A kind of high-efficiency oil and wax removal agent and preparation method thereof

Abstract

The present application relates to the field of water treatment, and in particular to a highly efficient degreasing and dewaxing agent and a preparation method thereof. The highly efficient degreasing and dewaxing agent, in terms of mass percentage, comprises the following raw materials: 10-12% alkaline auxiliary agent, 20-35% surfactant, 2-4% dispersant, 6-10% solubilizer, 5-10% modified polymer, 3.5-6% functional particles, and the balance is supplemented by deionized water. The highly efficient degreasing and dewaxing agent prepared by the present application not only has excellent degreasing and dewaxing effects on industrial oily wastewater, but also can ensure its own excellent stability during use and storage. On the other hand, it has strong adaptability to oily wastewater, can effectively meet the oil removal needs of industrial oily wastewater from various sources and different properties, and has very excellent application and market prospects.

Description

Technical Field

[0001] The present application relates to the field of water treatment, and in particular to a highly efficient oil and wax removal agent and a preparation method thereof. Background Art

[0002] The treatment of oily wastewater is an important part of environmental protection and resource recovery, especially in the fields of oil extraction, refining, mechanical processing and daily sewage discharge. This type of wastewater contains a large amount of suspended or dissolved oil, which not only affects the water quality, but also may cause serious damage to the ecosystem, so the treatment technology of oily wastewater is particularly important.

[0003] In the oily wastewater treatment technology, oil and wax removal agents play a key role. Traditionally, oil and wax removal agents mainly include surfactants, emulsifiers, flocculants, etc., which separate oil and water through chemical reactions. With the advancement of technology, more targeted designs have emerged, such as special oil and wax removal agents for specific types of oil pollution (such as heavy oil, light oil) and different water quality conditions (such as high temperature, high salt environment), and high-efficiency oil and wax removal agents containing more oil removal raw materials (such as adsorbent materials, degradation materials). For example, some patented technologies mention temperature-resistant and high-efficiency oil and wax removal agents, which improve oil removal efficiency through special formulas and can maintain the effect over a wide temperature range. In addition to the usual surfactants, solubilizers and corrosion inhibitors, these oil and wax removal agents also include specific adsorbents or degradation materials to achieve the purpose of rapid penetration, decomposition, degradation, adsorption and stripping of oil pollution.

[0004] The existing traditional oil and wax removal agents have unsatisfactory oil removal efficiency when facing heavy oil pollution or complex oil-water systems, especially acidic oil and wax removal agents are even worse when the oil pollution is heavy and cannot completely remove the oil pollution; on the other hand, the oil and wax removal agents themselves are limited by the compatibility of their own systems and other problems, and are prone to stratification, flocculation, precipitation and hydration during use and storage, which reduces the stability of the oil and wax removal agents and increases the cost of use and storage; finally, in the face of oily wastewater from different sources and properties, a single oil and wax removal agent is often difficult to be widely used, and it is necessary to adjust the formula or replace the oil and wax removal agent according to the specific situation. In order to solve the above problems, the present application provides a high-efficiency oil and wax removal agent and a preparation method thereof. The high-efficiency oil and wax removal agent prepared in the present application not only has excellent oil and wax removal effects for industrial oily wastewater, but also can ensure its own excellent stability during use and storage. On the other hand, it has strong adaptability to oily wastewater and can effectively meet the oil removal needs of industrial oily wastewater from multiple sources and different properties, and has very excellent application and market prospects. Summary of the invention

[0005] In order to solve the above problems, the first aspect of the present application provides a high-efficiency oil and wax removal agent. The raw materials include, by mass percentage: 10-12% alkaline auxiliary agent, 20-35% surfactant, 2-4% dispersant, 6-10% solubilizer, 5-10% modified polymer, 3.5-6% functional particles, and deionized water to make up the balance.

[0006] As a preferred solution, the mass ratio of the surfactant, the modified polymer and the functional particles is (24-30): (6-9): (4.2-5).

[0007] As a preferred solution, the mass ratio of the surfactant, the modified polymer and the functional particles is (25-28): (7-8): (4.2-4.5).

[0008] As a preferred solution, the alkaline auxiliary agent is at least one of sodium hydroxide, sodium carbonate, sodium silicate, sodium tripolyphosphate, sodium metasilicate, and trisodium phosphate.

