An emulsion breaker

Abstract

The present invention discloses a demulsifier, which relates to the technical field of wastewater treatment. In terms of parts by weight, it is composed of the following components: 58.5 - 79.5 parts of polyacrylamide, 3.5 - 6.5 parts of cationic organosilicon-modified polyacrylamide, 14.5 - 35.5 parts of polyethylene oxide, 0.2 - 1.8 parts of ammonium sulfate, 0.1 - 0.5 parts of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, 1 - 3 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.3 - 0.8 parts of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.1 - 0.3 parts of water-soluble hyperbranched polyamide resin, 0.8 - 1.2 parts of lauryl hydroxyethyl imidazoline, 0.6 - 1 part of amphoteric organic ion salt, and 80 - 100 parts of water. This demulsifier has a small dosage, remarkable demulsification effect and high efficiency at room temperature, a wide application range, and can effectively achieve oil removal and demulsification of coking wastewater.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and particularly to a demulsifier. Background Art

[0002] Coking wastewater is industrial wastewater containing volatile phenols, polycyclic aromatic hydrocarbons, and heterocyclic compounds such as oxygen, sulfur, and nitrogen generated during the processes of coking, gasification, high-temperature dry distillation, purification, and by-product recovery of coke oven gas. It is a kind of industrial organic wastewater with high CODcr, high phenol value, high ammonia nitrogen, and is very difficult to treat. The treatment of coking wastewater is an important environmental challenge faced by industries such as coking and coal chemical industries.

[0003] The existing methods for treating coking wastewater mainly include physical adsorption, flocculation sedimentation, activated sludge method, etc., and then through methods such as membrane filtration technology to make it meet the discharge standards or be recycled. However, due to the characteristics of coking wastewater such as large variations in water quality and quantity, complex composition, high content of organic substances, especially refractory organic substances, and high ammonia nitrogen concentration, and the inappropriate selection of reagents, the biodegradability of coking wastewater is poor. The above methods all have certain limitations in terms of treatment cost, treatment effect, etc. The non-biodegradable substances in coking wastewater are often very difficult to remove, and the treatment effect often cannot meet the standards for recycling or the water quality requirements of membrane filtration. It is in this situation that the tar demulsifier came into being, and its appearance has attracted great attention in the industry.

[0004] As an effective chemical agent, the tar demulsifier has good dispersibility, interfacial activity, compatibility, and effectiveness. It can quickly destroy the surface tension between tar particles in the emulsified suspension, separating them into small particles for convenient subsequent treatment and removal. At the same time, the tar demulsifier also has the function of viscosity reduction, which can appropriately reduce the surface tension of tar and accelerate the separation of tar and tar slag to obtain tar with lower water and slag content. It has significant advantages in improving the treatment efficiency of coking wastewater and reducing the treatment cost. However, the existing tar demulsifiers more or less have technical defects such as a small applicable range, large dosage, unsatisfactory demulsification effect at normal temperature, high input cost, long demulsification time, and instability of active substances in the demulsifier, resulting in the inability to fully play their roles.

[0005] To solve the above problems, a Chinese invention patent with the authorization announcement number CN106495241B discloses an oil-displacing demulsifier for coking wastewater treatment, which contains the following components in volume percentages: 20% - 50% of dodecyl dimethyl benzyl ammonium chloride, 10% - 30% of tetradecyl dimethyl benzyl ammonium chloride, 0.1% - 0.5% of cationic polyacrylamide, 0.1% - 0.3% of polysiloxane emulsion, and the balance is water. The invention also discloses the preparation process and uses of the oil-displacing demulsifier. The demulsifier formula of the invention is simple, and synergistic effects are achieved among the components, which can effectively remove oil, ammonia nitrogen, CODcr, and suspended solids in coking wastewater. However, its application range is limited, and the demulsification effect still needs to be further improved.

[0006] It can be seen that developing a demulsifier with a small dosage, significant demulsification effect at room temperature, high efficiency, wide application range, and capable of effectively achieving oil removal and demulsification of coking wastewater meets the market demand, has broad market value and application prospects, and is of great significance for promoting the development of the demulsifier field. Summary of the Invention

[0007] The purpose of the present invention is to provide a demulsifier with a small dosage, significant demulsification effect at room temperature, high efficiency, wide application range, and capable of effectively achieving oil removal and demulsification of coking wastewater to overcome the deficiencies of the prior art.

