技术领域technical field
本发明涉及旨在用作液体可燃物的包含含碳材料颗粒的浆料悬浮液领域。The invention relates to the field of slurry suspensions containing particles of carbonaceous material intended to be used as liquid combustibles.
背景技术Background technique
为了减少污染环境的来自燃料燃烧的硫的排放并且符合关于燃料消耗的法规，炼油厂提供了可获得的由柴油的精炼的重质燃料构成的低硫含量燃料。然而，由于昂贵的工艺，这些燃料替代物通常与较不精炼的那些相比更昂贵。In order to reduce environmentally polluting sulfur emissions from fuel combustion and to comply with regulations on fuel consumption, refineries make available low sulfur content fuels consisting of refined heavy fuel from diesel. However, these fuel alternatives are generally more expensive than less refined ones due to expensive processes.
另外，由于归因于天然储量下降的预期原油短缺，比以往更迫切的是找到一些有效的替代物来减少化石基能源的部分。In addition, due to the expected shortage of crude oil due to the decline of natural reserves, it is more urgent than ever to find some effective alternatives to reduce the portion of fossil-based energy sources.
进一步精炼燃料的一些替代方案在于用生物燃料替换化石基可燃物，这种开发通常目的在于设计新的催化过程以将固体生物质转化为液体燃料。然而，这种破坏性方法通常因由生物质制成生物燃料或制造生物燃料的竞争性价格而受到损害。Some alternatives to further refine fuels lie in the replacement of fossil-based combustibles with biofuels, often with the aim of designing new catalytic processes to convert solid biomass into liquid fuels. However, this disruptive approach is often compromised by the competitive prices of making biofuels from biomass or making biofuels.
最近提出了一些其他替代方案来增加燃料组合物中的可再生燃料部分。例如，其中将煤分散到水中的基于煤/水浆料(CWS)的技术提供了与现有液体锅炉相容的液体燃料。Several other alternatives have recently been proposed to increase the renewable fuel portion of the fuel mix. For example, coal/water slurry (CWS) based technology, where coal is dispersed in water, provides a liquid fuel that is compatible with existing liquid boilers.
然而，煤/水浆料的缺点是水对于燃烧是惰性的，并且因此降低了水性煤或生物煤悬浮液的总热值。However, a disadvantage of coal/water slurries is that water is inert to combustion and thus reduces the gross calorific value of aqueous coal or biocoal suspensions.
可以探索的另一个替代方案是使用经焙烧的生物质来用于具有成本竞争性特点地生产可再生能源，并且考虑到与白色未经焙烧的生物质相比为高能量密度材料而主要用于运输。Another alternative that could be explored is the use of torrefied biomass for the production of renewable energy with cost-competitive characteristics and mainly used in transportation.
这种“热处理的生物质”提供了有意义的特性，诸如低硫含量、低氮含量、和优异的燃烧特性。This "heat-treated biomass" provides interesting properties such as low sulfur content, low nitrogen content, and excellent combustion characteristics.
此外，如与未经焙烧的、白色的生物质相比，经焙烧的生物质是惰性材料，并且由于在焙烧过程中氧的损失，该材料获得疏水特性。Furthermore, torrefied biomass is an inert material as compared to unfired, white biomass, and due to the loss of oxygen during the torrefaction process, the material acquires hydrophobic properties.
在本领域中仍然存在对于提供产生低硫排放的液体可燃配制品的需要，其中化石基能源仅占减少的部分。There remains a need in the art to provide liquid combustible formulations that produce low sulfur emissions, with fossil-based energy sources accounting for only the reduced portion.
更特别地，因为含碳材料提供良好的燃烧特性，在本领域中仍然存在在液体载体中提供包含所述含碳材料的悬浮液的需要，所述悬浮液均匀且稳定地分散。More particularly, because carbonaceous materials provide good combustion characteristics, there remains a need in the art to provide a suspension comprising said carbonaceous materials in a liquid carrier that is uniformly and stably dispersed.
此外，在本领域中仍然对于提供与现有系统(诸如发动机和锅炉)相容的液体可燃配制品的需要。Furthermore, there remains a need in the art to provide liquid flammable formulations that are compatible with existing systems such as engines and boilers.
