Defoaming agent for sand-containing foam and preparation method thereof

Abstract

The invention discloses a defoaming agent for sand-containing foam, and also discloses a preparation method of the defoaming agent for sand-containing foam, the defoaming agent for sand-containing foam comprises 45%-60% of phenylalanine modified silicone oil, 4%-5% of white carbon black, 10%-20% of a low-molecular inorganic flocculant, 2%-5% of an emulsifier, 3%-5% of a penetrant, 1%-3% of a viscosity reducer, and the balance of water, and the sum of the mass percentages of the components is 100%. The preparation method comprises the following steps: heating phenylalanine modified silicone oil to 90-100 DEG C, adding white carbon black while stirring, and cooling the stirred mixed solution to 70-80 DEG C to obtain an intermediate product A; the preparation method comprises the following steps: heating water to 70-80 DEG C, adding a low-molecular inorganic flocculant, stirring, and adding an emulsifier, a penetrant and a viscosity reducer into the stirred mixed solution to obtain an intermediate product B; and adding the intermediate product B into the intermediate product A under the reaction conditions that the temperature is 70-80 DEG C and the rotating speed is 300-500rp, stirring, and cooling to room temperature to obtain the defoaming agent for the sand-containing foam, so that the problem of low defoaming efficiency of the sand-containing foam is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of defoamers and relates to a defoamer for sand-containing foam. The invention also relates to a preparation method of the defoamer. Background Art

[0002] In the process of foam drainage, gas wells that are prone to sand production often fail to completely defoam the ground foam, causing the foam to flip over in the separator, which affects the downstream production. Taking the Sebei gas field as an example, the reservoir is loosely cemented, has poor lithology, and the gas and water layers are intertwined. It has the characteristics of strong speed sensitivity and medium-strong water sensitivity. It is very easy to produce sand. The sand particle size is 0.04-0.07mm, and the clay content is as high as 20%-30%. It was found on site that the foam formed in the foam drainage well is difficult to eliminate. The defoaming agents in the prior art, such as CN108726913A "A silicon ether composite defoaming agent and its preparation method and application", CN109200632A "A multifunctional non-toxic high-temperature organosilicon-modified polyether industrial defoaming agent and its preparation method", and CN109173351A "An emulsion-type organosilicon-modified castor oil polyether defoaming agent and preparation method" are not specifically used for defoaming sand-containing foam; and the various defoaming agents used on site have not achieved significant results.

[0003] Therefore, it is necessary to develop a defoamer suitable for sand-containing foam to solve the technical problem that the defoamer in the prior art has a poor defoaming effect on sand-containing foam. Summary of the invention

[0004] The purpose of the invention is to provide a defoamer for sand-containing foam, which solves the technical problem that the defoamer in the prior art has a poor defoaming effect on sand-containing foam.

[0005] Another object of the present invention is to provide a method for preparing the defoamer.

[0006] The technical solution adopted by the present invention is to provide a defoamer for sand-containing foam, which is composed of the following components in terms of mass percentage: 45% to 60% of phenylalanine modified silicone oil, 4% to 5% of white carbon black, 10% to 20% of low molecular inorganic flocculant, 2% to 5% of emulsifier, 3% to 5% of penetrant, 1% to 3% of viscosity reducer, and the balance is water, and the sum of the mass percentages of the above components is 100%.

[0007] The present invention is also characterized in that: the molecular structure of the phenylalanine modified silicone oil is as follows, wherein the value of n is 8-16.

[0008]

[0009] White carbon black is precipitated silica with a specific surface area of ​​150-250m 2 / g, the low molecular inorganic flocculant is any one of potassium aluminum sulfate, aluminum chloride, ferric sulfate, and ferric chloride, the penetrant is any one of sodium succinate sulfonate, sodium edetate and its derivatives, the viscosity reducer is ethylene glycol monobutyl ether, and the emulsifier is a non-ionic surfactant with an HLB value of 10 to 14, and any one of polyoxyethylene lauryl ether, polyoxyethylene alkylphenol, and polyoxyethylene monolaurate is selected.

