Polyether-base emulsion breaker for sludges with high water and oil contents, manufacturing method, and use thereof

Abstract

To provide especially a polyether-base emulsion breaker for sludges with high water and oil contents, a manufacturing method, and use thereof in a technical field of sludge treatments.SOLUTION: A polyether-base emulsion breaker includes 4-20 pts.wt. of propylene glycol block polyether, 5-20 pts.wt. of ethylenediamine polyoxyethylene polyoxypropylene ether, 2-10 pts.wt. of a fatty alcohol polyoxyethylene ether, 1-5 pts.wt. of secondary alkyl sulfonate, and 60-90 pts.wt. of water. Propylene glycol block polyether, ethylenediamine polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, secondary alkyl sulfonate, and water are blended and a mass ratio is adjusted so as to improve emulsification destruction efficiency of the polyether-base emulsion breaker to oil-containing sludges with a high water content and containing sands.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to the technical field of sludge treatment, and specifically relates to a polyether-based emulsion breaker for sludge with high water and oil content, a production method, and uses thereof.

Background Art

[0002] Solid waste generated in offshore oil and gas fields is mainly classified into two types: general waste and hazardous waste. Among them, general waste includes household waste, office waste, construction waste, etc., and hazardous waste includes oily sludge, chemical packaging barrels, waste lubricating oil, etc. Oily sludge contains water-in-oil (W / O) or oil-in-water (O / W) emulsions, suspended solids, and other components. Oily sludge has a complex composition and properties and contains a large amount of organic pollutants, so it is listed in the "National List of Hazardous Wastes". In the prior art, emulsion breakers are usually used to remove moisture from oily sludge. However, water-in-oil type oily sludge generated from offshore oilfields has the characteristics of high water content and low sediment ratio. Its water content can be more than 40%, and the sediment ratio is about 5%. When the water content is high, the apparent viscosity of water-in-oil type oily sludge increases, making it difficult for the emulsion breaker to diffuse into the oily sludge system. Solid sediment is adsorbed on the oil-water interface of water-in-oil type oily sludge, playing a role in steric stabilization, forming an interfacial film with higher strength than a simple oil-water interfacial film, improving the stability of the oily sludge system, and further increasing the difficulty of emulsion breaking.

[0003] In the invention with application number 202110153456.1, a non-polyether type emulsion breaker was synthesized and formulated to prepare a neutral oily sludge cleaning agent. The treatment system of such an oily sludge cleaning agent is close to neutral and environmentally friendly, but the emulsion breaking efficiency is low, and it is difficult to apply to oily sludge with high water content and containing sediment.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Regarding the problem that the efficiency of non-polyether type emulsion breakers in the prior art is low and it is difficult to apply to oil-containing sludge with high water content and containing earth and sand, the present invention mixes propylene glycol block polyether, ethylenediamine polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, secondary alkyl sulfonate and water, adjusts the mass ratio, and improves the emulsion breaking efficiency of the polyether-based emulsion breaker for oil-containing sludge with high water content and containing earth and sand, and provides a polyether-based emulsion breaker for sludge with high water and oil content, a manufacturing method and uses.

[0005] In a first aspect, the present invention provides a polyether-based emulsion breaker for sludge with high water and oil content, comprising 4 to 20 parts by weight of propylene glycol block polyether, 5 to 20 parts by weight of ethylenediamine polyoxyethylene polyoxypropylene ether, 2 to 10 parts by weight of fatty alcohol polyoxyethylene ether, 1 to 5 parts by weight of secondary alkyl sulfonate, and 60 to 90 parts by weight of water.

[0006] Here, the propylene glycol block polyether is preferably 4 to 10 parts by weight, the ethylenediamine polyoxyethylene polyoxypropylene ether is preferably 5 to 10 parts by weight, the fatty alcohol polyoxyethylene ether is preferably 2 to 5 parts by weight, and the secondary alkyl sulfonate is preferably 2 to 5 parts by weight.