[0009] As a preferred solution, the alkaline auxiliary agent is a combination of sodium carbonate, sodium silicate and sodium tripolyphosphate.

[0010] As a preferred solution, the mass ratio of sodium carbonate, sodium silicate and sodium tripolyphosphate is (4-6): (2-3): (0.5-1.5).

[0011] As a preferred solution, the mass ratio of sodium carbonate, sodium silicate and sodium tripolyphosphate is (4.5-5): (2-2.5): (0.8-1.2).

[0012] As a preferred solution, the surfactant is a composition of isomeric C13-15 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether.

[0013] As a preferred solution, the mass ratio of the isomeric C13-15 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether is (3-4): (1.5-2.5): (0.8-1.4).

[0014] As a preferred solution, the mass ratio of the isomeric C13-15 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether is (3.2-3.6): (1.5-2): (0.8-1.2).

[0015] As a preferred solution, the hydroxyl value of the isomeric C13-15 fatty alcohol polyoxyethylene ether is 60-140 mgKOH / g.

[0016] As a preferred solution, the hydroxyl value of the isomeric C13-15 fatty alcohol polyoxyethylene ether is 80-120 mgKOH / g.

[0017] As a preferred solution, the HLB value of the trimethylstyrene phenol polyoxyethylene ether is 12-18.

[0018] As a preferred solution, the HLB value of the trimethylstyrene phenol polyoxyethylene ether is 14.5-16.

[0019] As a preferred solution, the weight average molecular weight of the epoxy block polyether is 1000-5000.

[0020] As a preferred solution, the epoxy block polyether is a composition of an epoxy block polyether with a weight average molecular weight of 1000-2000 and an epoxy block polyether with a weight average molecular weight of 4000-4400.

[0021] As a preferred solution, the mass ratio of the epoxy block polyether with a weight average molecular weight of 1000-2000 to the epoxy block polyether with a weight average molecular weight of 4000-4400 is (3-4): (1-1.2).

[0022] As a preferred solution, the mass ratio of the epoxy block polyether with a weight average molecular weight of 1000-2000 to the epoxy block polyether with a weight average molecular weight of 4000-4400 is (3.4-3.5): (1.1-1.15).

[0023] The above-mentioned compound surfactant added in the present application can not only play an excellent auxiliary effect in oil removal and wax removal, but also greatly improve the stability of the oil removal and wax removal agent itself and its adaptability to oily wastewater. The combination of the added specific fatty alcohol polyoxyethylene ether, arylphenol polyoxyethylene ether and epoxy block polyether can form a laminated protective interface film structure with good order in the oil removal and wax removal agent system by utilizing the rigid structure of arylphenol polyoxyethylene ether and the hydrogen bonding of fatty alcohol polyoxyethylene ether, thereby arranging the active molecules and active particles in the oil removal and wax removal agent in an orderly manner in different regions in the system, avoiding excessive collision and contact between regions due to molecular activity, reducing the contact probability, and thus greatly reducing the probability of differentiation, flocculation, agglomeration and precipitation during use and storage; on the other hand, when used, the above-mentioned compound surfactant can enhance the guiding and dispersing effect of the functional particles in the present application on the water body, can play a certain role as a dispersing carrier in the initial stage, and can be used as a carrying phase of the functional particles after oil removal and wax removal, adding the precipitation of the functional particles, and reducing the content of impurities in the treated water.

[0024] As a preferred solution, the dispersant is at least one of sodium pyrophosphate, polymerized organic ester, polycarboxylate, polyacrylic acid, and polyquaternary ammonium salt.

[0025] As a preferred solution, the dispersant is sodium pyrophosphate.

[0026] As a preferred solution, the solubilizer is at least one of short-chain alcohol, polyethylene glycol, povidone, alkyl phosphate, and hydrogenated castor oil.

[0027] As a preferred solution, the solubilizer is a combination of polyethylene glycol and hydrogenated castor oil.

[0028] As a preferred solution, the mass ratio of the polyethylene glycol to hydrogenated castor oil is (3-4): (0.5-1).