[0008] To achieve the above object, the technical solution adopted by the present invention is: A demulsifier, in parts by weight, is composed of the following components: 58.5 - 79.5 parts of polyacrylamide, 3.5 - 6.5 parts of cationic organosilicon-modified polyacrylamide, 14.5 - 35.5 parts of polyethylene oxide, 0.2 - 1.8 parts of ammonium sulfate, 0.1 - 0.5 parts of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, 1 - 3 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.3 - 0.8 parts of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.1 - 0.3 parts of water-soluble hyperbranched polyamide resin, 0.8 - 1.2 parts of lauryl hydroxyethyl imidazoline, 0.6 - 1 part of amphoteric organic ion salt, and 80 - 100 parts of water.

[0009] Preferably, the M of the polyacrylamide n = 12 million g / mol, and M W / M n = 1.428.

[0010] Preferably, there are no special requirements for the source of the cationic organosilicon-modified polyacrylamide. In an embodiment of the present invention, the cationic organosilicon-modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B.

[0011] Preferably, the M of the polyethylene oxide n = 1.2 million g / mol, and M W / M n = 1.317.

[0012] Preferably, for the preparation method of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344 - 345.

[0013] Preferably, the water-soluble hyperbranched polyamide resin is hyperbranched polyamide resin Hyper HPN202, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.

[0014] Preferably, the zwitterionic organic salt is at least one of 1-benzylpyridinium-3-carboxylate and pyridinium hydroxypropanesulfonate.

[0015] Another object of the present invention is to provide a preparation method of the demulsifier, which includes the following steps: mixing the components evenly by weight, then stirring at 35 - 40 °C for 35 - 55 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0016] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0017] (1) The preparation method of the demulsifier disclosed in the present invention has a simple process, convenient operation, does not require special equipment, has high preparation efficiency and finished product qualification rate, low labor intensity, little environmental impact, high cost performance, and is suitable for industrial production.

[0018] (2) The demulsifier disclosed in the present invention, by weight, is composed of the following components: 58.5 - 79.5 parts of polyacrylamide, 3.5 - 6.5 parts of cationic organosilicon-modified polyacrylamide, 14.5 - 35.5 parts of polyethylene oxide, 0.2 - 1.8 parts of ammonium sulfate, 0.1 - 0.5 parts of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, 1 - 3 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.3 - 0.8 parts of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.1 - 0.3 parts of water-soluble hyperbranched polyamide resin, 0.8 - 1.2 parts of lauryl hydroxyethyl imidazoline, 0.6 - 1 part of zwitterionic organic salt, and 80 - 100 parts of water; through the mutual cooperation and joint action of each component, the prepared demulsifier product has a small dosage, significant demulsification effect and high efficiency at room temperature, a wide application range, and can effectively achieve oil removal and demulsification of coking wastewater.

[0019] (3) The demulsifier disclosed in the present invention, through the reasonable selection of the types and dosage ratios of components, enables the prepared product to have good interfacial activity and permeability, can quickly reach the oil-water interface, form an unstable oil-water interfacial film, and has good demulsification performance for coking wastewater. Detailed implementation manners

[0020] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments in the following description are only examples, and those skilled in the art can think of other obvious variations.

[0021] Example 1

[0022] A demulsifier, by weight, is composed of the following components: 58.5 parts of polyacrylamide, 3.5 parts of cationic organosilicon-modified polyacrylamide, 14.5 parts of polyethylene oxide, 0.2 part of ammonium sulfate, 0.1 part of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, 1 part of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.3 part of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.1 part of water-soluble hyperbranched polyamide resin, 0.8 part of lauryl hydroxyethyl imidazoline, 0.6 part of amphoteric organic ion salt, and 80 parts of water.

[0023] The M of the polyacrylamide n = 12 million g / mol, M W / M n = 1.428; the cationic organosilicon-modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B; the M of the polyethylene oxide n = 1.2 million g / mol, M W / M n = 1.317; for the preparation method of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and characterization of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344 - 345.

[0024] The water-soluble hyperbranched polyamide resin is hyperbranched polyamide resin Hyper HPN202 provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; the amphoteric organic ion salt is 1-benzylpyridinium-3-carboxylate.

[0025] A preparation method of the demulsifier includes the following steps: mixing the components evenly by weight, and then stirring at 35 °C for 35 minutes, while stirring and cooling to room temperature to obtain the demulsifier.