[0007] Also, the molecular formula of the propylene glycol block polyether is HO(C2H4O) m (C3H6O) n H, the average molecular weight is 2000 to 3500, and the cloud point (1% aqueous solution) is 57 to 61 °C. m and n are each 0 or a positive integer, and m + n ≠ 0.

[0008] In addition, the molecular formula of ethylenediamine polyoxyethylene polyoxypropylene ether is (C3H6O - C2H8N2 - C2H4O). x The average molecular weight is 200,000 or more, the pH value (1% aqueous solution) is 10 - 11, the cloud point is 27 - 30 °C (25% BDG solution), and x is a positive integer.

[0009] In addition, the molecular formula of fatty alcohol polyoxyethylene ether is C 12 H 25 O(CH2CH2O) y H, the average molecular weight is 500 or more, the cloud point (1% aqueous solution) is 79 °C, and y is a positive integer.

[0010] In addition, the secondary alkyl sulfonate is sodium secondary alkyl sulfonate, and the molecular formula of sodium secondary alkyl sulfonate is RSO3Na, where R is an alkyl group with 14 - 17 carbon atoms.

[0011] In a second aspect, the present invention provides a method for producing the polyether - type emulsion breaker as described above. After mixing propylene glycol block polyether, ethylenediamine polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, secondary alkyl sulfonate and water, stir to obtain a polyether - type emulsion breaker.

[0012] In addition, the stirring time is 28 - 32 minutes, and the stirring speed is 180 - 220 rpm.

[0013] In addition, the stirring temperature is 25 - 28 °C.

[0014] In a third aspect, the present invention provides the use of the polyether - type emulsion breaker as described above in the treatment of sludge with high water and oil content.

[0015] In addition, the oil content of the sludge is 55% - 60%, the water content is 38% - 43%, and the sediment content is 4% - 6%. The dosage of the polyether-based emulsion breaker is 1000 - 5000 ppm.

Advantages of the Invention

[0016] The advantageous effects of the present invention are as follows. The present invention provides a polyether-based emulsion breaker for sludge with high water and oil content, a manufacturing method, and uses thereof. The polyether-based emulsion breaker is prepared by stirring and mixing propylene glycol block polyether, ethylenediamine polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, secondary alkyl sulfonate, and water as raw materials, and the manufacturing method is simple. In the present invention, by adjusting the dosage of each raw material in the polyether-based emulsion breaker, when the polyether-based emulsion breaker acts on the oil-containing sludge system, its surface activity is higher than that of the film-forming substance, so it can be quickly diffused to the interface. Therefore, a part of the natural emulsifier on the original interface film can be replaced or substituted, the oil-water interfacial tension can be reduced, and the active substance molecules in the bulk phase can be prevented from moving to the interface, forming an unstable mixed film. Finally, since the strength of the interface film decreases, the interface film is broken, emulsion breaking is achieved, and the three-phase separation rate of water, oil, and sand in the oil-containing sludge with high water content and containing sand is promoted, and the emulsion breaking efficiency of the polyether-based emulsion breaker is greatly improved. The polyether-based emulsion breaker provided by the present invention can achieve a dehydration rate of 90% or more for oil-containing sludge with high water content and containing sediment, and the water content of the separated crude oil is reduced to less than 3%, which can meet the requirements of crude oil export.

Modes for Carrying Out the Invention

[0017] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below. It is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] The model of the propylene glycol block polyether used in Example 1 and Example 5 is L64, the average molecular weight is 2900, and the cloud point (1% aqueous solution) is 57 - 61 °C. The molecular formula of ethylenediamine polyoxyethylene polyoxypropylene ether EDEP is (C3H6O - C2H8N2 - C2H4O) x wherein the average molecular weight is about 350000, the pH value (1% aqueous solution) is about 10 - 11, and the cloud point is 27 - 30E (25% BDG solution). The model of the fatty alcohol polyoxyethylene ether is AEO - 9, the average molecular weight is 582, the cloud point (1% aqueous solution) is 79 °C, and the model of the secondary alkyl sulfonate is SAS - 60, and the average molecular weight is 300.