[0029] As a preferred solution, the preparation method of the modified polymer comprises the following steps: S1: adding ethyl acrylate, hydroxyethyl acrylate and glycidyl acrylate to an organic solution, introducing nitrogen, adding an initiator, heating to 60-80°C for reaction for 3-5 hours to generate a pre-product solution; S2: adding acrylamide, deionized water and an initiator to the pre-product solution, and after nitrogen fully replaces the reaction system gas, heating to 65-75°C for reaction for 4-8 hours; S3: after the reaction is completed, adding succinic anhydride and 3-aminopropyltriethoxysilane, maintaining the temperature at 55-65°C for reaction for 2-3 hours, and adding acetone and deionized water in turn for cleaning, and vacuum drying to obtain the product.

[0030] As a preferred solution, the mass ratio of ethyl acrylate, hydroxyethyl acrylate, glycidyl acrylate and acrylamide is (6-9):(4-5):(0.5-1):(30-35).

[0031] As a preferred solution, the mass ratio of ethyl acrylate, hydroxyethyl acrylate, glycidyl acrylate and acrylamide is (7-8.5):(4-4.5):(0.6-0.8):(32-33).

[0032] As a preferred solution, the initiator is ammonium persulfate or potassium persulfate.

[0033] The modified polymer added in the present application can greatly improve the degreasing and dewaxing effect of the degreasing and dewaxing agent, as well as its own stability, and ensure a lower particle content in the water after degreasing and dewaxing. The modified polymer prepared in the present application can use its long molecular chain to guide the orderly dispersion of functional particles in the degreasing and dewaxing agent system, and can form a good internal connection network system of the degreasing and dewaxing agent with the compound surfactant, under which the excessive movement of raw material molecules or particles can be effectively restricted and the movement efficiency can be reduced, so that it still has excellent stability under the storage environment; on the other hand, after the degreasing and dewaxing agent is used, its long-chain molecules can still form a guiding effect on the particles in the water body through good hydrophilicity, thereby strengthening the precipitation effect of solid particles (including functional particles) in the water body, and then the degreasing and dewaxing agent obtains excellent self-stability and a lower particle content after water treatment.

[0034] As a preferred solution, the functional particles are composite structure particles.

[0035] As a preferred scheme, the preparation method of the composite structure particles includes the following steps: S1: adding zinc oxide, succinic anhydride and 3-aminopropyltriethoxysilane to deionized water, heating to 60-65°C and keeping warm for 2-3 hours; S2: adding activated carbon powder, cooling to 50-55°C, stirring and reacting with 200-300W ultrasonic vibration for 2-4 hours, and after completion, centrifuging, filtering, washing and drying the product.

[0036] As a preferred solution, the mass ratio of zinc oxide, succinic anhydride and 3-aminopropyltriethoxysilane is (1-1.5): (1-1.2): (0.2-0.3).

[0037] As a preferred solution, the mass ratio of zinc oxide to activated carbon powder is (1-1.5):(3.8-4.5).

[0038] As a preferred solution, the specific surface area of ​​the activated carbon powder is 2200-2400m 2 / g.

[0039] The second aspect of the present application provides a method for preparing the above-mentioned high-efficiency oil and wax removal agent, and the preparation method comprises the following steps: S1: stirring and pre-mixing the functional particles and the modified polymer in a container; S2: after the pre-mixing is completed, the pre-mixture and the alkaline auxiliary agent, the surfactant, the dispersant, and the solubilizer are sequentially added into a small amount of deionized water, and stirred evenly to ensure that there is no agglomeration; S3: slowly adding the remaining deionized water into the container, accompanied by stirring at a speed of 60 to 100 rpm, and continuing stirring until it is completely uniform.

[0040] The beneficial effects of this application are:

[0041] 1. The present application provides a highly efficient oil and wax removal agent, which not only has excellent oil and wax removal effects on industrial oily wastewater, but also can ensure its own excellent stability during use and storage. On the other hand, it has strong adaptability to oily wastewater and can effectively meet the oil removal needs of industrial oily wastewater from various sources and different properties, and has very excellent application and market prospects.

