Chemical additive with demulsification and separation functions and preparation method thereof

Abstract

The invention relates to the technical field of demulsifiers, and provides a chemical additive with demulsification and separation functions and a preparation method of the chemical additive with the demulsification and separation functions. Comprising the following components in parts by weight: 15-40 parts of allyl polyoxyethylene polyoxypropylene ether, 10-15 parts of polyacrylamide, 8-17 parts of polyaluminum chloride, 3-12 parts of zinc-doped aluminum oxide, 4-6 parts of a surfactant, 2-4 parts of inorganic salt, 0.5-1 part of a defoaming agent and 15-25 parts of water. According to the technical scheme, the problem that in the prior art, the dehydration effect of a chemical additive with demulsification and separation functions is not ideal is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of demulsifier, in particular to a chemical additive with demulsification and separation functions and a preparation method thereof. BACKGROUND

[0002] The stability of crude oil emulsion mainly depends on the rigid interface film formed by natural interfacial active substances such as asphaltene, naphthenic acid, fatty acid and resin in the crude oil, so the demulsification technology is crucial in the process of oil exploitation, transportation and processing. At present, the demulsification methods developed at home and abroad are mainly divided into physical method, biological method and chemical method, among which the chemical method becomes the mainstream technology due to its high efficiency and wide adaptability. This method is to destroy the interface film by adding demulsifier, which has the advantages of rapid demulsification, low energy consumption and small dosage, and its core mechanism is that the active components of the demulsifier molecules compete to replace the original interfacial active substances (such as asphaltene, resin, etc.) by diffusing and migrating to the oil-water interface, thereby reducing the strength of the interface film, promoting the coalescence of small droplets into large droplets, and finally realizing the effective separation of oil and water phases. However, the traditional demulsifier has the problem of poor dewatering effect, and further increasing the dosage not only can not improve the dewatering efficiency, but also will lead to the increase of the cost of dewatering of crude oil emulsion. Based on this situation, the development of low-cost and high-dewatering-effect chemical additives has become the key demand for the development of demulsification technology. SUMMARY

[0003] The present application provides a chemical additive with demulsification and separation functions and a preparation method thereof, which solves the problem of poor dewatering effect of the chemical additive with demulsification and separation functions in the related art.

[0004] The technical scheme of the present application is as follows: The present application provides a chemical additive with demulsification and separation functions, which comprises the following components by weight: allyl polyoxyethylene polyoxypropylene ether 15-40 parts, polyacrylamide 10-15 parts, polyaluminum chloride 8-17 parts, zinc-doped alumina 3-10 parts, surfactant 4-6 parts, inorganic salt 2-4 parts, defoaming agent 0.5-1 part, and water 15-25 parts.

[0005] As a further technical scheme, the mass ratio of the polyaluminum chloride and the zinc-doped alumina is 3:1-2.

[0006] In the present application, the mass ratio of the polyaluminum chloride and the zinc-doped alumina is 3:1-2, and the dewatering effect of the chemical additive with demulsification and separation functions is better.

[0007] As a further technical scheme, the preparation method of the zinc-doped alumina comprises the following steps: Mixing zinc nitrate solution and aluminum nitrate solution, adding polyvinyl alcohol solution, stirring, drying, and obtaining precursor powder; The precursor powder is calcined and ground to obtain zinc-doped alumina.

[0008] As a further technical solution, the mass fraction of the polyvinyl alcohol solution is 6% to 8%.

[0009] As a further technical solution, the zinc nitrate solution is a saturated zinc nitrate solution.

[0010] As a further technical solution, the aluminum nitrate solution is a saturated aluminum nitrate solution.

[0011] As a further technical solution, the mass ratio of the zinc nitrate solution and the aluminum nitrate solution is 1:5 to 15.

[0012] Preferably, the mass ratio of the zinc nitrate solution and the aluminum nitrate solution is 1:7.5.

[0013] In the preparation of zinc-doped alumina according to the present application, when the mass ratio of the zinc nitrate solution and the aluminum nitrate solution is 1:7.5, an appropriate amount of zinc ions is incorporated, optimizing the number and distribution of active sites on the surface of the alumina, making it have stronger adsorption affinity for oil droplets or emulsion particles. At the same time, the charge density and hydrophilicity of the alumina surface change, and the moderate change in hydrophilicity allows the alumina to better play a role in interfacial regulation at the oil-water interface, reducing the oil-water interfacial tension and accelerating the coalescence process of oil droplets, making the chemical additive with both demulsification and separation functions have better oil removal performance.

[0014] As a further technical solution, the mass ratio of the polyvinyl alcohol solution to the total mass of the zinc nitrate solution and the aluminum nitrate solution is 25:1 to 1.5.