[0019] <Example 1> The manufacturing method of the polyether - based emulsifying demulsifier for sludge with high water and oil content is as follows. Add 5 parts by weight of propylene glycol block polyether, 5 parts by weight of ethylenediamine polyoxyethylene polyoxypropylene ether, 2 parts by weight of fatty alcohol polyoxyethylene ether, 5 parts by weight of secondary alkyl sulfonate, and 83 parts by weight of water to a stirring tank, stir at 25 °C at a stirring speed of 200 rpm for 30 minutes, take out the material, and obtain the polyether - based emulsifying demulsifier for sludge with high water and oil content.

[0020] <Examples 2 - 4> Using the polyether - based emulsifying demulsifier obtained in Example 1, treat the oil - containing sludge with different water contents respectively, and the treatment method includes the following steps. Step 1: Mix the polyether-based emulsion breaker obtained in Example 1 with the oily sludge to obtain a mixed system with a mass fraction of the polyether-based emulsion breaker of 3000 ppm. Step 2: Raise the temperature of the mixed system to 60 °C and stir at a stirring rate of 100 rpm for 5 minutes at a constant temperature to obtain an emulsion-breaking system. Step 3: Centrifuge the emulsion-breaking system at a rotational speed of 4000 rpm for 6 minutes to obtain dehydrated crude oil. After centrifugation, record the amount of dehydrated water and calculate the dehydration rate. Sample from the upper layer of the emulsion-broken and dehydrated crude oil, and use the detection method of Karl Fischer coulomb titration method (GB / T 11133-2015) to detect the water content of the emulsion-broken crude oil. Sample from the mud sample at the bottom of the emulsion-broken and dehydrated crude oil, and use the detection method of petroleum spectrophotometry (HJ 637-2012) to detect the oil content of the emulsion-broken earth and sand.

[0021] In Examples 2 to 4, the water content before emulsion breaking of the oily sludge, the earth and sand content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the oil content of the earth and sand after emulsion breaking are as shown in Table 1.

[0022] JPEG2025110399000001.jpg30170

[0023] <Example 5> The manufacturing method of the polyether-based emulsion breaker for sludge with high water and oil content is as follows. Add 4 parts by weight of propylene glycol block polyether, 6 parts by weight of ethylenediamine polyoxyethylene polyoxypropylene ether, 2 parts by weight of fatty alcohol polyoxyethylene ether, 3 parts by weight of secondary alkyl sulfonate, and 85 parts by weight of water to a stirring tank, and stir at a stirring speed of 200 rpm for 30 minutes at 25 °C, then take out the material to obtain a polyether-based emulsion breaker for sludge with high water and oil content.

[0024] <Examples 6 to 8> Using the polyether-based emulsion breaker obtained in Example 5, the above-mentioned oily sludge with different water contents was treated respectively, and the treatment method included the following steps. Step 1: Mix the polyether-based emulsion breaker obtained in Example 5 with the oily sludge to obtain a mixed system with a mass fraction of the polyether-based emulsion breaker of 4000 ppm. Step 2: Raise the temperature of the mixed system to 60 °C and stir at a stirring rate of 100 rpm for 5 minutes at a constant temperature to obtain an emulsion-breaking system. Step 3: Centrifuge the emulsion-breaking system at a rotational speed of 4000 rpm for 6 minutes to obtain dehydrated crude oil. After centrifugation, record the amount of dehydrated water and calculate the dehydration rate. Sample from the upper layer of the emulsion-broken and dehydrated crude oil, and use the detection method of Karl Fischer Coulometric Titration Method (GB / T 11133-2015) to detect the water content of the crude oil after emulsion breaking. Sample from the mud sample at the bottom of the emulsion-broken and dehydrated crude oil, and use the detection method of Petroleum Spectrophotometry (HJ 637-2012) to detect the oil content in the soil and sand after emulsion breaking.