[0010] Another technical solution adopted by the present invention is to provide a method for preparing the above-mentioned defoaming agent, comprising the following steps:

[0011] Step 1: Weigh the following components by mass percentage: 45% to 60% phenylalanine modified silicone oil, 4% to 5% white carbon black, 10% to 20% low molecular inorganic flocculant, 2% to 5% emulsifier, 3% to 5% penetrant, 1% to 3% viscosity reducer, and the balance is water. The sum of the mass percentages of the above components is 100%;

[0012] Step 2: heating the phenylalanine modified silicone oil to 90-100° C., adding white carbon black at a speed of 300-500 rpm, stirring for 0.5-1 h, and cooling the stirred mixed solution to 70-80° C. to obtain an intermediate product A;

[0013] Step 3: Heat the water to 70-80° C., add a low molecular inorganic flocculant, stir at 300-500 rpm for 15-30 min, add an emulsifier, a penetrant, and a viscosity reducer to the stirred mixture to obtain an intermediate product B;

[0014] Step 4: Under the reaction conditions of temperature 70-80°C and rotation speed 300-500 rpm, add intermediate product B to intermediate product A, stir for 1-1.5 hours, and cool to room temperature to obtain a defoaming agent for sand-containing foam.

[0015] The beneficial effects of the present invention are:

[0016] (1) The defoamer for sand-containing foam prepared by the present invention has good storage stability and does not delaminate when placed at 10-40° C. for 6 months;

[0017] (2) The defoamer for sand-containing foam prepared by the invention has good dispersibility and can be quickly dispersed in water under manual stirring without obvious stratification;

[0018] (3) The defoaming agent for sand-containing foam prepared by the present invention has good defoaming effect. Under the condition that the on-site sand content is 0-2%, the amount of the defoaming agent is 0.5-3 times the amount of the foaming agent to achieve complete defoaming, the initial defoaming rate is 99%, and the 3-minute defoaming rate is 100%. This solves the technical problem that the defoaming agent in the prior art is prone to secondary foaming and poor defoaming effect when defoaming sand-containing foam. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the synthetic reaction equation of the phenylalanine modified silicone oil of the present invention. DETAILED DESCRIPTION

[0020] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0021] The defoamer for sand-containing foam is composed of the following components by mass percentage: 45% to 60% of phenylalanine modified silicone oil, 4% to 5% of white carbon black, 10% to 20% of low molecular inorganic flocculant, 2% to 5% of emulsifier, 3% to 5% of penetrant, 1% to 3% of viscosity reducer, and 1% to 3% of water, and the sum of the mass percentages of the above components is 100%. The molecular structure of the phenylalanine modified silicone oil is as follows, wherein n is 8 to 16.

[0022]

[0023] like Figure 1 As shown in the figure, the molecular synthesis equation of phenylalanine modified silicone oil is prepared by reacting silicone oil with phenylalanine under the conditions of thionyl chloride and dichloromethane. For silicone oil, is phenylalanine, SOCl2 is dichlorothionyl, and DCM is dichloromethane. It spreads on the surface of the foam liquid film to play a defoaming role. The low molecular inorganic flocculant is at least one of potassium aluminum sulfate, aluminum chloride, ferric sulfate, and ferric chloride. It mainly flocculates the negatively charged sand into clumps and relies on gravity to settle, thereby promoting the defoaming of sand-containing foam; the viscosity reducer is ethylene glycol monobutyl ether, which reduces the viscosity of the foam liquid film, thereby increasing the drainage rate on the surface of the foam liquid film and improving the defoaming rate; the emulsifier is a non-ionic surfactant with an HLB value of 10-14, and at least one of polyoxyethylene lauryl ether, polyoxyethylene alkylphenol, and polyoxyethylene monolaurate is selected to emulsify each component into a uniform phase; white carbon black is precipitated silica: the specific surface area is 150-250m 2 / g. The silanol bonds contained in the phenylalanine modified silicone oil are used to form hydrogen bonds with water molecules, so that the phenylalanine modified silicone oil is dispersed and stabilized in water. The further penetrant is at least one of sodium succinate octyl sulfonate, sodium edetate and its derivatives: the function is to disperse the phenylalanine modified silicone oil and further improve the defoaming effect.

