CN105969433A - Nano compound pour point depressant and preparation method thereof - Google Patents
Nano compound pour point depressant and preparation method thereof Download PDFInfo
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- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 17
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229920000193 polymethacrylate Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002114 nanocomposite Substances 0.000 abstract description 43
- 239000002283 diesel fuel Substances 0.000 abstract description 42
- 239000000463 material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 238000009833 condensation Methods 0.000 abstract description 10
- 230000005494 condensation Effects 0.000 abstract description 10
- 239000000155 melt Substances 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 9
- 230000000881 depressing effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006011 modification reaction Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/106—Liquid carbonaceous fuels containing additives mixtures of inorganic compounds with organic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
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Abstract
本发明公开了一种纳米复合降凝剂及其制备方法。本发明的纳米复合降凝剂由纳米材料和聚合物降凝剂通过熔融共混法复合而成。本发明通过将十六烷基三甲基溴化铵改性的蒙脱石纳米材料与聚合物降凝剂以一定质量比，采用熔融共混法进行复合，得到一种纳米复合降凝剂。本发明的纳米复合降凝剂在原有降凝剂的降凝基础上进一步增强了降凝效果。将其应用于0#柴油中，降凝效果优于市售降凝剂，使其冷滤点和冷凝点分别降低12‑20℃和18‑26℃。The invention discloses a nanocomposite pour point depressant and a preparation method thereof. The nanocomposite pour point depressant of the invention is compounded by a nanometer material and a polymer pour point depressant through a melt blending method. The invention obtains a nanocomposite pour point depressant by compounding the montmorillonite nanometer material modified by cetyltrimethylammonium bromide and the polymer pour point depressant in a certain mass ratio through a melt blending method. The nanocomposite pour point depressant of the invention further enhances the pour point depressant effect on the basis of the original pour point depressant. When it is applied to 0 # diesel oil, the pour point depressant effect is better than that of commercially available pour point depressants, and its cold filter point and condensation point are reduced by 12‑20°C and 18‑26°C, respectively.
Description
技术领域technical field
本发明具体涉及一种纳米复合降凝剂及其制备方法，属于生物质能源添加剂技术领域。The invention specifically relates to a nanocomposite pour point depressant and a preparation method thereof, belonging to the technical field of biomass energy additives.
背景技术Background technique
随着世界经济的不断发展，人类对能源的需求越来越大，石化柴油已经成为人们赖以生存的能源。但在我国北方的冬天及一些寒冷地区，由于柴油是一种含有多组分复杂烃类的混合物，在温度降低时会析出蜡晶，随着温度的降低，蜡晶不断增多，最终形成三维网状结构，阻塞了发动机输油管路与过滤器，使发动机不能正常工作。With the continuous development of the world economy, human beings have an increasing demand for energy, and petrochemical diesel has become the energy that people rely on for survival. However, in the winter in northern my country and some cold regions, since diesel oil is a mixture containing multi-component complex hydrocarbons, wax crystals will be precipitated when the temperature drops. structure, blocking the engine oil pipeline and filter, so that the engine cannot work normally.
近年来，随着纳米技术的发展，聚合物/无机纳米复合材料、无机纳米杂化材料已成为国内外学者研究的热点。通过引入无机纳米粒子在聚合物材料中，可以使其性能(如机械、热、磁、电等)大大提高。另外，纳米材料因其特有的表面效应、量子尺寸效应、小尺寸效应和宏观量子隧道效应，使其具有广阔的应用前景，在石化领域应用的纳米催化剂、纳米驱油技术等都起到了良好的效果。In recent years, with the development of nanotechnology, polymer/inorganic nanocomposites and inorganic nanohybrid materials have become the research hotspots of scholars at home and abroad. By introducing inorganic nanoparticles into polymer materials, its performance (such as mechanical, thermal, magnetic, electrical, etc.) can be greatly improved. In addition, nanomaterials have broad application prospects due to their unique surface effects, quantum size effects, small size effects, and macroscopic quantum tunneling effects. Nanocatalysts and nanooil flooding technologies used in the petrochemical field have played a good role. Effect.