发明内容Contents of the invention
本发明的第一方面涉及一种浆料悬浮液，该浆料悬浮液包含：A first aspect of the present invention relates to a slurry suspension comprising:
(a)具有包括在0.1μm与200μm之间的平均直径D50的含碳材料颗粒；(a) particles of carbonaceous material having an average diameterD50 comprised between 0.1 μm and 200 μm;
(b)非离子表面活性剂；(b) nonionic surfactants;
(c)水相；以及(c) an aqueous phase; and
(d)有机相。(REV 1)(d) Organic phase. (REV 1)
本发明的另一方面涉及一种用于制备根据本发明的浆料悬浮液的方法，该方法包括以下步骤：Another aspect of the present invention relates to a method for preparing a slurry suspension according to the present invention, the method comprising the steps of:
i.至少混合成分(b)、(c)和(d)以形成乳液；i. mixing at least ingredients (b), (c) and (d) to form an emulsion;
ii将成分(a)与步骤i.中获得的乳液混合以形成浆料悬浮液。(REV 16)ii Mixing ingredient (a) with the emulsion obtained in step i. to form a slurry suspension. (REV 16)
本发明的另一方面涉及一种用于发电的方法，该方法包括燃烧根据本发明的浆料悬浮液。(REV 18)Another aspect of the invention relates to a method for generating electricity comprising combusting a slurry suspension according to the invention. (REV 18)
本发明的还另一方面涉及非离子表面活性剂用来稳定化包含具有包括在0.1μm与200μm之间的平均直径D50的含碳材料颗粒的乳液的用途。(REV 19)Yet another aspect of the invention relates to the use of a nonionic surfactant to stabilize an emulsion comprising carbonaceous material particles having a mean diameter D50 comprised between 0.1 μm and 200 μm. (REV 19)
具体实施方式detailed description
诸位发明人出人意料地发现，可以将含碳材料颗粒加入到乳液中、特别是水包油乳液中，以获得可以进一步用作用于燃烧的液体生物燃料的稳定且均匀分散的浆料悬浮液。The inventors have surprisingly found that carbonaceous material particles can be added to emulsions, especially oil-in-water emulsions, to obtain stable and homogeneously dispersed slurry suspensions that can be further used as liquid biofuels for combustion.
乳液、特别是水包油乳液通过非离子表面活性剂的存在来稳定化。Emulsions, especially oil-in-water emulsions, are stabilized by the presence of nonionic surfactants.
浆料悬浮液pulp suspension
因此，本发明的第一方面涉及一种浆料悬浮液，该浆料悬浮液包含：Accordingly, a first aspect of the present invention relates to a slurry suspension comprising:
(a)具有包括在0.1μm与200μm之间的平均直径D50的含碳材料颗粒；(a) particles of carbonaceous material having an average diameterD50 comprised between 0.1 μm and 200 μm;
(b)非离子表面活性剂；(b) nonionic surfactants;
(c)水相；以及(c) an aqueous phase; and
(d)有机相。(REV 1)(d) Organic phase. (REV 1)
在本发明的范围内，术语“悬浮液”是指包含以具有大于胶体尺寸的颗粒分散在包含水相、有机相和非离子表面活性剂的液相中的含碳材料颗粒(即固体材料)的体系。Within the scope of the present invention, the term "suspension" means particles comprising carbonaceous material (i.e. solid material) dispersed in a liquid phase comprising an aqueous phase, an organic phase and a nonionic surfactant as particles having a size larger than a colloid system.
在某些实施例中，术语“悬浮液”是指包含在其中分散有含碳材料颗粒的乳液(即液相)的体系(乳液态)。In certain embodiments, the term "suspension" refers to a system (emulsion state) comprising an emulsion (ie, liquid phase) of carbonaceous material particles dispersed therein.
在某些实施例中，术语“悬浮液”是指在其中水性液相和有机液相是分开的相并且不形成乳液的体系；含碳材料颗粒被分散在这些液相中(非乳液状态)。In certain embodiments, the term "suspension" refers to a system in which the aqueous liquid phase and the organic liquid phase are separate phases and do not form an emulsion; the carbonaceous material particles are dispersed in these liquid phases (non-emulsion state) .
在本发明的范围内，术语“约”是指可以从所提及的值变化从+/-10％的值。Within the scope of the present invention, the term "about" refers to a value that may vary by +/- 10% from the value mentioned.
含碳材料颗粒carbonaceous material particles
在本发明的范围内，术语“含碳材料”是指含有大量碳的材料。Within the scope of the present invention, the term "carbonaceous material" means a material containing a large amount of carbon.