[0024] The preparation method of the sand-containing foam defoamer of the present invention is specifically implemented according to the following steps:

[0025] Step 1: Weigh the following components by mass percentage: 45% to 60% phenylalanine modified silicone oil, 4% to 5% white carbon black, 10% to 20% low molecular inorganic flocculant, 2% to 5% emulsifier, 3% to 5% penetrant, 1% to 3% viscosity reducer, and the balance is water. The sum of the mass percentages of the above components is 100%;

[0026] Step 2: heating the phenylalanine modified silicone oil to 90-100° C., adding white carbon black at a speed of 300-500 rpm, stirring for 0.5-1 h, and cooling the stirred mixed solution to 70-80° C. to obtain an intermediate product A;

[0027] Step 3: Heat the water to 70-80° C., add a low molecular inorganic flocculant, stir at 300-500 rpm for 15-30 min, add an emulsifier, a penetrant, and a viscosity reducer to the stirred mixture to obtain an intermediate product B;

[0028] Step 4: Under the reaction conditions of temperature 70-80°C and rotation speed 300-500 rpm, add intermediate product B to intermediate product A, stir for 1-1.5 hours, and cool to room temperature to obtain a defoaming agent for sand-containing foam.

[0029] Embodiment 1:

[0030] Preparation of phenylalanine modified silicone oil: 458 g of silicone oil with n=10 and 330 g of phenylalanine were reacted in the presence of 330 g of thionyl chloride and 165 g of dichloromethane. The synthesis equation is:

[0031]

[0032] The specific implementation is as follows: 458g of silicone oil (n=10), 330g of phenylalanine, and 165g of thionyl chloride are sequentially added into a reaction flask and mixed evenly to obtain a mixture A; 165g of thionyl chloride and 165g of dichloromethane are mixed evenly in a titration container to obtain a mixture B; the agitator in the reaction flask containing the mixture A is turned on at a stirring speed of 200rpm, and the mixture B is added dropwise into the mixture A, and the addition is completed within 30min, and stirring is continued for 60min; the reaction flask is heated to a constant temperature of 60°C, and the reaction solvent is evaporated, and the residue obtained after evaporation for 2h is the preparation of the phenylalanine-modified silicone oil.

[0033] Preparation of defoamers for sand-containing foams:

[0034] Step 1: Heat 200g of the phenylalanine modified silicone oil prepared above to 90°C, and slowly add 16g of a 150m 2 / g precipitated silica, stirred for 1h, cooled to 70°C to obtain intermediate product A;

[0035] Step 2: 109 g of water was heated to 70° C., 48 g of potassium aluminum sulfate was added at 400 rpm, and stirred for 20 min. Then, 12 g of polyoxyethylene lauryl ether, 12 g of sodium octyl succinate sulfonate and 4 g of ethylene glycol monobutyl ether were added, and stirring was continued for 1 h to obtain intermediate product B;

[0036] Step 3: Under the conditions of 70° C. and 400 rpm, add the intermediate product B to the intermediate product A, continue stirring for 1 hour, and cool to room temperature to obtain a defoaming agent for sand-containing foam.

[0037] Embodiment 2:

[0038] Preparation of phenylalanine modified silicone oil: 546 g of the above silicone oil with n=12 was reacted with 330 g of phenylalanine in the presence of 330 g of thionyl chloride and 165 g of dichloromethane. The synthesis equation is:

[0039]

[0040] The above 546g of silicone oil, n=12, 330g of phenylalanine, and 165g of thionyl chloride are sequentially added into a reaction flask and mixed evenly to obtain a mixture A; 165g of thionyl chloride and 165g of dichloromethane are mixed evenly in a titration container to obtain a mixture B; the agitator in the reaction flask containing the mixture 1 is turned on at a stirring speed of 150rpm, and the mixture 2 is added dropwise into the mixture 1, and the addition is completed within 30min, and stirring is continued for 50min; the reaction flask is heated to a constant temperature of 60°C, and the reaction solvent is evaporated. The residue obtained after evaporation for 2h is the phenylalanine-modified silicone oil.

[0041] Preparation of defoamers for sand-containing foams:

[0042] Step 1: Heat the 220 g phenylalanine modified silicone oil prepared above to 95 °C, and slowly add 18 g of an average specific surface area of ​​200 m 2 / g precipitated silica, stirred for 1h, cooled to 80°C to obtain intermediate product A;

[0043] Step 2: 82 g of water was heated to 80° C., 40 g of aluminum chloride was added at 300 rpm, and stirred for 15 min. Then, 16 g of polyoxyethylene alkylphenol, 16 g of sodium edetate and 8 g of ethylene glycol monobutyl ether were added, and stirring was continued for 0.5 h to obtain intermediate product B;

[0044] Step 3: Under the conditions of 80°C and 300 rpm, add intermediate product B to intermediate product A, continue stirring for 1 hour, cool to room temperature, and obtain a defoaming agent for sand-containing foam.