目前针对于改善柴油低温流动性的降凝剂虽种类较多，但是并不能达到很好的降凝效果，因此研发一种新型降凝剂，来提高柴油低温流动性是亟待解决的问题。将传统降凝剂与新兴的纳米材料进行复合，研发出一种新型纳米复合降凝剂用于改善柴油低温流动性，为柴油降凝剂的发展开辟了一条新的道路。At present, although there are many kinds of pour point depressants aimed at improving the low-temperature fluidity of diesel oil, they cannot achieve a good pour point depressant effect. Therefore, it is an urgent problem to be solved to develop a new type of pour point depressant to improve the low-temperature fluidity of diesel oil. Combining traditional pour point depressants with emerging nanomaterials, a new nanocomposite pour point depressant has been developed to improve the low temperature fluidity of diesel oil, which has opened up a new path for the development of diesel pour point depressants.
发明内容Contents of the invention
本发明的目的之一是为了在普通降凝剂的降凝基础上进一步增强降凝效果而提供一种新型纳米复合降凝剂，该新型纳米复合降凝剂，不仅具有普通降凝剂的降凝效果，而且还具备纳米材料的优良特性，在对于柴油的降凝机理提供了一种更加深入、直观的认识。One of the purposes of the present invention is to provide a novel nanocomposite pour point depressant in order to further enhance the pour point depressant effect on the basis of common pour point depressants. This novel nanocomposite pour point depressant not only has the It also has the excellent characteristics of nano-materials, which provides a more in-depth and intuitive understanding of the pour point depressing mechanism of diesel.
本发明的目的之二是提供上述的一种新型纳米复合降凝剂的制备方法。The second object of the present invention is to provide a method for preparing the above-mentioned novel nanocomposite pour point depressant.
本发明技术方案具体介绍如下。The technical solution of the present invention is specifically introduced as follows.
本发明提供一种纳米复合降凝剂的制备方法，其以有机改性纳米蒙脱石和聚合物降凝剂为原料，通过熔融共混法制备得到。The invention provides a method for preparing a nanocomposite pour point depressant, which uses organically modified nano-montmorillonite and a polymer pour point depressant as raw materials, and is prepared by a melt blending method.
本发明中，有机改性纳米蒙脱石和聚合物降凝剂的质量比为1：1～1:8。In the present invention, the mass ratio of the organically modified nano-montmorillonite to the polymer pour point depressant is 1:1˜1:8.
本发明中，所述有机改性纳米蒙脱石通过将纳米蒙脱石和十六烷基三甲基溴化铵混合在水中，75-85℃的温度下进行反应得到。In the present invention, the organically modified nano-montmorillonite is obtained by mixing nano-montmorillonite and cetyltrimethylammonium bromide in water and reacting at a temperature of 75-85°C.
本发明中，纳米蒙脱石和十六烷基三甲基溴化铵的质量比为1:2。In the present invention, the mass ratio of nano-montmorillonite to cetyltrimethylammonium bromide is 1:2.
本发明中，所述聚合物降凝剂选自聚甲基丙烯酸酯类降凝剂10-330或聚乙烯-醋酸乙烯酯类降凝剂T1804中的一种或两种。In the present invention, the polymer pour point depressant is selected from one or both of polymethacrylate pour point depressant 10-330 or polyethylene-vinyl acetate pour point depressant T1804.
本发明中，熔融共混时的温度为120℃。In the present invention, the temperature at the time of melt blending is 120°C.
本发明还提供一种上述的制备方法得到的纳米复合降凝剂。The present invention also provides a nanocomposite pour point depressant obtained by the above preparation method.
