Demulsifier

Abstract

The invention discloses a demulsifier, and relates to the technical field of wastewater treatment, and the demulsifier comprises the following components in parts by weight: 58.5-79.5 parts of polyacrylamide, 3.5-6.5 parts of cationic organosilicon modified polyacrylamide, 14.5-35.5 parts of polyoxyethylene, 0.2-1.8 parts of ammonium sulfate, 0.1-0.5 part of Meso-tetramethyl-meso-tetra-p-aminophenyl calix [4] pyrrole, 1-3 parts of 1, 3-bis ((trihydroxymethyl) methylamino) propane, 1-3 parts of 1, 3-bis (trihydroxymethyl) methylamino) propane, 0.1-0.5 part of 1, 2, 3, 4-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5 The invention relates to a water-soluble hyperbranched polyamide resin paint, which is prepared from the following components in parts by weight: 0.3 to 0.8 part of 2, 3-bis (2-hydroxyethyl)-2-imidazolone, 0.1 to 0.3 part of water-soluble hyperbranched polyamide resin, 0.8 to 1.2 parts of lauryl hydroxyethyl imidazoline, 0.6 to 1 part of amphoteric organic ionic salt and 80 to 100 parts of water. The demulsifier is small in dosage, remarkable in normal-temperature demulsification effect, high in efficiency, wide in application range and capable of effectively achieving oil removal and demulsification of the coking wastewater.

Description

Technical Field

[0001] The invention relates to the technical field of wastewater treatment, in particular 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, which is produced during the high-temperature distillation, purification, and by-product recovery of coking and coal gas. It is a kind of industrial organic wastewater with high CODcr, high phenol value, high ammonia nitrogen, and is difficult to treat. Coking wastewater treatment is an important environmental challenge faced by industries such as coking and coal chemical industry.

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

[0004] As an effective chemical agent, tar demulsifier has good dispersibility, interfacial activity, compatibility and effectiveness. It can quickly destroy the surface tension between tar particles in the emulsion suspension, separate them into small particles, and facilitate subsequent treatment and removal. At the same time, tar demulsifier also has a viscosity reduction function, which can appropriately reduce the surface tension of tar and accelerate the separation of tar and tar residue to obtain tar with lower water content and residue; it has significant advantages in improving the efficiency of coking wastewater treatment and reducing treatment costs. However, the existing tar demulsifiers have more or less technical defects such as small scope of application, large dosage, unsatisfactory demulsification effect at room temperature, high investment cost, long demulsification time, and instability of the active substances in the demulsifier, which makes it unable to fully play its role.

[0005] In order to solve the above problems, the Chinese invention patent with the authorization announcement number CN106495241B discloses an oil displacement demulsifier for coking wastewater treatment, which contains the following components in volume percentage: 20% to 50% dodecyl dimethyl benzyl ammonium chloride, 10% to 30% tetradecyl dimethyl benzyl ammonium chloride, 0.1% to 0.5% cationic polyacrylamide, 0.1% to 0.3% polysiloxane emulsion and water balance. The invention also discloses the preparation process and use of the oil displacement demulsifier. The oil displacement demulsifier of the invention has a simple formula, and the components achieve synergistic synergy, which can effectively remove oil, ammonia nitrogen, CODcr and suspended matter in coking wastewater. However, its scope of application is limited, and the demulsification effect still needs to be further improved.

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

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

[0008] To achieve the above object, the technical solution adopted by the present invention is: a demulsifier, which 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-tetraaminophenyl 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.

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

[0010] Preferably, there is no special requirement for the source of the cationic silicone-modified polyacrylamide. In one embodiment of the present invention, the cationic silicone-modified polyacrylamide is prepared according to the method of Example 1 of the Chinese invention patent with authorization announcement number CN102649830B.

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

[0012] Preferably, the preparation method of the meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

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

[0014] Preferably, the amphoteric organic ion salt is at least one of 1-benzylpyridine-3-carboxylate and hydroxypropanesulfonic acid pyridinium salt.

[0015] Another object of the present invention is to provide a method for preparing the demulsifier, comprising the steps of: uniformly mixing the components by weight, stirring at 35 to 40° C. for 35 to 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 simple process, convenient operation, no need for special equipment, high preparation efficiency and finished product qualification rate, low labor intensity, small impact on the environment, high cost performance, and is suitable for industrial production.

[0018] (2) The demulsifier disclosed in the present invention is composed of the following components, 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-tetraaminophenylcalix[4]pyrrole, 1-3 parts of 1,3-bis((trihydroxymethyl)methylamino)propane, 1 , 0.3-0.8 parts of 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; through the mutual coordination and joint action of the components, the demulsifier product is produced with a small dosage, significant demulsification effect at room temperature, high efficiency, a wide range of applications, and can effectively achieve oil removal and demulsification of coking wastewater.

[0019] (3) The demulsifier disclosed in the present invention has good interfacial activity and permeability through the reasonable selection of component types and dosage ratios, can quickly reach the oil-water interface, form an unstable oil-water interface film, and has good demulsification performance for coking wastewater. DETAILED DESCRIPTION

[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 described below are only examples, and those skilled in the art may think of other obvious variations.

