An efficient demulsifier for oily sludge and its preparation method

Abstract

The present invention discloses a high-efficiency demulsifier for oily sludge and a preparation method thereof, belonging to the technical field of sludge treatment. Octylphenol polyoxyethylene ether is dissolved in water, stirred and then transferred to a flask. The temperature is raised to 60 °C, and an aqueous solution of peroxide is added. Under nitrogen protection, the temperature is raised to 80 °C, and methyl methacrylate, butyl acrylate and an auxiliary agent are added. After maintaining the temperature for 30-60 minutes, the temperature is lowered to 60 °C, and an aqueous solution of hydroquinone is added. After maintaining the temperature for 30 minutes, a primary demulsifier is obtained; the primary demulsifier, sodium silicate and water are stirred to prepare a high-efficiency demulsifier for oily sludge; there is a chemical interaction between the auxiliary agent containing a quaternary ammonium salt structure and methyl methacrylate and butyl acrylate, and graft crosslinking occurs, and then they act synergistically to jointly improve the demulsification effect of the demulsifier. In addition, due to the combined action of raw materials such as the non-ionic demulsifier - octylphenol polyoxyethylene ether, the inorganic demulsifier - sodium silicate and hydroquinone, the demulsifier for sludge in the present invention has an efficient and stable demulsification effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of sludge treatment, and specifically relates to a demulsifier for high-efficiency oily sludge and a preparation method thereof. Background Art

[0002] Oily sludge is a relatively stable suspension emulsion system containing water-in-oil, oil-in-water, and suspended solids. Oily sludge has a complex composition, containing a large amount of organic pollutants such as benzene series, phenols, anthracenes, radioactive elements, and heavy metal elements, and is listed as a hazardous waste in the "National Hazardous Waste List".

[0003] Currently, the main treatment methods for oily sludge include water washing method, extraction method, demulsification method, microbial method, etc. The demulsification method plays a role in preventing droplet combination by reducing the demulsification rate constant, and it is a very efficient oil sludge separation method compared to the water washing method, extraction method, and microbial method, etc. However, the oil recovery rate that can be achieved by the demulsifiers used in the prior art still needs to be improved. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a demulsifier for high-efficiency oily sludge and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A preparation method of a demulsifier for high-efficiency oily sludge includes the following steps:

[0007] (1) Dissolve octylphenol polyoxyethylene ether in water, stir for 10 - 15 min, then transfer it to a three-necked flask, heat up to 60 °C, slowly add an aqueous solution of peroxide, heat up to 80 °C under nitrogen protection, then slowly add methyl methacrylate, butyl acrylate, and an auxiliary agent in sequence, keep the temperature for 30 - 60 min, finally cool down to 60 °C, slowly add an aqueous solution of hydroquinone, and keep the temperature for 30 min to obtain a primary demulsifier;

[0008] (2) Stir and mix the primary demulsifier, sodium silicate, and water to prepare a demulsifier for high-efficiency oily sludge.

[0009] Hydroquinone is used as a polymerization inhibitor. By slowing down or preventing the formation of free radicals in the polymerization reaction, the molecular weight distribution of the polymer is controlled, so that the finally prepared demulsifier has a better dehydration and deoiling effect. The addition of hydroquinone helps to improve the performance of the demulsifier, ensuring that it can effectively reduce the viscosity of the oil-water interface and promote oil-water separation during application. In addition, the stability and high antioxidant properties of hydroquinone also contribute to improving the overall stability and service life of the demulsifier.

[0010] Further, the step (1) comprises raw materials in the following parts by weight: 0.5 - 1.5 parts of octylphenol polyoxyethylene ether, 0.12 - 0.18 parts of peroxide, 2 - 6 parts of methyl methacrylate, 5 - 10 parts of butyl acrylate, 1.0 - 1.5 parts of auxiliary agent, 0.01 - 0.015 parts of hydroquinone, and 85 - 100 parts of water.

[0011] Further, the octylphenol polyoxyethylene ether is one or more of octylphenol polyoxyethylene ether - 4, octylphenol polyoxyethylene ether - 10, octylphenol polyoxyethylene ether - 40, and octylphenol polyoxyethylene ether - 50.