和现有技术相比，本发明的有益效果在于：Compared with the prior art, the beneficial effects of the present invention are:
本发明的一种新型纳米复合降凝剂，其中降凝剂与有机改性纳米蒙脱石共同起到降凝作用，降凝剂的非极性烷基链能够与蜡分子有序排列，起到一定的增溶蜡分子的作用，改性纳米蒙脱石会拓宽降凝剂的结晶温度区间，优化降凝剂与柴油的共晶改性性能。另外，由于改性纳米蒙脱石具有较高的表面能，为了维持体系能量稳定，在添加纳米复合降凝剂的柴油中蜡晶在析出聚集时趋向于比添加等量纯降凝剂柴油中蜡晶更紧凑的排布方式，以减小界面面积降低表面能。紧凑的蜡晶聚集体使得更多原来被包裹的液态油被释放出来，大大降低了蜡-油界面面积，进而使得柴油流动时蜡晶与液态柴油间摩擦耗散能量减少，流动性进一步得到改善。A novel nano-composite pour point depressant of the present invention, wherein the pour point depressant and organically modified nano-montmorillonite jointly play a pour point depressant effect, and the non-polar alkyl chains of the pour point depressant can be arranged in an orderly manner with wax molecules to play a role To a certain degree of solubilizing wax molecules, the modified nano-montmorillonite will widen the crystallization temperature range of the pour point depressant, and optimize the eutectic modification performance of the pour point depressant and diesel. In addition, due to the high surface energy of the modified nano-montmorillonite, in order to maintain the energy stability of the system, the wax crystals in the diesel fuel with nano-composite pour point depressant tend to precipitate and aggregate more than those in diesel fuel with the same amount of pure pour point depressant. Wax crystals are more compactly arranged to reduce the interface area and reduce the surface energy. The compact wax crystal aggregates release more liquid oil that was originally wrapped, greatly reducing the wax-oil interface area, thereby reducing the frictional energy dissipation between wax crystals and liquid diesel oil when diesel oil flows, and further improving fluidity .
进一步，本发明的一种新型纳米复合降凝剂，将其应用于0#柴油中，降凝效果优于市售降凝剂，添加的质量是柴油的0.05％-0.3％时，可使其冷滤点和冷凝点分别降低12-20℃和18-26℃。Further, when a novel nanocomposite pour point depressant of the present invention is applied to 0 # diesel oil, the pour point depressant effect is better than commercially available pour point depressants, and when the added quality is 0.05%-0.3% of diesel oil, it can make it The cold filtration point and condensation point are lowered by 12-20°C and 18-26°C, respectively.
具体实施方式detailed description
下面结合具体的实施例对本发明的技术方案做进一步的描述,但本发明并不限于下述实施例。The technical solutions of the present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples.
本发明中冷凝点的测量方法依据《GB510-83石油产品凝点测定》进行，冷滤点的测量方法依据《SH/T0248-2006柴油和民用取暖油冷滤点测定法》进行。The measurement method of the freezing point in the present invention is carried out according to "GB510-83 Determination of the freezing point of petroleum products", and the measurement method of the cold filter point is carried out according to "SH/T0248-2006 Diesel and civil heating oil cold filter point measurement method".
本发明所用原料：Raw materials used in the present invention:
蒙脱石(分析纯)购自泰坦科技；Montmorillonite (analytical pure) was purchased from Titan Technology;
十六烷基三甲基溴化铵(分析纯)购自泰坦科技；Hexadecyltrimethylammonium bromide (analytical pure) was purchased from Titan Technology;
降凝剂购自上海海联润滑材料科技有限公司；The pour point depressant was purchased from Shanghai Hailian Lubricating Material Technology Co., Ltd.;
0#石化柴油购自上海松江加油站公司。0 #Petrochemical diesel was purchased from Shanghai Songjiang Gas Station Company.
实施例1Example 1
一种新型纳米复合降凝剂，其通过包括如下步骤的方法制备而成：A novel nanocomposite pour point depressant prepared by a method comprising the following steps:
(1)一定量纳米蒙脱石与十六烷基三甲基溴化铵在水为溶剂下，80℃条件下进行有机改性反应，即得到有机改性蒙脱石；(1) A certain amount of nano-montmorillonite and hexadecyltrimethylammonium bromide are subjected to an organic modification reaction at 80°C under water as a solvent to obtain an organically modified montmorillonite;
(2)将有机改性后的纳米蒙脱石材料与聚合物降凝剂置于烧瓶中，采用熔融共混法，在120℃下反应3小时，即得一种新型纳米复合降凝剂；(2) Place the organically modified nano-montmorillonite material and the polymer pour point depressant in a flask, and react at 120° C. for 3 hours by a melt blending method to obtain a novel nanocomposite pour point depressant;
上述反应所用的聚合物降凝剂、有机改性纳米蒙脱石的量，按质量比计算，即聚合物降凝剂：有机改性纳米蒙脱石为2:1；The amount of polymer pour point depressant used in the above-mentioned reaction, organically modified nano-montmorillonite is calculated by mass ratio, that is, polymer pour point depressant: organically modified nano-montmorillonite is 2:1;
所述的聚合物降凝剂为聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant is polyethylene-vinyl acetate pour point depressant T1804;
将上述纳米复合降凝剂添加质量比优选为0.1％，加入到0#柴油中，经测试与0#柴油相比，含有新型纳米复合降凝剂柴油的冷滤点和冷凝点分别降低16℃和22℃。The above-mentioned nanocomposite pour point depressant is preferably added at a mass ratio of 0.1%, and added to 0 # diesel oil. Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing the new nanocomposite pour point depressant are respectively lowered by 16°C and 22°C.