[0026] Example 2

[0027] A demulsifier, calculated by weight parts, is composed of the following components: 61.5 parts of polyacrylamide, 4.5 parts of cationic organosilicon modified polyacrylamide, 17.5 parts of polyethylene oxide, 0.8 part of ammonium sulfate, 0.2 part of Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 1.5 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.4 part of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.15 part of water-soluble hyperbranched polyamide resin, 0.9 part of lauryl hydroxyethyl imidazoline, 0.7 part of amphoteric organic ion salt, and 85 parts of water.

[0028] The M of the polyacrylamide n = 12 million g / mol, M W / M n = 1.428; the cationic organosilicon modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B; the M of the polyethylene oxide n = 1.2 million g / mol, M W / M n = 1.317; for the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344-345.

[0029] The water-soluble hyperbranched polyamide resin is Hyper HPN202 hyperbranched polyamide resin, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; the amphoteric organic ion salt is hydroxypropane sulfonic acid pyridine salt.

[0030] A preparation method of the demulsifier includes the following steps: mixing the components evenly by weight parts, and then stirring at 37°C for 40 minutes, while stirring, cooling to room temperature to obtain the demulsifier.

[0031] Example 3

[0032] A demulsifier, calculated by weight parts, is composed of the following components: 69.5 parts of polyacrylamide, 5 parts of cationic organosilicon modified polyacrylamide, 25.5 parts of polyethylene oxide, 1.2 parts of ammonium sulfate, 0.35 part of Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 2 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.5 part of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.2 part of water-soluble hyperbranched polyamide resin, 1 part of lauryl hydroxyethyl imidazoline, 0.8 part of amphoteric organic ion salt, and 90 parts of water.

[0033] The M of the polyacrylamide n = 12 million g / mol, M W / M n = 1.428; The cationic organosilicon-modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B; The M of the polyethylene oxide n = 1.2 million g / mol, M W / M n = 1.317; For the preparation method of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344-345.

[0034] The water-soluble hyperbranched polyamide resin is Hyper HPN202 hyperbranched polyamide resin, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; The zwitterionic organic salt is 1-benzylpyridinium-3-carboxylate.

[0035] A preparation method of the demulsifier includes the following steps: Mix the components evenly by weight, and then stir at 38 °C for 45 minutes, while stirring, cool to room temperature to obtain the demulsifier.

[0036] Example 4

[0037] A demulsifier, by weight, consists of the following components: 58.5-79.5 parts of polyacrylamide, 6 parts of cationic organosilicon-modified polyacrylamide, 35 parts of polyethylene oxide, 1.7 parts of ammonium sulfate, 0.4 part of Meso-tetramethyl-meso-tetra(p-aminophenyl)calix[4]pyrrole, 2.5 parts of 1,3-bis((tris(hydroxymethyl)methylamino)propane), 0.7 part of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.25 part of water-soluble hyperbranched polyamide resin, 1.1 parts of lauryldihydroxyethylimidazoline, 0.9 part of zwitterionic organic salt, and 95 parts of water.

[0038] The M of the polyacrylamide n = 12 million g / mol, M W / M n = 1.428; The cationic organosilicon-modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B; The M of the polyethylene oxide n = 1.2 million g / mol, M W / M n= 1.317; For the preparation method of Meso - tetramethyl - meso - tetra - p - aminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso - tetramethyl - meso - tetra - p - aminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344 - 345.

[0039] The water - soluble hyperbranched polyamide resin is hyperbranched polyamide resin Hyper HPN202, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; The zwitterionic organic salt is composed of 1 - benzylpyridinium - 3 - carboxylate and pyridinium hydroxypropylsulfonate mixed in a mass ratio of 1:3.

[0040] A preparation method of the demulsifier includes the following steps: Mix the components evenly by weight, then stir at 39 °C for 53 minutes, and cool to room temperature while stirring to obtain the demulsifier.

[0041] Example 5

[0042] A demulsifier, by weight, consists of the following components: 79.5 parts of polyacrylamide, 6.5 parts of cationic organosilicon - modified polyacrylamide, 35.5 parts of polyethylene oxide, 1.8 parts of ammonium sulfate, 0.5 part of Meso - tetramethyl - meso - tetra - p - aminophenylcalix[4]pyrrole, 3 parts of 1,3 - bis((tris(hydroxymethyl)methylamino)propane), 0.8 part of 1,3 - bis(2 - hydroxyethyl)-2 - imidazolidinone, 0.3 part of water - soluble hyperbranched polyamide resin, 1.2 parts of lauryldihydroxyethylimidazoline, 1 part of zwitterionic organic salt, and 100 parts of water.