[0045] Embodiment 3:

[0046] Preparation of phenylalanine modified silicone oil: 634 g of silicone oil with n=16 and 330 g of phenylalanine were reacted in the presence of 330 g of thionyl chloride and 165 g of dichloromethane. The synthesis equation is:

[0047]

[0048] The specific implementation is as follows: n is 14, 634g silicone oil, 330g phenylalanine, and 165g thionyl chloride are added to a reaction flask in sequence and mixed evenly to obtain a mixture A; 165g thionyl chloride and 165g dichloromethane are mixed evenly in a titration container to obtain a mixture B; the agitator in the reaction flask containing the mixture A is turned on at a stirring speed of 150rpm, and the mixture B is added dropwise to the mixture A, the addition is completed within 30min, and stirring is continued for 50min; the reaction flask is heated to a constant temperature of 60°C, the reaction solvent is evaporated, and the residue obtained after evaporation for 2h is the preparation of the phenylalanine-modified silicone oil.

[0049] Preparation of defoamers for sand-containing foams:

[0050] Step 1: Heat 212 g of the phenylalanine modified silicone oil prepared above to 100 °C, and slowly add 20 g of a 20% phenylalanine with an average specific surface area of ​​220 m 2 / g precipitated silica, stirred for 45 min, cooled to 75°C to obtain intermediate product A;

[0051] Step 2: 82 g of water was heated to 75° C., 36 g of potassium aluminum sulfate and 36 g of aluminum chloride were added at 350 rpm, and stirred for 20 min. Then, 8 g of polyoxyethylene lauryl ether, 8 g of polyoxyethylene alkylphenol, 8 g of octyl succinate sulfonic acid, 8 g of sodium edetate and 6 g of ethylene glycol monobutyl ether were added, and stirring was continued for 45 min to obtain intermediate product B;

[0052] Step 3: Under the conditions of 75°C and 350 rpm, add intermediate product B to intermediate product A, continue stirring for 1.5 hours, and cool to room temperature to obtain a defoaming agent for sand-containing foam.

[0053] Embodiment 4:

[0054] Preparation of phenylalanine modified silicone oil: 370g of silicone oil with n=8 and 330g of phenylalanine were reacted in the presence of 330g of thionyl chloride and 165g of dichloromethane. The synthesis equation is:

[0055]

[0056] The specific implementation is as follows: 370g of silicone oil with n being 8, 330g of phenylalanine, and 165g of thionyl chloride are sequentially added into a reaction flask and mixed evenly to obtain a mixture 1; 165g of thionyl chloride and 165g of dichloromethane are mixed evenly in a titration container to obtain a mixture 2; the stirrer in the reaction flask containing the mixture 1 is turned on at a stirring speed of 100rpm, and the mixture 2 is added dropwise into the mixture 1, and the addition is completed within 30min, and stirring is continued for 50min; the reaction flask is heated to a constant temperature of 60°C, and the reaction solvent is evaporated, and the residue obtained after evaporation for 2h is the preparation of the phenylalanine-modified silicone oil.

[0057] Preparation of defoamers for sand-containing foams:

[0058] Step 1: Heat 240 g of the phenylalanine-modified silicone oil prepared above to 90°C, and slowly add 20 g of a 250 m 2 / g precipitated silica, stirred for 0.5h, cooled to 70°C to obtain intermediate product A;

[0059] Step 2: Heat 82g of water to 70°C, add 32g of potassium aluminum sulfate, 8g of aluminum chloride and 4g of ferric chloride at 500rpm, stir for 30min, then add 6g of polyoxyethylene lauryl ether, 6g of polyoxyethylene alkylphenol, 6g of polyoxyethylene monolaurate, 8g of octyl succinate sulfonic acid, 8g of sodium edetate and 4.8g of ethylene glycol monobutyl ether, and continue stirring for 1h to obtain intermediate product B;

[0060] Step 3: Under the conditions of 70°C and 500 rpm, add intermediate product B to intermediate product A, continue stirring for 1.25 hours, and cool to room temperature to obtain a defoaming agent for sand-containing foam.