对照实施例1Comparative Example 1
将聚合物降凝剂以0.1％的质量比与0#柴油进行混合；The polymer pour point depressant is mixed with 0 # diesel oil at a mass ratio of 0.1%;
上述所用的聚合物降凝剂为聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant used above is polyethylene-vinyl acetate pour point depressant T1804;
经测试与0#柴油相比，含有聚合物降凝剂柴油的冷滤点和冷凝点分别降低8℃和13℃。After testing, compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing polymer pour point depressant were lowered by 8°C and 13°C respectively.
通过上述实施例1和对照实施例1进行对比，可以看出含有新型纳米复合降凝剂的柴油，降凝效果更佳，这主要是由于新型纳米复合降凝剂是聚合物降凝剂与纳米蒙脱石材料以2:1质量比进行复合，在高温下，聚合物降凝剂与纳米蒙脱石二者都同时达到熔点，形成一种混合均匀的熔融态物质，使新型纳米复合降凝剂其不仅具有普通降凝剂的降凝效果，而且所含的纳米蒙脱石材料由于具有较高的表面能，还会进一步增强其降凝效果。Through the comparison of the above-mentioned Example 1 and Comparative Example 1, it can be seen that the diesel oil containing the new nanocomposite pour point depressant has a better pour point depressant effect, which is mainly because the new nanocomposite pour point depressant is a combination of polymer pour point depressant and nano The montmorillonite material is compounded at a mass ratio of 2:1. At high temperature, both the polymer pour point depressant and the nano-montmorillonite reach the melting point at the same time, forming a uniformly mixed molten substance, which makes the new nanocomposite pour point depressant It not only has the pour point depressing effect of ordinary pour point depressants, but also the nano-montmorillonite material contained in it will further enhance its pour point depressing effect due to its high surface energy.
实施例2Example 2
一种新型纳米复合降凝剂，其通过包括如下步骤的方法制备而成：A novel nanocomposite pour point depressant prepared by a method comprising the following steps:
(1)一定量纳米蒙脱石与十六烷基三甲基溴化铵在水为溶剂下，80℃条件下进行有机改性反应，即得到有机改性蒙脱石；(1) A certain amount of nano-montmorillonite and hexadecyltrimethylammonium bromide are subjected to an organic modification reaction at 80°C under water as a solvent to obtain an organically modified montmorillonite;
(2)将有机改性后的纳米蒙脱石材料与聚合物降凝剂置于烧瓶中，采用熔融共混法，在120℃下反应3小时，即得一种新型纳米复合降凝剂；(2) Place the organically modified nano-montmorillonite material and the polymer pour point depressant in a flask, and react at 120° C. for 3 hours by a melt blending method to obtain a novel nanocomposite pour point depressant;
上述反应所用的聚合物降凝剂、有机改性纳米蒙脱石的量，按质量比计算，即聚合物降凝剂：有机改性纳米蒙脱石为4:1；The amount of polymer pour point depressant used in the above-mentioned reaction, organically modified nano-montmorillonite is calculated by mass ratio, that is, polymer pour point depressant: organically modified nano-montmorillonite is 4:1;
所述的聚合物降凝剂为聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant is polyethylene-vinyl acetate pour point depressant T1804;
将上述纳米复合降凝剂添加质量比优选为0.1％，加入到0#柴油中，经测试与0#柴油相比，含有新型纳米复合降凝剂柴油的冷滤点和冷凝点分别降低20℃和26℃。The above-mentioned nanocomposite pour point depressant is preferably added at a mass ratio of 0.1%, and added to 0 # diesel oil. Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing the new nanocomposite pour point depressant are respectively lowered by 20°C and 26°C.