[0021] Example 1

[0022] A demulsifier is composed of the following components, measured by weight: 58.5 parts of polyacrylamide, 3.5 parts of cationic silicone-modified polyacrylamide, 14.5 parts of polyethylene oxide, 0.2 parts of ammonium sulfate, 0.1 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 1 part of 1,3-bis ((trihydroxymethyl) methylamino) propane, 0.3 parts of 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, 0.1 parts of water-soluble hyperbranched polyamide resin, 0.8 parts of lauryl hydroxyethyl imidazoline, 0.6 parts 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 silicone modified polyacrylamide is prepared according to 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-tetraaminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

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

[0025] A method for preparing the demulsifier comprises the following steps: uniformly mixing the components by weight, stirring at 35° C. for 35 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0026] Example 2

[0027] A demulsifier is composed of the following components, measured by weight: 61.5 parts of polyacrylamide, 4.5 parts of cationic silicone-modified polyacrylamide, 17.5 parts of polyethylene oxide, 0.8 parts of ammonium sulfate, 0.2 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 1.5 parts of 1,3-bis ((trihydroxymethyl) methylamino) propane, 0.4 parts of 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, 0.15 parts of water-soluble hyperbranched polyamide resin, 0.9 parts of lauryl hydroxyethyl imidazoline, 0.7 parts 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 silicone modified polyacrylamide is prepared according to 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-tetraaminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

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

[0030] A method for preparing the demulsifier comprises the following steps: uniformly mixing the components by weight, stirring at 37° C. for 40 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0031] Example 3

[0032] A demulsifier is composed of the following components, measured by weight: 69.5 parts of polyacrylamide, 5 parts of cationic silicone-modified polyacrylamide, 25.5 parts of polyethylene oxide, 1.2 parts of ammonium sulfate, 0.35 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 2 parts of 1,3-bis ((trihydroxymethyl) methylamino) propane, 0.5 parts of 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, 0.2 parts of water-soluble hyperbranched polyamide resin, 1 part of lauryl hydroxyethyl imidazoline, 0.8 parts 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 silicone modified polyacrylamide is prepared according to 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-tetraaminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

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

[0035] A method for preparing the demulsifier comprises the following steps: uniformly mixing the components by weight, stirring at 38° C. for 45 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0036] Example 4

[0037] A demulsifier is composed of the following components, measured by weight: 58.5-79.5 parts of polyacrylamide, 6 parts of cationic silicone-modified polyacrylamide, 35 parts of polyethylene oxide, 1.7 parts of ammonium sulfate, 0.4 parts of meso-tetramethyl-meso-tetraaminophenyl cup [4] pyrrole, 2.5 parts of 1,3-bis ((trihydroxymethyl) methylamino) propane, 0.7 parts of 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, 0.25 parts of water-soluble hyperbranched polyamide resin, 1.1 parts of lauryl hydroxyethyl imidazoline, 0.9 parts of amphoteric organic ion 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 silicone modified polyacrylamide is prepared according to 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-tetraaminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

[0039] The water-soluble hyperbranched polyamide resin is a hyperbranched polyamide resin Hyper HPN202, provided by Wuhan Hyperbranched Resin Technology Co., Ltd.; the amphoteric organic ion salt is a mixture of 1-benzylpyridine-3-carboxylate and hydroxypropane sulfonic acid pyridinium salt in a mass ratio of 1:3.

[0040] A method for preparing the demulsifier comprises the following steps: uniformly mixing the components by weight, stirring at 39° C. for 53 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0041] Example 5

[0042] A demulsifier is composed of the following components, measured by weight: 79.5 parts of polyacrylamide, 6.5 parts of cationic silicone-modified polyacrylamide, 35.5 parts of polyethylene oxide, 1.8 parts of ammonium sulfate, 0.5 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole, 3 parts of 1,3-bis ((trihydroxymethyl) methylamino) propane, 0.8 parts of 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, 0.3 parts of water-soluble hyperbranched polyamide resin, 1.2 parts of lauryl hydroxyethyl imidazoline, 1 part of amphoteric organic ion 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 silicone modified polyacrylamide is prepared according to 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-tetraaminophenylcalix[4]pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetraaminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345.

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

[0045] A method for preparing the demulsifier comprises the following steps: uniformly mixing the components by weight, stirring at 40° C. for 55 minutes, and cooling to room temperature while stirring to obtain the demulsifier.

[0046] Comparative Example 1

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

[0048] Comparative Example 2

[0049] A demulsifier is substantially the same as Example 1, except that an equal amount of polyacrylamide is used to replace the cationic silicone-modified polyacrylamide, and lauryl hydroxyethyl imidazoline and amphoteric organic ion salt are not added.

[0050] In order to further illustrate the beneficial technical effects of the demulsifiers involved in each embodiment of the present invention, the demulsifiers involved in Examples 1-5 and Comparative Examples 1-2 were tested for relevant performances. The test results are shown in Table 1. The test method is as follows: the wastewater used in the experiment is wastewater from a coal coking plant, and the dosage of the demulsifier is 500 mL / m 3 (wastewater), mix well, let stand for 30 minutes, take the supernatant and analyze the water samples after demulsification. The water quality indicators of a coal coking plant wastewater before demulsification are as follows: oil 30.03mg / L, CODcr 630.22mg / L, NH 3 -N 160.12mg / L, suspended solids 280.57mg / L, turbidity 920.45TU; statistics and calculation of oil removal rate, CODcr removal rate, NH 3 -N removal rate, suspended solids removal rate and turbidity removal rate.

[0051] As can be seen from Table 1, the demulsifier involved in the embodiment of the present invention has a better demulsification effect than the comparative example product. The addition of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole, 1,3-bis (2-hydroxyethyl) -2-imidazolidinone, lauryl hydroxyethyl imidazoline, amphoteric organic ion salt and cationic silicone modified polyacrylamide is beneficial to improving the above performance.

[0052] Table 1

[0053]

[0054] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in 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, cooling to room temperature while stirring, and obtaining a demulsifier.

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