[0015] As a further technical solution, the stirring time is 2 to 3 hours.

[0016] As a further technical solution, the drying temperature is 90 to 100℃, and the time is 6 to 8 hours.

[0017] As a further technical solution, the calcination is carried out at a temperature increase of 5 to 8℃ / min to 1050 to 1150℃ for 3.5 to 4.5 hours.

[0018] As a further technical solution, the particle size of the zinc-doped alumina is 15 to 30 nm.

[0019] As a further technical solution, the surfactant includes one or both of fatty alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

[0020] As a further technical solution, the inorganic salt includes one or more of ferric chloride, aluminum sulfate, and calcium chloride.

[0021] As a further technical solution, the defoaming agent comprises an organic silicon defoaming agent.

[0022] The application further provides a preparation method of the chemical additive with the demulsification and separation functions. The inorganic salt, the polyaluminum chloride, the zinc-doped alumina and the allyl polyoxyethylene polyoxypropylene ether are sequentially added into water to form a mixture A by stirring; the polyacrylamide and the surfactant are sequentially added into the mixture A to perform second stirring; finally, the defoaming agent is added to perform third stirring, so as to obtain the chemical additive with the demulsification and separation functions.

[0023] The working principle and beneficial effects of the application are as follows: In the application, the polyaluminum chloride and the zinc-doped alumina are used together, and the dehydration rate of the chemical additive with the demulsification and separation functions is significantly improved; a plurality of positively charged polynuclear hydroxyl complexes are generated in the hydrolysis process of the polyaluminum chloride, the particles are coagulated through electrostatic neutralization, and a large specific surface area of aluminum hydroxide colloid is generated in the hydrolysis, the oil droplets or emulsion particles are connected through adsorption and bridging, and a large flocculation structure is formed; the surface active sites of the zinc-doped alumina are increased, the hydrophilicity and adsorption performance are significantly improved, the flocculation structure provides an attachment site for the zinc-doped alumina, so that the zinc-doped alumina can more effectively participate in the demulsification and separation process, and when the polyaluminum chloride and the zinc-doped alumina are used together, the dehydration effect of the chemical additive with the demulsification and separation functions is significantly improved. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor also fall within the protection scope of the application.

[0025] In the following examples and comparative examples, The allyl polyoxyethylene polyoxypropylene ether is from Haian Petroleum Chemical Plant in Jiangsu Province; The polyacrylamide is cationic, and is from Zhengzhou Fangcheng Environmental Protection Co., Ltd.; The polyaluminum chloride is dy-042, and is from Shandong De Yuan New Material Co., Ltd.; The fatty alcohol polyoxyethylene ether is AE0-9; The nonylphenol polyoxyethylene ether is NP-10; The organic silicon defoaming agent is kx-98, and is from Henan Runquan Purification Material Co., Ltd.

[0026] Example 1 A chemical additive that combines demulsification and separation functions comprises the following components in parts by weight: 15 parts allyl polyoxyethylene polyoxypropylene ether, 10 parts polyacrylamide, 8 parts polyaluminum chloride, 3 parts zinc-doped alumina, 4 parts fatty alcohol polyoxyethylene ether, 2 parts ferric chloride, 0.5 parts organosilicon defoamer, and 15 parts water. A method for preparing zinc-doped alumina includes the following steps: At room temperature, a saturated zinc nitrate solution and a saturated aluminum nitrate solution were mixed (the mass ratio of the saturated zinc nitrate solution to the saturated aluminum nitrate solution was 1:15), and a 6% polyvinyl alcohol solution was added and stirred for 2 hours. The mixture was then dried at 90°C for 8 hours to obtain the precursor powder. The precursor powder was heated to 1050℃ at 5℃ / min and calcined for 4.5h, then ground to obtain zinc-doped alumina with a particle size of 15nm. A chemical additive that combines demulsification and separation functions includes the following steps: Ferric chloride, polyaluminum chloride, zinc-doped alumina, and allyl polyoxyethylene polyoxypropylene ether were added to water in sequence and stirred to form mixture A. Polyacrylamide and fatty alcohol polyoxyethylene ether were added to mixture A in sequence and stirred a second time. Finally, an organosilicon defoamer was added and stirred a third time to obtain a chemical auxiliary agent with both demulsification and separation functions.