[0012] Further, the peroxide is one or more of potassium persulfate, sodium persulfate, and ammonium persulfate.

[0013] Further, the auxiliary agent is prepared through the following steps:

[0014] S1. Under nitrogen protection, add glucosamine methylamine, 5 - chloro - 1 - pentene, triethylamine, and DMSO (dimethyl sulfoxide) into a dry three - necked flask, stir well and heat up to 60 °C, keep the temperature for reaction for 3 h, and perform reduced - pressure distillation after the reaction ends to obtain intermediate 1; the dosage ratio of glucosamine methylamine, 5 - chloro - 1 - pentene, triethylamine, and DMSO is 17.6 g:10.2 g:16.3 mL:120 mL;

[0015] Triethylamine is used as an acid - binding agent. Under heating, control the molar ratio of glucosamine methylamine to 5 - chloro - 1 - pentene to be 1:1.05 - 1.1, then the - NH - of glucosamine methylamine and the - Cl of 5 - chloro - 1 - pentene undergo a substitution reaction, and the reaction process is as follows:

[0016]

[0017] S2. Under nitrogen protection, add intermediate 1, chlorotetradecane, triethylamine, and DMSO into a dry three - necked flask, stir well and heat up to 70 °C, keep the temperature for reaction for 5 h, and perform reduced - pressure distillation after the reaction ends to obtain the auxiliary agent; the dosage ratio of intermediate 1, chlorotetradecane, triethylamine, and DMSO is 21.1 g:25.1 mL:14.5 mL:180 mL.

[0018] Triethylamine is used as an acid - binding agent. Under heating, control the molar ratio of intermediate 1 to chlorotetradecane to be 1:1.1 - 1.2, then intermediate 1 and chlorotetradecane undergo a substitution reaction, and the reaction process is as follows:

[0019]

[0020] The auxiliary agent is a quaternary ammonium salt demulsifier, with one end being a hydrophilic end rich in hydroxyl groups and the other end being a lipophilic end containing a long carbon chain. At the same time, the auxiliary agent contains carbon-carbon double bonds, which can chemically react with the carbon-carbon double bonds in methyl methacrylate and butyl acrylate under the action of peroxides. On the one hand, this is conducive to reducing the strength of the oil-water interfacial film and increasing the dynamic interfacial activity, thus showing excellent demulsification effects. On the other hand, it enables the auxiliary agent to be fully dispersed and stably exist in the primary demulsifier for a long time, giving full play to the demulsification effect.

[0021] In addition, the addition of sodium silicate causes a synergistic effect between the organic demulsifier and the inorganic demulsifier, and further enables the demulsifier for oily sludge of the present invention to have efficient and stable demulsification effects.

[0022] Further, in the step (2), the mass ratio of the primary demulsifier, sodium silicate and water is 12 - 25:0.5 - 0.8:74 - 88.

[0023] The present invention also discloses a highly efficient demulsifier for oily sludge, which is prepared according to the preparation method of the highly efficient demulsifier for oily sludge described above.

[0024] The beneficial effects of the present invention: The auxiliary agent containing a quaternary ammonium salt structure has a chemical reaction and graft crosslinking with methyl methacrylate and butyl acrylate, and then acts synergistically to jointly improve the demulsification effect of the demulsifier. Coupled with the combined action of raw materials such as the non-ionic demulsifier - octylphenol polyoxyethylene ether, the inorganic demulsifier - sodium silicate and hydroquinone, the demulsifier for oily sludge of the present invention has efficient and stable demulsification effects. Specific Embodiments

[0025] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0026] Example 1

[0027] Prepare the auxiliary agent, and the specific steps are as follows:

[0028] S1. Under nitrogen protection, add 17.6 g of glucosamine, 10.2 g of 5-chloro-1-pentene, 16.3 mL of triethylamine and 120 mL of DMSO into a 250 mL dry three-necked flask, stir well and heat up to 60 °C, keep the temperature for reaction for 3 h, and after the reaction is completed, carry out reduced pressure distillation to obtain intermediate 1;

[0029] S2. Under nitrogen protection, add 21.1 g of Intermediate 1, 25.1 mL of tetradecyl chloride, 14.5 mL of triethylamine, and 180 mL of DMSO into a 500 mL dry three-necked flask. Stir well and heat up to 70 °C, keep the temperature for reaction for 5 h. After the reaction is completed, distill under reduced pressure to obtain the auxiliary agent.