对照实施例2Comparative Example 2
将聚合物降凝剂以0.1％的质量比与柴油进行混合；The polymer pour point depressant is mixed with diesel oil at a mass ratio of 0.1%;
上述所用的聚合物降凝剂为聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant used above is polyethylene-vinyl acetate pour point depressant T1804;
经测试与0#柴油相比，含有聚合物降凝剂柴油的冷滤点和冷凝点分别降低8℃和13℃。After testing, compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing polymer pour point depressant were lowered by 8°C and 13°C respectively.
通过上述对照实施例2和应用实施例2进行对比，可以看出新型纳米复合降凝剂对于柴油的降凝效果更佳。应用实施例2中新型纳米复合降凝剂是由聚合物降凝剂与纳米蒙脱石以质量比为4:1的条件下制备而成，对于柴油的降凝效果最佳，这主要是因为在高温下，聚合物降凝剂与纳米蒙脱石二者都同时达到熔点，形成一种混合均匀的熔融态物质，二者相辅相成，共同起到降凝作用，而且所含的纳米蒙脱石材料由于具有较高的表面能，还会进一步增强其降凝效果，因此达到了最佳的降凝效果。Through the comparison of the above-mentioned comparative example 2 and application example 2, it can be seen that the new nanocomposite pour point depressant has a better pour point depressant effect on diesel. The new nano-composite pour point depressant in application example 2 is prepared from polymer pour point depressant and nano-montmorillonite with a mass ratio of 4:1, and has the best pour point depressant effect on diesel, mainly because At high temperature, both the polymer pour point depressant and the nano-montmorillonite reach the melting point at the same time, forming a uniformly mixed molten substance. Due to the high surface energy of the material, its pour point depressing effect will be further enhanced, thus achieving the best pour point depressing effect.
实施例3Example 3
一种新型纳米复合降凝剂，其通过包括如下步骤的方法制备而成：A novel nanocomposite pour point depressant prepared by a method comprising the following steps:
(1)一定量纳米蒙脱石与十六烷基三甲基溴化铵在水为溶剂下，80℃条件下进行有机改性反应，即得到有机改性蒙脱石；(1) A certain amount of nano-montmorillonite and hexadecyltrimethylammonium bromide are subjected to an organic modification reaction at 80°C under water as a solvent to obtain an organically modified montmorillonite;
(2)将有机改性后的纳米蒙脱石材料与降凝剂置于烧瓶中，采用熔融共混法，在120℃下反应3小时，即得一种新型纳米复合降凝剂；(2) Place the organically modified nano-montmorillonite material and the pour point depressant in a flask, and react at 120° C. for 3 hours by a melt blending method to obtain a novel nanocomposite pour point depressant;
上述反应所用的聚合物降凝剂、有机改性纳米蒙脱石的量，按质量比计算，即聚合物降凝剂：有机改性纳米蒙脱石为4:1；The amount of polymer pour point depressant used in the above-mentioned reaction, organically modified nano-montmorillonite is calculated by mass ratio, that is, polymer pour point depressant: organically modified nano-montmorillonite is 4:1;
所述的聚合物降凝剂为聚甲基丙烯酸酯类降凝剂10-330；The polymer pour point depressant is polymethacrylate pour point depressant 10-330;
将上述纳米复合降凝剂添加质量比优选为0.1％，加入到0#柴油中，经测试与0#柴油相比，含有新型纳米复合降凝剂柴油的冷滤点和冷凝点分别降低18℃和24℃。The above-mentioned nanocomposite pour point depressant is preferably added at a mass ratio of 0.1%, and added to 0 # diesel oil. Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing the new nanocomposite pour point depressant are respectively lowered by 18°C and 24°C.