[0027] Example 2 A chemical additive that combines demulsification and separation functions comprises the following components in parts by weight: 40 parts allyl polyoxyethylene polyoxypropylene ether, 15 parts polyacrylamide, 17 parts polyaluminum chloride, 12 parts zinc-doped alumina, 6 parts nonylphenol polyoxyethylene ether, 4 parts aluminum sulfate, 1 part organosilicon defoamer, and 25 parts water. A method for preparing zinc-doped alumina includes the following steps: At room temperature, a saturated zinc nitrate solution and a saturated aluminum nitrate solution were mixed (the mass ratio of the saturated zinc nitrate solution to the saturated aluminum nitrate solution was 1:15), and an 8% polyvinyl alcohol solution was added and stirred for 3 hours. The mixture was then dried at 100°C for 6 hours to obtain the precursor powder. The precursor powder was heated to 1150℃ at 8℃ / min and calcined for 3.5h, then ground to obtain zinc-doped alumina with a particle size of 30nm. A chemical additive that combines demulsification and separation functions includes the following steps: Aluminum sulfate, polyaluminum chloride, zinc-doped alumina, and allyl polyoxyethylene polyoxypropylene ether were added to water in sequence and stirred to form mixture A. Polyacrylamide and nonylphenol polyoxyethylene ether were added to mixture A in sequence and stirred a second time. Finally, an organosilicon defoamer was added and stirred a third time to obtain a chemical auxiliary agent with both demulsification and separation functions.

[0028] Example 3 A chemical additive that combines demulsification and separation functions comprises the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 10.5 parts polyaluminum chloride, 9.5 parts zinc-doped alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water. A method for preparing zinc-doped alumina includes the following steps: At room temperature, a saturated zinc nitrate solution and a saturated aluminum nitrate solution were mixed (the mass ratio of the saturated zinc nitrate solution to the saturated aluminum nitrate solution was 1:15), and a 7% polyvinyl alcohol solution was added and stirred for 2.5 h. The mixture was then dried at 95 °C for 7 h to obtain the precursor powder. The precursor powder was calcined at 1100℃ for 4 hours at a rate of 6℃ / min and then ground to obtain zinc-doped alumina with a particle size of 20nm. A chemical additive that combines demulsification and separation functions includes the following steps: Calcium chloride, polyaluminum chloride, zinc-doped alumina, and allyl polyoxyethylene polyoxypropylene ether were added to water in sequence and stirred to form mixture A. Polyacrylamide and fatty alcohol polyoxyethylene ether were added to mixture A in sequence and stirred a second time. Finally, an organosilicon defoamer was added and stirred a third time to obtain a chemical auxiliary agent with both demulsification and separation functions.

[0029] Example 4 The difference between this embodiment and Embodiment 3 lies only in the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 12 parts polyaluminum chloride, 8 parts zinc-doped alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water.

[0030] Example 5 The difference between this embodiment and Embodiment 3 lies only in the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 15 parts polyaluminum chloride, 5 parts zinc-doped alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water.

[0031] Example 6 The difference between this embodiment and Embodiment 3 lies only in the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 16.5 parts polyaluminum chloride, 3.5 parts zinc-doped alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water.

[0032] Example 7 The only difference between this embodiment and Example 4 is the preparation method of zinc-doped alumina, which includes the following steps: At room temperature, a saturated zinc nitrate solution and a saturated aluminum nitrate solution were mixed (the mass ratio of the saturated zinc nitrate solution to the saturated aluminum nitrate solution was 1:7.5), and a 7% polyvinyl alcohol solution was added and stirred for 2.5 h. The mixture was then dried at 95 °C for 7 h to obtain the precursor powder. The precursor powder was heated to 1100℃ at 6℃ / min and calcined for 4 hours, then ground to obtain zinc-doped alumina with a particle size of 20nm.

[0033] Example 8 The only difference between this embodiment and Example 4 is the preparation method of zinc-doped alumina, which includes the following steps: At room temperature, a saturated zinc nitrate solution and a saturated aluminum nitrate solution were mixed (the mass ratio of the saturated zinc nitrate solution to the saturated aluminum nitrate solution was 1:5), and a 7% polyvinyl alcohol solution was added and stirred for 2.5 h. The mixture was then dried at 95 °C for 7 h to obtain the precursor powder. The precursor powder was heated to 1100℃ at 6℃ / min and calcined for 4 hours, then ground to obtain zinc-doped alumina with a particle size of 20nm.

[0034] Comparative Example 1 The only difference between this comparative example and Example 3 is the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 20 parts polyaluminum chloride, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water.

[0035] Comparative Example 2 The only difference between this comparative example and Example 3 is the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 20 parts zinc-doped alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts silicone defoamer, and 20 parts water.

[0036] Comparative Example 3 The only difference between this comparative example and Example 3 is the presence of a chemical additive that combines demulsification and separation functions, comprising the following components in parts by weight: 28 parts allyl polyoxyethylene polyoxypropylene ether, 12 parts polyacrylamide, 10.5 parts polyaluminum chloride, 9.5 parts alumina, 5 parts fatty alcohol polyoxyethylene ether, 3 parts calcium chloride, 0.8 parts organosilicon defoamer, and 20 parts water.