[0042] 2. The highly efficient degreasing and dewaxing agent provided in the present application can not only play an excellent degreasing and dewaxing assisting effect by adding a compound surfactant, but also can greatly improve the stability of the degreasing and dewaxing agent itself and its adaptability to oily wastewater. The combination of the added specific fatty alcohol polyoxyethylene ether, aromatic phenol polyoxyethylene ether and epoxy block polyether can utilize the rigid structure of aromatic phenol polyoxyethylene ether and the hydrogen bonding of fatty alcohol polyoxyethylene ether to form a laminated protective interface film structure with good order in the degreasing and dewaxing agent system, thereby arranging the active molecules and active particles in the degreasing and dewaxing agent in an orderly manner in different regions in the system, avoiding excessive collision and contact between regions due to molecular activity, reducing the contact probability, and thus greatly reducing the probability of differentiation, flocculation, agglomeration and precipitation during use and storage.

[0043] 3. The high-efficiency oil and wax removal agent provided in the present application, the combination of the added specific fatty alcohol polyoxyethylene ether, aromatic phenol polyoxyethylene ether and epoxy block polyether can enhance the guiding and dispersing effect of the functional particles in the present application on the water body, can play a certain role as a dispersing carrier in the initial stage, and can serve as a carrying phase for the functional particles after oil and wax removal, adding the precipitate of the functional particles to reduce the content of impurities in the treated water.

[0044] 4. The present application provides a highly efficient degreasing and dewaxing agent, in which the added modified polymer can greatly improve the degreasing and dewaxing effect of the degreasing and dewaxing agent, as well as its own stability, and ensure a lower particle content in the water after degreasing and dewaxing; the modified polymer can use its long molecular chain to guide the orderly dispersion of functional particles in the degreasing and dewaxing agent system, and can form a good internal connection network system of the degreasing and dewaxing agent with the compound surfactant, under which the excessive movement of raw material molecules or particles can be effectively restricted and the movement efficiency can be reduced, so that it still has excellent stability under storage conditions; on the other hand, after the degreasing and dewaxing agent is used, its long-chain molecules can still form a guiding effect on the particles in the water body through good hydrophilicity, thereby enhancing the precipitation effect of solid particles (including functional particles) in the water body, thereby enabling the degreasing and dewaxing agent to obtain excellent self-stability and a lower particle content after water treatment. DETAILED DESCRIPTION

[0045] The following will further explain and demonstrate the technical solutions in the above invention content of this application in the form of specific implementation schemes. The following embodiments are only practical examples used to illustrate and explain the contents of the technical solutions in the specification, and should not limit the scope of the claims to be protected by this application. All technical products based on the technical solutions described in the invention content of this application should be included in the scope to be protected by this application.

[0046] In the following examples, unless otherwise specified, the raw materials are all commercially available products, or can be prepared by methods well known to those skilled in the art.

[0047] Example 1

[0048] Example 1 The first aspect provides a high-efficiency oil and wax removal agent, in which the raw materials include, by mass percentage: 10.8% alkaline auxiliary agent, 27.8% surfactant, 3.2% dispersant, 8.5% solubilizer, 7.6% modified polymer, 4.4% functional particles, and deionized water to make up the balance.

[0049] The alkaline auxiliary agent is a composition of sodium carbonate, sodium silicate and sodium tripolyphosphate, and the mass ratio of the three is 4.8:2.2:1.

[0050] The surfactant is a composition of isomeric C13 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether, and the mass ratio of the three is 3.5:1.6:0.8.

[0051] The hydroxyl value of isomeric C13 fatty alcohol polyoxyethylene ether is 100 mgKOH / g, and it was purchased from the E-1308 model product sold by Haian Guoyun Chemical.

[0052] The trimethylstyrenephenol polyoxyethylene ether has an HLB value of 15.5 and is purchased from LEVACO as a product of model LUCRAMUL PMS29.

[0053] The epoxy block polyether is a composition of BASF L31 epoxy block polyether (weight average molecular weight 1100) and BASF L84 epoxy block polyether (weight average molecular weight 4200), and the mass ratio of the two is 3.4:1.1.

[0054] The dispersant is sodium pyrophosphate; the solubilizer is a combination of polyethylene glycol (PEG400) and hydrogenated castor oil, with a mass ratio of 3.2:0.8; the hydrogenated castor oil is a premium product purchased from Jiangsu Nantong Rongsheng New Material Technology Co., Ltd.