对于本发明有用的含碳材料颗粒的含碳量典型地基于含碳材料颗粒的总重量超过30wt.％；它经常是超过40wt.％。基于含碳材料颗粒的总重量，它优选超过45wt.％、更优选超过50wt.％。在另一方面，基于含碳材料颗粒的总重量，它典型地是高达90wt.％、并且经常高达80wt.％。基于含碳材料颗粒的总重量，它可以是高达70wt.％或者甚至高达60wt.％。对于本发明有用的含碳材料颗粒的含碳量的某些有用的范围是基于含碳材料颗粒的总重量的从约40wt.％至约80wt.％、或从约45wt.％至约75wt.％。含碳材料颗粒的含碳量可以通过本领域技术人员已知的任何方法来确定。例如，它可以通过以下步骤来确定：在烘箱中在100℃下干燥含碳材料颗粒12h(以去除水和其他挥发物)，然后将干燥的颗粒保持在干燥器中(以避免水分吸收)，然后在燃烧炉中在能够将含碳材料颗粒的基本上全部(当不是时，全部)含碳量转化为二氧化碳的条件下燃烧含碳材料颗粒，然后通过红外检测(通过经由燃烧形成的CO2)定量C含量。The carbon content of the carbonaceous material particles useful for the present invention is typically in excess of 30 wt.%, based on the total weight of the carbonaceous material particles; it is often in excess of 40 wt.%. It is preferably more than 45 wt.%, more preferably more than 50 wt.%, based on the total weight of the carbonaceous material particles. On the other hand, it is typically up to 90 wt.%, and often up to 80 wt.%, based on the total weight of the carbonaceous material particles. It may be up to 70 wt.% or even up to 60 wt.%, based on the total weight of the carbonaceous material particles. Some useful ranges for the carbon content of the carbonaceous material particles useful in the present invention are from about 40 wt.% to about 80 wt.%, or from about 45 wt.% to about 75 wt.%, based on the total weight of the carbonaceous material particles. %. The carbon content of the carbonaceous material particles can be determined by any method known to those skilled in the art. For example, it can be determined by drying carbonaceous material particles in an oven at 100 °C for 12 h (to remove water and other volatiles), and then keeping the dried particles in a desiccator (to avoid moisture absorption), The carbonaceous material particles are then combusted in a combustion furnace under conditions capable of converting substantially all (if not all) of the carbon content of the carbonaceous material particles into carbon dioxide, which is then detected by infrared detection (byCO2 formed via combustion) ) Quantitative C content.
在一个实施例中，该含碳材料颗粒选自下组，该组包含植物生物质、煤、焦炭、石墨、炭、生物煤及其混合物。(REV 3)In one embodiment, the carbonaceous material particles are selected from the group consisting of plant biomass, coal, coke, graphite, charcoal, biocoal, and mixtures thereof. (REV 3)
根据本发明，植物生物质包含木质纤维素纤维，并且可以由易于提供合适的生物质的任何植物、木材和作物提供。According to the present invention, plant biomass comprises lignocellulosic fibers and can be provided by any plant, wood and crop that readily provides suitable biomass.
植物诸如芒属、柳枝稷、大麻；木材，诸如杨树、竹子、桉树、油棕榈树、柳树、松树、橡树、树胶、山杨、山毛榉、椰子树和云杉；以及作物，诸如玉米、高粱、甘蔗和甜菜适合于实施本发明。Plants such as miscanthus, switchgrass, hemp; wood such as poplar, bamboo, eucalyptus, oil palm, willow, pine, oak, gum, aspen, beech, coconut tree, and spruce; and crops such as corn, sorghum, Sugar cane and sugar beets are suitable for practicing the invention.
在某些实施例中，植物生物质选自下组，该组包含植物或其一部分，例如叶、茎、根，包括作物或其一部分；木材，木片或木屑；稻草；树皮；草；林业剩余物；农业剩余物，诸如玉米棒、玉米秸、玉米秆、麦秸、竹草、藤蔓(vineshoot)、甘蔗渣、高粱渣、杏仁壳、向日葵籽壳及其混合物。In certain embodiments, plant biomass is selected from the group comprising plants or parts thereof, such as leaves, stems, roots, including crops or parts thereof; wood, wood chips or sawdust; straw; bark; grasses; forestry Residues; agricultural residues such as corn cobs, corn stover, corn stover, wheat straw, bamboo grass, vineshoot, bagasse, sorghum bagasse, almond hulls, sunflower seed hulls, and mixtures thereof.