对照实施例3Comparative Example 3
将聚合物降凝剂以0.1％的质量比与0#柴油进行混合；The polymer pour point depressant is mixed with 0 # diesel oil at a mass ratio of 0.1%;
上述所用的聚合物降凝剂为聚甲基丙烯酸酯类降凝剂10-330；The polymer pour point depressant used above is polymethacrylate pour point depressant 10-330;
经测试与0#柴油相比，含有聚合物降凝剂柴油的冷滤点和冷凝点分别降低7℃和12℃。Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing polymer pour point depressant were lowered by 7°C and 12°C, respectively.
通过上述实施例1和应用实施例1进行对比，可以看出含有新型纳米复合降凝剂的柴油，降凝效果更佳，这主要是由于新型纳米复合降凝剂在聚合物降凝剂与纳米蒙脱石材料以4:1的质量比，在高温下，聚合物降凝剂与纳米蒙脱石二者都同时达到熔点，形成一种混合均匀的熔融态物质，二者相辅相成，共同起到降凝作用不仅具有普通降凝剂的降凝效果，而且所含的纳米蒙脱石材料由于具有较高的表面能，还会进一步增强其降凝效果。Through the comparison of the above Example 1 and Application Example 1, it can be seen that the diesel oil containing the new nanocomposite The mass ratio of montmorillonite material is 4:1. At high temperature, both the polymer pour point depressant and the nano-montmorillonite reach the melting point at the same time, forming a uniformly mixed molten substance. The two complement each other and play a role together. The pour point depressing effect not only has the pour point depressing effect of ordinary pour point depressants, but also the nano-montmorillonite material contained in it will further enhance its pour point depressing effect due to its high surface energy.
实施例4Example 4
一种新型纳米复合降凝剂，其通过包括如下步骤的方法制备而成：A novel nanocomposite pour point depressant prepared by a method comprising the following steps:
(1)一定量纳米蒙脱石与十六烷基三甲基溴化铵在水为溶剂下，80℃条件下进行有机改性反应，即得到有机改性蒙脱石；(1) A certain amount of nano-montmorillonite and hexadecyltrimethylammonium bromide are subjected to an organic modification reaction at 80°C under water as a solvent to obtain an organically modified montmorillonite;
(2)将有机改性后的纳米蒙脱石材料与降凝剂置于烧瓶中，采用熔融共混法，在120℃下反应3小时，即得一种新型纳米复合降凝剂；(2) Place the organically modified nano-montmorillonite material and the pour point depressant in a flask, and react at 120° C. for 3 hours by a melt blending method to obtain a novel nanocomposite pour point depressant;
上述反应所用的聚合物降凝剂、有机改性纳米蒙脱石的量，按质量比计算，即聚合物降凝剂：有机改性纳米蒙脱石为1:1；The amount of polymer pour point depressant and organically modified nano-montmorillonite used in the above reaction is calculated by mass ratio, that is, polymer pour point depressant: organically modified nano-montmorillonite is 1:1;
所述的聚合物降凝剂为聚甲基丙烯酸酯类降凝剂10-330，聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant is polymethacrylate type pour point depressant 10-330, polyethylene-vinyl acetate type pour point depressant T1804;
将上述纳米复合降凝剂添加质量比优选为0.1％，加入到0#柴油中，经测试与0#柴油相比，含有新型纳米复合降凝剂柴油的冷滤点和冷凝点分别降低12℃和18℃。The above-mentioned nanocomposite pour point depressant is preferably added at a mass ratio of 0.1%, and added to 0 # diesel oil. Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing the new nanocomposite pour point depressant are respectively lowered by 12°C and 18°C.