[0043] The M of the polyacrylamide n = 12 million g / mol, M W / M n = 1.428; The cationic organosilicon - modified polyacrylamide is prepared by the method of Example 1 of the Chinese invention patent with the authorization announcement number CN102649830B; The M of the polyethylene oxide n = 1.2 million g / mol, M W / M n = 1.317; For the preparation method of Meso - tetramethyl - meso - tetra - p - aminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso - tetramethyl - meso - tetra - p - aminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6): 344 - 345.

[0044] The water - soluble hyperbranched polyamide resin is hyperbranched polyamide resin Hyper HPN202, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; The zwitterionic organic salt is 1 - benzylpyridinium - 3 - carboxylate.

[0045] A preparation method of the demulsifier comprises the following steps: Mix the components evenly by weight, then stir at 40 °C for 55 minutes, and cool to room temperature while stirring to obtain the demulsifier.

[0046] Comparative Example 1

[0047] A demulsifier is basically the same as that in Example 1, except that Meso-tetramethyl-meso-tetra(4-aminophenyl)calix[4]pyrrole and 1,3-bis(2-hydroxyethyl)-2-imidazolidinone are not added.

[0048] Comparative Example 2

[0049] A demulsifier is basically the same as that in Example 1, except that an equal amount of polyacrylamide is used to replace cationic organosilicon modified polyacrylamide, and lauryl hydroxyethyl imidazoline and zwitterionic organic salt are not added.

[0050] To further illustrate the beneficial technical effects of the demulsifiers involved in the embodiments of the present invention, relevant performance tests were carried out on the demulsifiers involved in Examples 1-5 and Comparative Examples 1-2. The test results are shown in Table 1, and the test method is as follows: The experimental wastewater is the wastewater from a certain coal coking plant. The dosage of the demulsifier is 500 mL / m 3 (wastewater). Mix well and let stand for 30 min. Then take the supernatant to analyze the water sample after demulsification. The water quality indexes of the wastewater from a certain coal coking plant before demulsification are as follows: oil 30.03 mg / L, CODcr 630.22 mg / L, NH3-N 160.12 mg / L, suspended solids 280.57 mg / L, turbidity 920.45 TU; The oil removal rate, CODcr removal rate, NH3-N removal rate, suspended solids removal rate and turbidity removal rate are statistically calculated.

[0051] As can be seen from Table 1, the demulsifiers involved in the embodiments of the present invention have more excellent demulsification effects than the products in the comparative examples. The addition of Meso-tetramethyl-meso-tetra(4-aminophenyl)calix[4]pyrrole, 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, lauryl hydroxyethyl imidazoline, zwitterionic organic salt and cationic organosilicon modified polyacrylamide is beneficial to improving the above performances.

[0052] Table 1

[0053]

[0054] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. It should not be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A demulsifier, characterized in that: The invention is composed of the following components in parts by weight: 58.5-79.5 parts of polyacrylamide, 3.5-6.5 parts of cationic silicone modified polyacrylamide, 14.5-35.5 parts of polyethylene oxide, 0.2-1.8 parts of ammonium sulfate, 0.1-0.5 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole, 1-3 parts of 1,3-bis((trihydroxymethyl)methylamino)propane, 0.3-0.8 parts of 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 0.1-0.3 parts of water-soluble hyperbranched polyamide resin, 0.8-1.2 parts of lauryl hydroxyethyl imidazoline, 0.6-1 parts of amphoteric organic ion salt and 80-100 parts of water.

2. The demulsifier according to claim 1, characterized in that The M of the polyacrylamide n =12 million g / mol, M W / M n =1.

428.

3. The demulsifier according to claim 1, characterized in that The M of the polyethylene oxide n =1.2 million g / mol, M W / M n =1.

317.

4. The demulsifier according to claim 1, characterized in that The water-soluble hyperbranched polyamide resin is a hyperbranched polyamide resin Hyper HPN202.

5. The demulsifier according to claim 1, characterized in that The amphoteric organic ion salt is at least one of 1-benzylpyridine-3-carboxylate and hydroxypropanesulfonic acid pyridinium salt.

6. A method for preparing the demulsifier according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: uniformly mixing the components according to weight, stirring at 35-40 DEG C for 35-55 minutes, and cooling to room temperature while stirring to obtain a demulsifier.

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