[0025] In Examples 6 to 8, the water content before emulsion breaking of the oily sludge, the soil and sand content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the oil content in the soil and sand after emulsion breaking are as shown in Table 2.

[0026] JPEG2025110399000002.jpg30170

[0027] As can be seen from Table 1 and Table 2, the polyether-based emulsion breaker produced according to the present invention can effectively remove water from the oily sludge with a high original water content, and obtain crude oil with a water content of less than 2.076% in the crude oil after emulsion breaking.

[0028] <Comparative Examples 1 to 3> The differences between Comparative Examples 1 to 3 and Examples 2 to 4 are only that in Comparative Examples 1 to 3, the commercially available non-polyether-based emulsion breaker M550 was used to treat the oily sludge with water contents of 38.67%, 39.85%, and 42.61% respectively.

[0029] In Comparative Examples 1 to 3, the water content of the oily sludge before emulsion breaking, the earth and sand content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the earth and sand oil content after emulsion breaking are as shown in Table 3.

[0030] JPEG2025110399000003.jpg30170

[0031] <Comparative Examples 4 to 6> The differences between Comparative Examples 4 to 6 and Examples 2 to 4 are only that in Comparative Examples 4 to 6, a commercially available non-polyether emulsion breaker LAS-30 is used to treat oily sludge with water contents of 38.67%, 39.85%, and 42.61% respectively.

[0032] In Comparative Examples 4 to 6, the water content of the oily sludge before emulsion breaking, the earth and sand content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the earth and sand oil content after emulsion breaking are as shown in Table 4.

[0033] JPEG2025110399000004.jpg30170

[0034] As can be seen from Tables 3 and 4, in Comparative Examples 1 to 3 and Comparative Examples 4 to 6, when the same oily sludge was treated using commercially available non-polyether emulsion breakers M550 and LAS-30 respectively, the water content of the crude oil after emulsion breaking was significantly higher than that of the crude oil after emulsion breaking in Examples 2 to 4, and the earth and sand oil content after emulsion breaking was significantly higher than that in Examples 2 to 4. This explains that the polyether-based emulsion breaker produced according to the present invention can achieve better separation of water, oil, and earth and sand than commercially available non-polyether emulsion breakers in the treatment of oily sludge.

[0035] <Comparative Examples 7 to 9> The differences between Comparative Examples 7 to 9 and Examples 2 to 4 are that the emulsion-breaking agents used in Comparative Examples 7 to 9 are prepared from 2 parts by weight of propylene glycol block polyether, 3 parts by weight of ethylenediamine polyoxyethylene polyoxypropylene ether, 1 part by weight of fatty alcohol polyoxyethylene ether, 6 parts by weight of secondary alkyl sulfonate, and 88 parts by weight of water.

[0036] In Comparative Examples 7 to 9, the water content of the oily sludge before emulsion breaking, the sediment content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the sediment oil content after emulsion breaking are as shown in Table 5.

[0037] JPEG2025110399000005.jpg30170

[0038] <Comparative Examples 10 to 12> The differences between Comparative Examples 10 to 12 and Examples 2 to 4 are only that the emulsion-breaking agents used in Comparative Examples 10 to 12 are prepared from 5 parts by weight of propylene glycol block polyether, 5 parts by weight of disodium ethylenediaminetetraacetate, 5 parts by weight of fatty alcohol polyoxyethylene ether, 6 parts by weight of sodium dodecylbenzenesulfonate, and 80 parts by weight of water. Here, the model of propylene glycol block polyether is L65, the average molecular weight is 3500, the model of fatty alcohol polyoxyethylene ether is AEO-3, the molecular weight is 318.56, and the model of sodium dodecylbenzenesulfonate is LAS-30.