[0055] The preparation method of the modified polymer comprises the following steps, calculated by mass: S1: adding 7.8 parts of ethyl acrylate, 4.2 parts of hydroxyethyl acrylate and 0.75 parts of glycidyl acrylate to an acryloyl chloride solution, introducing nitrogen, adding 0.08 parts of potassium persulfate, heating to 75°C for reaction for 4 hours to generate a pre-product solution; S2: adding 32 parts of acrylamide, 150 parts of deionized water and 0.18 parts of potassium persulfate to the pre-product solution, fully replacing the reaction system gas with nitrogen, heating to 70°C for reaction for 6 hours; S3: adding 3.5 parts of succinic anhydride and 1.1 parts of 3-aminopropyltriethoxysilane after the reaction is completed, maintaining the temperature at 60°C for reaction for 2.5 hours, and adding acetone and deionized water in turn after completion to clean, and vacuum drying to obtain the product.

[0056] The functional particles are composite structure particles; the preparation method of the composite structure particles includes the following steps, calculated by mass: S1: adding 1.2 parts of zinc oxide, 1 part of succinic anhydride and 0.22 parts of 3-aminopropyltriethoxysilane to 60 parts of deionized water, heating to 60°C and keeping warm for 3 hours; S2: adding 4.1 parts of activated carbon powder, cooling to 55°C, stirring and reacting with 280W ultrasonic vibration for 4 hours, and after completion, centrifuging, filtering, washing and drying the product to obtain the product.

[0057] The specific surface area of ​​activated carbon powder is 2250m 2 / g, purchased from Beijing Hengying Environmental Protection Technology Co., Ltd.

[0058] The second aspect of the present embodiment provides a method for preparing the above-mentioned high-efficiency oil and wax removal agent, and the preparation method comprises the following steps: S1: stirring and pre-mixing the functional particles and the modified polymer in a container; S2: after the pre-mixing is completed, the pre-mixture and the alkaline auxiliary agent, the surfactant, the dispersant, and the solubilizer are sequentially added into a small amount of deionized water, and stirred evenly to ensure that there is no agglomeration; S3: slowly adding the remaining deionized water into the container, accompanied by stirring at a speed of 80 rpm, and continuing stirring until it is completely uniform.

[0059] Example 2

[0060] Example 2 The first aspect provides a high-efficiency oil and wax removal agent. The raw materials include, by mass percentage: 10.8% alkaline auxiliary agent, 24.8% surfactant, 3.2% dispersant, 8.5% solubilizer, 8.6% modified polymer, 4.2% functional particles, and deionized water to make up the balance.

[0061] The alkaline auxiliary agent is a composition of sodium carbonate, sodium silicate and sodium tripolyphosphate, and the mass ratio of the three is 4.5:2.5:0.8.

[0062] The surfactant is a composition of isomeric C13 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether, and the mass ratio of the three is 3.3:2:1.1.

[0063] The hydroxyl value of isomeric C13 fatty alcohol polyoxyethylene ether is 100 mgKOH / g, and it was purchased from the E-1308 model product sold by Haian Guoyun Chemical.

[0064] The trimethylstyrenephenol polyoxyethylene ether has an HLB value of 15.5 and is purchased from LEVACO as a product of model LUCRAMUL PMS29.

[0065] The epoxy block polyether is a composition of BASF L31 epoxy block polyether (weight average molecular weight 1100) and BASF L84 epoxy block polyether (weight average molecular weight 4200), and the mass ratio of the two is 3.4:1.1.

[0066] The dispersant is sodium pyrophosphate; the solubilizer is a combination of polyethylene glycol (PEG400) and hydrogenated castor oil, with a mass ratio of 3.2:0.8; the hydrogenated castor oil is a premium product purchased from Jiangsu Nantong Rongsheng New Material Technology Co., Ltd.