[0030] Example 2

[0031] To prepare a demulsifier for oily sludge, the specific steps are as follows: 85

[0032] (1) Dissolve 0.5 part of octylphenol polyoxyethylene ether-4 in 65 parts of water, stir for 10 min and then transfer it into a three-necked flask. Heat up to 60 °C, slowly add 0.12 part of ammonium persulfate aqueous solution (wherein, there are 15 parts of water). Under nitrogen protection, heat up to 80 °C, and then slowly add 2 parts of methyl methacrylate, 5 parts of butyl acrylate, and 1 part of the auxiliary agent in sequence. Keep the temperature for 30 min, finally cool down to 60 °C, slowly add 0.01 part of hydroquinone aqueous solution (wherein, there are 5 parts of water), and keep the temperature for 30 min to obtain the primary demulsifier.

[0033] (2) Stir and mix the primary demulsifier, sodium silicate, and water (the mass ratio of the primary demulsifier, sodium silicate, and water is 12:0.5:88) to prepare a demulsifier for oily sludge.

[0034] Example 3

[0035] To prepare a demulsifier for oily sludge, the specific steps are as follows:

[0036] (1) Dissolve 1.2 parts of octylphenol polyoxyethylene ether-40 in 80 parts of water, stir for 14 min and then transfer it into a three-necked flask. Heat up to 60 °C, slowly add 0.16 part of sodium persulfate aqueous solution (wherein, there are 10 parts of water). Under nitrogen protection, heat up to 80 °C, and then slowly add 5 parts of methyl methacrylate, 8 parts of butyl acrylate, and 1.3 parts of the auxiliary agent in sequence. Keep the temperature for 50 min, finally cool down to 60 °C, slowly add 0.012 part of hydroquinone aqueous solution (wherein, there are 5 parts of water), and keep the temperature for 30 min to obtain the primary demulsifier.

[0037] (2) Stir and mix the primary demulsifier, sodium silicate, and water (the mass ratio of the primary demulsifier, sodium silicate, and water is 20:0.7:80) to prepare a demulsifier for oily sludge.

[0038] Example 4

[0039] To prepare a demulsifier for oily sludge, the specific steps are as follows:

[0040] (1) Dissolve 1.5 parts of octylphenol polyoxyethylene ether - 10 in 85 parts of water. After stirring for 15 min, transfer it to a three - necked flask, heat up to 60 °C, slowly add 0.18 parts of potassium persulfate aqueous solution (wherein, there are 10 parts of water). Under nitrogen protection, heat up to 80 °C, then slowly add 6 parts of methyl methacrylate, 10 parts of butyl acrylate and 1.5 parts of auxiliary agent in sequence, keep the temperature for 60 min, finally cool down to 60 °C, slowly add 0.015 parts of hydroquinone aqueous solution (wherein, there are 5 parts of water), keep the temperature for 30 min to obtain the primary demulsifier;

[0041] (2) Stir and mix the primary demulsifier, sodium silicate and water (the mass ratio of the primary demulsifier, sodium silicate and water is 25:0.8:74) to prepare a demulsifier for oily sludge.

[0042] Comparative Example 1

[0043] Prepare a demulsifier for oily sludge, and the specific steps are as follows:

[0044] Keep the rest of the steps unchanged, only remove the auxiliary agent in Example 2 to prepare a demulsifier for oily sludge.

[0045] Comparative Example 2

[0046] Prepare a demulsifier for oily sludge, and the specific steps are as follows:

[0047] Keep the rest of the steps unchanged, only replace the auxiliary agent in Example 2 with dodecyl dimethyl benzyl ammonium chloride to prepare a demulsifier for oily sludge.