[0037] The chemical additives with both demulsifying and separating functions prepared in Examples 1-8 and Comparative Examples 1-3 were tested according to the following method: Demulsification test: According to the test method specified in SY / T 5280-2018 "General Technical Conditions for Crude Oil Demulsifiers", the dehydration rate and oil content of the dehydrated sample were tested, and the treatment time was 30 min. The test results are shown in Table 1: Table 1. Performance test results of the chemical auxiliaries with demulsification and separation functions prepared in Examples 1-8 and Comparative Examples 1-3.

[0038] 1. Compared with Comparative Examples 1-3, the dehydration rate of the chemical auxiliaries with demulsification and separation functions prepared in Examples 1-8 was significantly higher than that in Comparative Examples 1-3, indicating that the combined use of polyaluminum chloride and zinc-doped alumina can improve the dehydration effect of the chemical auxiliaries with demulsification and separation functions.

[0039] 2. Compared with Examples 3 to 6, the dehydration rate of the chemical additives with demulsification and separation functions prepared in Examples 4 to 5 is higher than that in Examples 3 and 6. This indicates that further limiting the mass ratio of polyaluminum chloride to zinc-doped alumina to 3:1 to 2 can further improve the dehydration effect of the chemical additives with demulsification and separation functions.

[0040] 3. Compared with Examples 4 and 7-8, the dewatering oil content of the chemical auxiliary agent with demulsification and separation functions prepared in Example 7 was lower than that in Examples 4 and 8. This indicates that when the mass ratio of zinc nitrate solution to aluminum nitrate solution is 1:7.5 when preparing zinc-doped alumina, the degreasing performance of the chemical auxiliary agent with demulsification and separation functions is better.

[0041] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A chemical additive having both demulsification and separation functions, characterized in that, The components include the following weight parts: allyl polyoxyethylene polyoxypropylene ether 15-40 parts, polyacrylamide 10-15 parts, polyaluminum chloride 8-17 parts, zinc-doped alumina 3-12 parts, surfactant 4-6 parts, inorganic salt 2-4 parts, defoaming agent 0.5-1 part, and water 15-25 parts.

2. The chemical additive with both demulsification and separation functions according to claim 1, characterized in that, The mass ratio of the polyaluminum chloride and the zinc-doped alumina is 3:1-2.

3. The chemical additive with both demulsification and separation functions according to claim 1, characterized in that, The preparation method of the zinc-doped alumina comprises the following steps: The zinc nitrate solution and the aluminum nitrate solution are mixed, a polyvinyl alcohol solution is added, stirred, dried, and a precursor powder is obtained. The precursor powder is calcined and ground to obtain the zinc-doped alumina.

4. The chemical additive with both demulsification and separation functions according to claim 3, characterized in that, The mass fraction of the polyvinyl alcohol solution is 6%-8%.

5. The chemical additive with both demulsification and separation functions according to claim 3, characterized in that, The mass ratio of the zinc nitrate solution and the aluminum nitrate solution is 1:5-15.

6. The chemical additive with both demulsification and separation functions according to claim 3, characterized in that, The ratio of the mass of the polyvinyl alcohol solution to the total mass of the zinc nitrate solution and the aluminum nitrate solution is 25:1-1.

5. The calcination is performed at a temperature increasing rate of 5-8 ℃ / min to 1050-1150 ℃ for 3.5-4.5 h. The particle size of the zinc-doped alumina is 15-30 nm.

7. The chemical additive with both demulsification and separation functions according to claim 1, characterized in that, The surfactant includes one or both of a fatty alcohol polyoxyethylene ether and a nonylphenol polyoxyethylene ether.

8. The chemical aid with both demulsification and separation functions according to claim 1, characterized in that, The inorganic salt includes one or more of ferric chloride, aluminum sulfate, and calcium chloride.

9. The chemical aid with both demulsification and separation functions according to claim 1, characterized in that, The defoaming agent includes a silicone-based defoaming agent.

10. A preparation method of the chemical aid with both demulsification and separation functions, for preparing the chemical aid with both demulsification and separation functions according to any one of claims 1-9, characterized in that, The method comprises the following steps: The inorganic salt, the polyaluminum chloride, the zinc-doped alumina, and the allyl polyoxyethylene polyoxypropylene ether are sequentially added to water, stirred to form a mixture A; the polyacrylamide and the surfactant are sequentially added to the mixture A, second stirring is performed, the defoaming agent is finally added, third stirring is performed, and a chemical additive with both demulsification and separation functions is obtained.

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