[0067] The preparation method of the modified polymer comprises the following steps, calculated by mass: S1: adding 7.8 parts of ethyl acrylate, 4.2 parts of hydroxyethyl acrylate and 0.75 parts of glycidyl acrylate to an acryloyl chloride solution, introducing nitrogen, adding 0.08 parts of potassium persulfate, heating to 75°C for reaction for 4 hours to generate a pre-product solution; S2: adding 32 parts of acrylamide, 150 parts of deionized water and 0.18 parts of potassium persulfate to the pre-product solution, fully replacing the reaction system gas with nitrogen, heating to 70°C for reaction for 6 hours; S3: adding 3.5 parts of succinic anhydride and 1.1 parts of 3-aminopropyltriethoxysilane after the reaction is completed, maintaining the temperature at 60°C for reaction for 2.5 hours, and adding acetone and deionized water in turn after completion to clean, and vacuum drying to obtain the product.

[0068] The functional particles are composite structure particles; the preparation method of the composite structure particles includes the following steps, calculated by mass: S1: adding 1.2 parts of zinc oxide, 1 part of succinic anhydride and 0.22 parts of 3-aminopropyltriethoxysilane to 60 parts of deionized water, heating to 60°C and keeping warm for 3 hours; S2: adding 4.1 parts of activated carbon powder, cooling to 55°C, stirring and reacting with 280W ultrasonic vibration for 4 hours, and after completion, centrifuging, filtering, washing and drying the product to obtain the product.

[0069] The specific surface area of ​​activated carbon powder is 2250m 2 / g, purchased from Beijing Hengying Environmental Protection Technology Co., Ltd.

[0070] The second aspect of the present embodiment provides a method for preparing the above-mentioned high-efficiency oil and wax removal agent, and the preparation method comprises the following steps: S1: stirring and pre-mixing the functional particles and the modified polymer in a container; S2: after the pre-mixing is completed, the pre-mixture and the alkaline auxiliary agent, the surfactant, the dispersant, and the solubilizer are sequentially added into a small amount of deionized water, and stirred evenly to ensure that there is no agglomeration; S3: slowly adding the remaining deionized water into the container, accompanied by stirring at a speed of 80 rpm, and continuing stirring until it is completely uniform.

[0071] Comparative Example 1

[0072] The specific implementation of this comparative example is basically the same as that of Example 1, except that the raw materials of the high-efficiency oil and wax removal agent, in terms of mass percentage, include: 10.8% alkaline auxiliary agent, 35.2% surfactant, 3.2% dispersant, 8.5% solubilizer, 2.2% modified polymer, 6.2% functional particles, and the balance is supplemented by deionized water.

[0073] Comparative Example 2

[0074] The specific implementation of this comparative example is basically the same as that of Example 1, except that the surfactant is a composition of isomeric C13 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether, and the mass ratio of the three is 5:0.5:0.1.

[0075] Comparative Example 3

[0076] The specific implementation method of this comparative example is basically the same as that of Example 1, except that: the hydroxyl value of the isomeric C13 fatty alcohol polyoxyethylene ether is 195 mgKOH / g, and it is purchased from the E-1302 model product sold by Hai'an Guoyun Chemical; the trimethylstyrene phenol polyoxyethylene ether is replaced by distyrylphenol polyoxyethylene ether, and the HLB value is 6.8, and it is purchased from the LUCRAMUL DSP 03 model product of LEVACO.

[0077] Comparative Example 4

[0078] The specific implementation of this comparative example is basically the same as that of Example 1, except that the epoxy block polyether is a composition of BASF L31 epoxy block polyether (weight average molecular weight 1100) and BASF L84 epoxy block polyether (weight average molecular weight 4200), and the mass ratio of the two is 1:1.5.

[0079] Comparative Example 5

[0080] The specific implementation of this comparative example is basically the same as that of Example 1, except that: the preparation method of the modified polymer comprises the following steps, calculated by mass: S1: adding 12 parts of ethyl acrylate, 1.5 parts of hydroxyethyl acrylate and 0.25 parts of glycidyl acrylate to an acryloyl chloride solution, introducing nitrogen, adding 0.08 parts of potassium persulfate, heating to 75°C for reaction for 4 hours to generate a pre-product solution; S2: adding 35 parts of acrylamide, 150 parts of deionized water and 0.18 parts of potassium persulfate to the pre-product solution, and after nitrogen fully replaces the reaction system gas, heating to 70°C for reaction for 6 hours; S3: after the reaction is completed, adding 3.5 parts of succinic anhydride and 1.1 parts of 3-aminopropyltriethoxysilane, maintaining 60°C for reaction for 2.5 hours, and adding acetone and deionized water in turn for cleaning and vacuum drying to obtain the product.

