;

[0063] (3) Add 24 mmol of 12-aminododecanoic acid, heat to 70°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 85 min;

[0064] (4) The viscous solid was obtained by vacuum distillation, 164 g of deionized water was added, and the mixture was heated to 60°C, stirred rapidly for 25 min, cooled to below 20°C, allowed to stand for 28 h, and the oil phase was separated to obtain the defoaming agent product.

[0065] Example 8

[0066] The defoaming effect of the defoaming agent of the present invention (Examples 1-7) was tested, and the test method was based on Q / SHCG 46-2012 "Technical Requirements for Crude Oil Defoaming Agents".

[0067] At the crude oil gathering pipeline of a joint station of Xianhe Oil Production Plant in Shengli Oilfield, oil and water samples without adding defoaming agent were collected. The temperature of the oil and water samples was 50℃, and the water at the bottom was left to stand and drain.

[0068] The defoaming agent of the present invention (Example 1-7) was prepared into a 1.0 wt % solution with a 5 wt % methanol solution and stirred evenly.

[0069] Add 400ml of oil sample to a 500ml measuring cylinder, put in a glass rod, and record the volume V of the oil sample. 1 Quickly add 0.4 ml of 1.0 wt% crude oil defoamer with a syringe, and immediately stir quickly with a glass rod at a speed of not less than 120 rpm. After stirring for 2 minutes, observe and record the crude oil volume V2 .

[0070] Add 1 ml of 1.0 wt% crude oil defoamer to the above sample, place it in a 60°C water bath for 30 min, and stir it quickly with a glass rod until all the crude oil foam disappears. Read the volume of crude oil without foam after stirring (V) 3 .

[0071] The defoaming rate calculation formula is as follows:

[0072] X = (V 1 -V 2 ) / (V 1 -V 3 )×100%

[0073] A comparative experiment was conducted using the crude oil defoamer produced by Dongguan Defeng Defoamer Co., Ltd.

[0074] The experimental results are shown in Table 1.

[0075] Table 1 Defoaming test results of defoaming agent

[0076]

[0077] From Table 1 we can see that:

[0078] The defoaming rates of the defoaming agents of the present invention (Examples 1-7) all reached over 95% when the concentration was 1.0wt%, with the highest reaching 99% (Examples 6 and 7). The defoaming rate of the crude oil defoaming agent of Guangdong Zhongke Hongtai New Materials Co., Ltd. in the comparative example was 85%, which was significantly lower than that of the present invention.

[0079] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for synthesizing a crude oil defoamer, characterized in that: The synthetic method specifically comprises the following steps: (1) Add cyanuric chloride, methanol and propylaminotris(trimethylsiloxy)silane into a four-necked flask, stir, and adjust and maintain the pH at 6-7 with sodium hydroxide solution, and continue the reaction for 20-30 minutes; (2) Add 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, stir, adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60-90 minutes; (3) Add 12-aminododecanoic acid, heat to 60-70°C while stirring, and adjust and maintain the pH at 7-8 with sodium hydroxide solution, and continue the reaction for 60-90 minutes; (4) Vacuum distillation to obtain a viscous solid, add deionized water, heat to 50-60°C, rapidly stir for 20-30 minutes, cool to below 20°C, stand for 24-32 hours, separate the oil phase, and obtain the defoaming agent product; Based on 1 mole of cyanuric chloride, the amounts of propylaminotris(trimethylsiloxy)silane, 1-amino-3,6,9,12,15,18-hexaoxaheneicosane-21-oic acid, and 12-aminododecanoic acid are 0.8-1.2 mole parts, 0.8-1.2 mole parts, and 0.9-1.3 mole parts, respectively; The molecular structural formula of the defoamer is as follows: 。 2. The synthesis method according to claim 1, characterized in that: The mass ratio of methanol to cyanuric chloride in step (1) is 40-50:

1.

3. The synthesis method according to claim 1, characterized in that: The mass ratio of deionized water to cyanuric chloride in step (4) is 40-50:

1.

4. The defoamer synthesized by the synthesis method according to any one of claims 1 to 3, characterized in that: The molecular structural formula of the defoamer is as follows: 。 5. Use of the defoamer according to claim 4 in oil production.

Images