[0048] Performance test

[0049] Weigh 40 parts of oily sludge samples, add 40 parts of water, heat and stir evenly to prepare a total of five samples of oily sludge water. Then add 4 parts of the demulsifiers for oily sludge prepared in Examples 2 - 4 and Comparative Examples 1 - 2 respectively, stir at 80 °C for 3 h, carry out air flotation for 40 min, let it stand for 20 min, then skim off the upper floating oil, and repeat the air flotation - standing - skimming steps twice. Finally, centrifuge for 10 min at a rotational speed of 2500 rpm, and pour off the upper water layer to obtain the cleaned oil sludge. The solid - phase oil content after cleaning is shown in the following table:

[0050] Test Items Solid Oil Content % Example 2 1.25 Example 3 1.23 Example 4 1.22 Comparative Example 1 1.89 Comparative Example 2 1.61

[0051] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above - mentioned terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0052] The above content is only an example and illustration of the present invention. Those skilled in the art to which the present technology pertains can make various modifications, supplements, or use similar methods for substitution to the specific embodiments described. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they shall fall within the protection scope of the present invention.

Claims

1. A method for preparing an efficient demulsifier for oily sludge, characterized in that: The following steps are involved: (1) dissolving octylphenol polyoxyethylene ether in water, stirring for 10-15 minutes, transferring the mixture into a flask, heating the mixture to 60° C., adding a peroxide aqueous solution, heating the mixture to 80° C. under nitrogen protection, adding methyl methacrylate, butyl acrylate and an auxiliary agent, keeping the temperature for 30-60 minutes, cooling the mixture to 60° C., adding a hydroquinone aqueous solution, and keeping the temperature for 30 minutes to obtain a primary demulsifier; (2) stirring the primary demulsifier, sodium silicate and water to prepare a high-efficiency demulsifier for oily sludge; Wherein, the auxiliary agent is prepared by the following steps: S1. Add glucose methylamine, 5-chloro-1-pentene, triethylamine and DMSO into a flask under nitrogen protection, stir and heat to 60°C for reaction for 3 hours, and distill under reduced pressure to obtain intermediate 1; the dosage ratio of glucose methylamine, 5-chloro-1-pentene, triethylamine and DMSO is 17.6 g:10.2 g:16.3 mL:120 mL; S2. Under nitrogen protection, add intermediate 1, tetradecane chloride, triethylamine and DMSO into a flask, stir and heat to 70°C for reaction for 5 hours, and distill under reduced pressure to obtain an auxiliary agent; the dosage ratio of intermediate 1, tetradecane chloride, triethylamine and DMSO is 21.1 g:25.1 mL:14.5 mL:180 mL.

2. The method for preparing a high-efficiency demulsifier for oily sludge according to claim 1, characterized in that: The step (1) comprises the following raw materials in parts by weight: 0.5-1.5 parts of octylphenol polyoxyethylene ether, 0.12-0.18 parts of peroxide, 2-6 parts of methyl methacrylate, 5-10 parts of butyl acrylate, 1.0-1.5 parts of auxiliary agent, 0.01-0.015 parts of hydroquinone, and 85-100 parts of water.

3. The method for preparing a high-efficiency demulsifier for oily sludge according to claim 2, characterized in that: The octylphenol polyoxyethylene ether is one or more of octylphenol polyoxyethylene ether-4, octylphenol polyoxyethylene ether-10, octylphenol polyoxyethylene ether-40, and octylphenol polyoxyethylene ether-50.

4. The method for preparing a high-efficiency demulsifier for oily sludge according to claim 2, characterized in that: The peroxide is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.

5. The method for preparing a high-efficiency demulsifier for oily sludge according to claim 1, characterized in that: In the step (2), the mass ratio of the primary demulsifier, sodium silicate and water is 12-25:0.5-0.8:74-88.

6. A highly efficient demulsifier for oily sludge, characterized in that: The demulsifier is prepared according to the method for preparing a high-efficiency oily sludge demulsifier according to any one of claims 1 to 5.

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