[0081] Comparative Example 6

[0082] The specific implementation of this comparative example is basically the same as that of Example 1, except that: the preparation method of the modified polymer comprises the following steps, calculated by mass: S1: adding 3.5 parts of ethyl acrylate, 10.2 parts of hydroxyethyl acrylate and 0.75 parts of glycidyl acrylate to an acryloyl chloride solution, introducing nitrogen, adding 0.08 parts of potassium persulfate, heating to 75°C for reaction for 4 hours to generate a pre-product solution; S2: adding 23.6 parts of acrylamide, 150 parts of deionized water and 0.18 parts of potassium persulfate to the pre-product solution, and heating to 70°C for reaction for 6 hours after nitrogen fully replaces the reaction system gas; S3: adding 3.5 parts of succinic anhydride and 1.1 parts of 3-aminopropyltriethoxysilane after the reaction is completed, maintaining the temperature at 60°C for reaction for 2.5 hours, and adding acetone and deionized water in turn for cleaning and vacuum drying to obtain the product.

[0083] Performance Evaluation

[0084] 1. Oil removal performance: The oil removal and wax removal agents prepared in the embodiments and comparative examples were added to oily wastewater for oil removal test. The oil content of the oily wastewater was 502.2 mg / L. The amount of oil removal and wax removal agent added was 15 mg / L. After addition, the mixture was stirred at 200 rpm for 120 s and then allowed to stand for 20 min. The lower layer of water was taken to test the oil content and the oil removal rate was obtained. The test values ​​were the average of 10 tests and recorded in Table 1.

[0085] 2. Wax removal performance: The degreasing and wax removal agents prepared in the embodiments and comparative examples were added to wax-containing wastewater for wax removal test. The wax content of the wax-containing wastewater was 282.6 mg / L. The amount of degreasing and wax removal agent added was 15 mg / L. After adding, the mixture was stirred at 200 rpm for 120 seconds and then allowed to stand for 20 minutes. The wax content of the lower layer of water was tested to obtain the wax removal rate. The test value was the average of 10 tests and recorded in Table 1.

[0086] 3. Stability test: The degreasing and dewaxing agents prepared in the examples and comparative examples were added to a constant temperature and humidity chamber at 55°C and 75% relative humidity, and kept for 48 hours. After 48 hours, the degreasing and dewaxing agents were taken out and observed to see if there were obvious stratification, flocculation, precipitation and settling. If there were, they were considered unqualified, otherwise they were qualified. Each group was tested 50 times, and the qualified rate was recorded in Table 1.

[0087] 4. Residual functional particle content: The performance test 1 was adopted to carry out the oil removal test, and after adding and stirring for 30 seconds, samples were taken from the surface area of ​​the water body to record the content of functional particles in the initial water body. After the oil removal test, samples were taken from the surface area of ​​the water body again to record the percentage of the content of functional particles after the test to the content of functional particles in the initial water body. The test value was the average value of 10 tests and recorded in Table 1.

[0088] Table 1 Performance test results

[0089]

[0090] From the examples and comparative examples of the present application and the data results in Table 1, it can be seen that the examples 1 and 2 of the present application have obvious advantages over the comparative examples 1 to 6 in terms of the degreasing and dewaxing effect, stability and residual amount of functional particles of the degreasing and dewaxing agent. However, because the comparative examples 1 to 6 did not adopt the correct limiting technical solution, there was an obvious gap in the corresponding performance test, which further proves the necessity of the limiting technical solution adopted in the examples 1 and 2 of the present application for the technical effect of the present application and solving the technical problems.