[0061] The defoaming performance of the present invention for sand-containing foam defoamer was tested, and the results were as follows:

[0062] At room temperature, 1000mL of mineralized water was prepared with 10gCaCl2 and 40gNaCl, and 5g / L of aqueous solution was prepared with 30% effective concentration of dodecyl dimethyl betaine and mineralized water, and then a certain amount of sand with a particle size of 0.04-0.07mm was added; 100mL of aqueous solution was added to a stirring container, and stirred at a speed of 11000r / min for 1min by high-speed stirring method, and then immediately poured into a 500mL measuring cylinder, and the foam volumes at the initial and 3min standing were recorded as V0 and V3 respectively. According to the above method, different amounts of defoamers were added to the aqueous solution, and the foam volumes at the initial and 3min standing were retested as V0 and V3 respectively.

[0063] The defoaming rate is calculated by the following formula:

[0064] The initial defoaming rate η0 is:

[0065] The defoaming rate η3 at 3min is:

[0066] The defoaming test results of Examples 1-4 are shown in the following table:

[0067]

[0068]

[0069] It can be seen that under the condition of sand content of 0-2%, the present embodiments 1-4 can achieve complete defoaming by using 0.5-3 times the amount of foaming agent, the initial defoaming rate is 99%-%99.4, and the defoaming rate within 3 minutes is 100%.

Claims

1. A defoamer for sand-containing foam, characterized in that: According to mass percentage, it is composed of the following components: Phenylalanine modified silicone oil 45%-60%, white carbon black 4%-5%, low molecular inorganic flocculant 10%-20%, emulsifier 2%-5%, penetrant 3%-5%, viscosity reducer 1%-3%, the balance is water, and the sum of the mass percentages of the above components is 100%.

2. The defoamer for sand-containing foam according to claim 1, characterized in that: The molecular structure of the phenylalanine modified silicone oil is shown below, where n is 8 to 16. .

3. The defoamer for sand-containing foam according to claim 1, characterized in that: The white carbon black is precipitated silica with a specific surface area of ​​150 to 250 m 2 / g.

4. The defoamer for sand-containing foam according to claim 1, characterized in that: The low molecular weight inorganic flocculant is any one of potassium aluminum sulfate, aluminum chloride, ferric sulfate and ferric chloride.

5. The defoamer for sand-containing foam according to claim 1, characterized in that: The permeation agent is any one of sodium octyl succinate sulfonate, sodium edetate and their derivatives.

6. The defoamer for sand-containing foam according to claim 1, characterized in that: The viscosity reducing agent is ethylene glycol monobutyl ether.

7. The defoamer for sand-containing foam according to claim 1, characterized in that: The emulsifier is a nonionic surfactant with an HLB value of 10 to 14, and is selected from any one of polyoxyethylene lauryl ether, polyoxyethylene alkylphenol, and polyoxyethylene monolaurate.

8. A method for preparing a defoamer for sand-containing foam, characterized in that: Using the above defoaming agent The method comprises the following steps: step 1: weighing the following components by mass percentage: 45% to 60% of phenylalanine modified silicone oil, 4% to 5% of white carbon black, 10% to 20% of low molecular inorganic flocculant, 2% to 5% of emulsifier, 3% to 5% of penetrant, 1% to 3% of viscosity reducer, and the balance being water, the sum of the mass percentages of the above components being 100%; step 2: heating the phenylalanine modified silicone oil to 90 to 100° C., adding white carbon black while stirring, and stirring The mixed solution is cooled to 70-80°C to obtain an intermediate product A; step 3: heating the water to 70-80°C, adding a low molecular inorganic flocculant, stirring, and adding an emulsifier, a penetrant, and a viscosity reducer to the stirred mixed solution to obtain an intermediate product B; step 4: under the reaction conditions of a temperature of 70-80°C and a rotation speed of 300-500rp, the intermediate product B is added to the intermediate product A, stirred, and cooled to room temperature to obtain a defoaming agent for sand-containing foam.

9. The method for preparing a defoamer for sand-containing foam according to claim 8, characterized in that , the stirring rate in step 2 is 300-500 rpm, and the stirring time is 0.5-1 h.

10. The method for preparing a defoamer for sand-containing foam according to claim 8, characterized in that , the stirring rate in step 3 is 300-500 rpm, and the stirring time is 15-30 min.

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