实施例5Example 5
一种新型纳米复合降凝剂，其通过包括如下步骤的方法制备而成：A novel nanocomposite pour point depressant prepared by a method comprising the following steps:
(1)一定量纳米蒙脱石与十六烷基三甲基溴化铵在水为溶剂下，80℃条件下进行有机改性反应，即得到有机改性蒙脱石；(1) A certain amount of nano-montmorillonite and hexadecyltrimethylammonium bromide are subjected to an organic modification reaction at 80°C under water as a solvent to obtain an organically modified montmorillonite;
(2)将有机改性后的纳米蒙脱石材料与降凝剂置于烧瓶中，采用熔融共混法，在120℃下反应3小时，即得一种新型纳米复合降凝剂；(2) Place the organically modified nano-montmorillonite material and the pour point depressant in a flask, and react at 120° C. for 3 hours by a melt blending method to obtain a novel nanocomposite pour point depressant;
上述反应所用的聚合物降凝剂、有机改性纳米蒙脱石的量，按质量比计算，即聚合物降凝剂：有机改性纳米蒙脱石为8:1；The amount of polymer pour point depressant used in the above-mentioned reaction, organically modified nano-montmorillonite is calculated by mass ratio, that is, polymer pour point depressant: organically modified nano-montmorillonite is 8:1;
所述的聚合物降凝剂为聚甲基丙烯酸酯类降凝剂10-330，聚乙烯-醋酸乙烯酯类降凝剂T1804；The polymer pour point depressant is polymethacrylate type pour point depressant 10-330, polyethylene-vinyl acetate type pour point depressant T1804;
将上述纳米复合降凝剂添加质量比优选为0.1％，加入到0#柴油中，经测试与0#柴油相比，含有新型纳米复合降凝剂柴油的冷滤点和冷凝点分别降低18℃和20℃。The above-mentioned nanocomposite pour point depressant is preferably added at a mass ratio of 0.1%, and added to 0 # diesel oil. Compared with 0 # diesel oil, the cold filter point and condensation point of diesel oil containing the new nanocomposite pour point depressant are respectively lowered by 18°C and 20°C.
综上所述，本发明的一种新型纳米复合降凝剂，其中所含的纳米材料与降凝剂共同起到降凝作用，所含的纳米材料由于具有较高的表面能，为了维持体系能量稳定，在添加纳米复合降凝剂的柴油中蜡晶在析出聚集时趋向于比添加等量纯降凝剂柴油中蜡晶更紧凑的排布方式，以减小界面面积降低表面能。紧凑的蜡晶聚集体使得更多原来被包裹的液态油被释放出来，大大降低了蜡-油界面面积。一方面使得柴油流动时蜡晶与液态柴油间摩擦耗散能量减少，使得柴油低温下黏度进一步降低，流动性进一步改善；另一方面蜡晶表面能的降低导致柴油体系形成的胶凝结构的温度和强度也大大降低，从而进一步使得柴油低温性能得到改善。In summary, a new type of nanocomposite pour point depressant of the present invention, the nanomaterial contained in it and the pour point depressant together play a depressant effect, and the contained nanomaterial has a high surface energy, in order to maintain the system The energy is stable, and the wax crystals in diesel fuel with nano-composite pour point depressant tend to be arranged more compactly than the wax crystals in diesel fuel with the same amount of pure pour point depressant when they precipitate and aggregate, so as to reduce the interface area and surface energy. The compact wax crystal aggregates release more of the originally encapsulated liquid oil, greatly reducing the wax-oil interfacial area. On the one hand, the energy dissipated by friction between wax crystals and liquid diesel oil is reduced when diesel oil is flowing, which further reduces the viscosity of diesel oil at low temperature and improves fluidity; And the strength is also greatly reduced, which further improves the low temperature performance of diesel.
上述内容仅为本发明构思下的基本说明，而依据本发明的技术方案所做的任何等效变换，均应属于本发明的保护范围。The above content is only a basic description of the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall belong to the protection scope of the present invention.
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| CN112694924A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Nano composite pour point depressant, preparation method thereof and pour point depressing working solution for high-water-content crude oil |
| CN112694924B (en) * | 2019-10-22 | 2022-06-14 | 中国石油化工股份有限公司 | Nano composite pour point depressant, preparation method thereof and pour point depressing working solution for high-water-content crude oil |
| CN110804191A (en) * | 2019-11-21 | 2020-02-18 | 东北石油大学 | Preparation method of nano wax-proof pour point depressant |
| CN113402724A (en) * | 2021-06-11 | 2021-09-17 | 东北石油大学 | Preparation method of nano composite pour point depressant |
| CN114479965A (en) * | 2022-01-18 | 2022-05-13 | 上海应用技术大学 | A kind of composite nano diesel pour point depressant and its preparation method and application |
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Application publication date: 20160928 |