Claims

1. A highly efficient oil and wax removal agent, characterized in that: High-efficiency oil and wax removal agent, calculated by mass percentage, the raw materials include: alkaline additive 10~12%, surfactant 20~35%, dispersant 2~4%, solubilizer 6~10%, modified polymer 5~10%, functional particles 3.5~6%, and deionized water to make up the balance; The alkaline auxiliary agent is at least one of sodium hydroxide, sodium carbonate, sodium silicate, sodium tripolyphosphate, sodium metasilicate, and trisodium phosphate; The surfactant is a composition of isomeric C13-15 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether; The mass ratio of the isomeric C13-15 fatty alcohol polyoxyethylene ether, trimethylstyrene phenol polyoxyethylene ether and epoxy block polyether is (3-4): (1.5-2.5): (0.8-1.4); The hydroxyl value of the isomeric C13-15 fatty alcohol polyoxyethylene ether is 60-140 mgKOH / g; The HLB value of the trimethylstyrene phenol polyoxyethylene ether is 12 to 18; The weight average molecular weight of the epoxy block polyether is 1000-5000; The dispersant is at least one of sodium pyrophosphate, polymerized organic ester, polycarboxylate, polyacrylic acid, and polyquaternary ammonium salt; The preparation method of the modified polymer comprises the following steps: S1: adding ethyl acrylate, hydroxyethyl acrylate and glycidyl acrylate to an organic solution, introducing nitrogen, adding an initiator, heating to 60-80° C. for reaction for 3-5 hours to generate a pre-product solution; S2: adding acrylamide, deionized water and an initiator to the pre-product solution, fully replacing the gas in the reaction system with nitrogen, heating to 65-75° C. for reaction for 4-8 hours; S3: adding succinic anhydride and 3-aminopropyltriethoxysilane after the reaction is completed, maintaining the temperature at 55-65° C. for reaction for 2-3 hours, and adding acetone and deionized water in turn for cleaning, and vacuum drying to obtain the product; The mass ratio of ethyl acrylate, hydroxyethyl acrylate, glycidyl acrylate and acrylamide is (6-9):(4-5):(0.5-1):(30-35); The functional particles are composite structure particles; the preparation method of the composite structure particles comprises the following steps: S1: adding zinc oxide, succinic anhydride and 3-aminopropyltriethoxysilane to deionized water, heating to 60-65°C and keeping warm for 2-3 hours; S2: adding activated carbon powder, cooling to 50-55°C, stirring and reacting with 200-300W ultrasonic vibration for 2-4 hours, and after completion, centrifuging, filtering, washing and drying the product to obtain; The mass ratio of zinc oxide, succinic anhydride and 3-aminopropyltriethoxysilane is (1-1.5): (1-1.2): (0.2-0.3); The mass ratio of the zinc oxide to the activated carbon powder is (1-1.5):(3.8-4.5).

2. The high-efficiency oil and wax removal agent according to claim 1, characterized in that: The alkaline auxiliary agent is a composition of sodium carbonate, sodium silicate and sodium tripolyphosphate; the mass ratio of the sodium carbonate, sodium silicate and sodium tripolyphosphate is (4-6): (2-3): (0.5-1.5).

3. The high-efficiency oil and wax removal agent according to claim 2, characterized in that: The epoxy block polyether is a composition of an epoxy block polyether with a weight average molecular weight of 1000-2000 and an epoxy block polyether with a weight average molecular weight of 4000-4400.

4. The high-efficiency oil and wax removal agent according to claim 3, characterized in that: The mass ratio of the epoxy block polyether with a weight average molecular weight of 1000-2000 to the epoxy block polyether with a weight average molecular weight of 4000-4400 is (3-4): (1-1.2).

5. The high-efficiency oil and wax removal agent according to claim 4, characterized in that: The dispersant is sodium pyrophosphate.

6. The high-efficiency oil and wax removal agent according to claim 5, characterized in that The solubilizer is a composition of polyethylene glycol and hydrogenated castor oil; the mass ratio of the polyethylene glycol to the hydrogenated castor oil is (3-4): (0.5-1).

7. A method for preparing a high-efficiency oil and wax removal agent according to any one of claims 1 to 6, characterized in that: S1: Pre-mix the functional particles and modified polymers in a container by stirring; S2: After the pre-mixing is completed, add the pre-mixture and the alkaline auxiliary agent, surfactant, dispersant, and solubilizer in turn into a small amount of deionized water, and stir evenly to ensure that there is no agglomeration; S3: Slowly add the remaining deionized water into the container, accompanied by stirring at a speed of 60~100rpm, and continue stirring until it is completely uniform.

Images