[0039] In Comparative Examples 10 to 12, the water content of the oily sludge before emulsion breaking, the sediment content before emulsion breaking, the dehydration rate, the water content of the crude oil after emulsion breaking, and the sediment oil content after emulsion breaking are as shown in Table 6.

[0040] JPEG2025110399000006.jpg30170

[0041] As can be seen from Tables 5 and 6, the emulsion breakers of Comparative Examples 7 to 9 prepared not according to the ratio provided by the present invention have a water content of crude oil after emulsion breaking higher than 11% and an oil content in sediment after emulsion breaking all higher than 15%. Therefore, water, oil, and sediment in the oil-containing sludge could not be separated well. In Comparative Examples 10 to 12, when AEO-3 with similar effects and a similar molecular weight was used instead of AEO-9 and LAS-30 was used instead of SAS-60, respectively, the water content of the obtained crude oil after emulsion breaking was all higher than 10%, and the oil content in sediment after emulsion breaking was all higher than 14%. Therefore, water, oil, and sediment in the oil-containing sludge could not be separated well either. In the treatment of the polyether-based emulsion breaker used in Examples 2 to 4, the sludge with an oil content of 55% to 60%, a water content of 38% to 43%, and a sediment content of 4% to 6% has a remarkable separation effect compared with Comparative Examples 7 to 12.

[0042] Although the present invention has been described in detail by preferred embodiments, the present invention is not limited thereto. Without departing from the spirit and essence of the present invention, those skilled in the art can make various equivalent modifications or substitutions to the embodiments of the present invention, and these modifications or substitutions are intended to be within the scope of the present invention. / Those skilled in the art can easily come up with changes or substitutions within the technical scope disclosed in the present invention, and these should be included within the protection scope of the present invention.

Claims

1. A polyether-based emulsion breaker for sludge with high water and oil content, comprising 4 to 20 parts by weight of propylene glycol block polyether, 5 to 20 parts by weight of ethylenediamine polyoxyethylene polyoxypropylene ether, 2 to 10 parts by weight of fatty alcohol polyoxyethylene ether, 1 to 5 parts by weight of secondary alkyl sulfonate, and 60 to 90 parts by weight of water, The molecular formula of propylene glycol block polyether is HO(C 2 H 4 O) m (C 3 H 6 O) n H, and the average molecular weight is 2,000 to 3,500, The molecular formula of the fatty alcohol polyoxyethylene ether is C 12 H 25 O(CH 2 CH 2 O) y H, and the average molecular weight is 500 or more. The secondary alkyl sulfonate is sodium secondary alkyl sulfonate, and the molecular formula of sodium secondary alkyl sulfonate is RSO 3 Na, where R is an alkyl group having 14 to 17 carbon atoms, The molecular formula of ethylene diamine polyoxyethylene polyoxypropylene ether is (C 3 H 6 O-C 2 H 8 N 2 -C 2 H 4 O) x and the average molecular weight is 200,000 or more, and it is a polyether-based emulsion breaker.

2. A method for producing the polyether-based emulsion breaker according to Claim 1, wherein propylene glycol block polyether, ethylenediamine polyoxyethylene polyoxypropylene ether, fatty alcohol polyoxyethylene ether, secondary alkyl sulfonate and water are mixed and then stirred to obtain the polyether-based emulsion breaker, and the stirring temperature is 25 to 28 °C. A method for producing the polyether-based emulsion breaker according to Claim 1, characterized by this.

3. The stirring time is 28 to 32 minutes and the stirring speed is 180 to 220 rpm. A production method according to Claim 2, characterized by this.

4. Use of the polyether-based emulsion breaker according to Claim 1 in the treatment of sludge with high water and oil content.

5. The oil content of the sludge is 55% to 60%, the water content is 38% to 43%, and the soil and sand content is 4% to 6%. A use according to Claim 4, characterized by this.

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