在某些实施例中，植物生物质经受处理以去除其含水量，这种处理是干热处理、蒸汽爆破、真空蒸发、水热碳化、或从现有技术已知的任何合适的处理。In certain embodiments, plant biomass is subjected to a treatment to remove its water content, such treatment being dry heat treatment, steam explosion, vacuum evaporation, hydrothermal carbonization, or any suitable treatment known from the prior art.
干热处理法可以包括在低于200℃至500℃的最高温度的温度下处理起始生物质持续从几分钟至几小时的时间段。The dry heat treatment process may involve treating the starting biomass at a temperature below a maximum temperature of 200°C to 500°C for a period of time from a few minutes to a few hours.
在某些实施例中，干热处理由在范围从约280℃至约320℃的温度内进行的焙烧持续范围从1min至15min、优选从2min至8min的时间段组成。In certain embodiments, the dry heat treatment consists of firing at a temperature ranging from about 280°C to about 320°C for a period ranging from 1 min to 15 min, preferably from 2 min to 8 min.
在某些优选的实施例中，植物生物质是经焙烧的植物生物质、优选是经焙烧的木材颗粒。(权利要求4)In certain preferred embodiments, the plant biomass is torrefied plant biomass, preferably torrefied wood particles. (claim 4)
在某些实施例中，含碳材料是煤，诸如无烟煤、半无烟煤、木炭、溶剂精炼煤、中等和高挥发性烟煤、次烟煤和褐煤。In certain embodiments, the carbonaceous material is coal, such as anthracite, semi-anthracite, charcoal, solvent refined coal, medium and high volatility bituminous coal, sub-bituminous coal, and lignite.
在某些实施例中，含碳材料是焦炭，诸如石油焦、高温焦炭、铸用焦炭、低温焦炭、中温焦炭、沥青焦炭、或者通过碳化煤、沥青、石油残渣、和某些其他含碳材料获得的任何产物。In certain embodiments, the carbonaceous material is coke, such as petroleum coke, high temperature coke, foundry coke, low temperature coke, medium temperature coke, pitch coke, or by carbonization of coal, pitch, petroleum residue, and certain other carbonaceous materials any product obtained.
在一些实施例中，煤和石油焦的混合物可以在本发明中使用。In some embodiments, a mixture of coal and petroleum coke may be used in the present invention.
当提到“含碳材料颗粒”时，人们可以理解所述颗粒具有低的含水量或是无水的。通过“低含水量”，人们可以理解如与起始材料的重量相比高达按重量计20％的含水量。因此，按重量计最高达20％的水包括如与起始材料的重量相比按重量计0％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％和20％的含水量。When referring to "particles of carbonaceous material", one understands that the particles have a low moisture content or are anhydrous. By "low moisture content" one understands eg a moisture content of up to 20% by weight compared to the weight of the starting material. Thus, up to 20% by weight of water includes 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight as compared to the weight of the starting material , 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% and 20% water content.
在本发明的范围内，表述“含碳材料颗粒”是指固态的含碳材料的颗粒。Within the scope of the present invention, the expression "carbonaceous material particles" refers to solid particles of carbonaceous material.
本发明所包含的含碳材料颗粒是在使用碾磨机对含碳材料进行精细的湿式或干式碾磨之后获得的。当进行湿式碾磨时，可以将含碳材料颗粒进一步处理以经历旨在将其含水量降低到最大20％的干热处理。相反地，当进行干式碾磨时，根据本发明的含碳材料颗粒具有如与起始材料的重量相比按重量计最大20％的含水量。The carbonaceous material particles included in the present invention are obtained after finely wet or dry milling the carbonaceous material using a mill. When wet milling is performed, the carbonaceous material particles can be further treated to undergo a dry heat treatment aimed at reducing their moisture content to a maximum of 20%. Conversely, when dry milling is performed, the carbonaceous material particles according to the present invention have a water content of at most 20% by weight as compared to the weight of the starting material.
在某些实施例中，这些含碳材料颗粒提供如下尺寸分布：In certain embodiments, the carbonaceous material particles provide the following size distribution:
-D10是包括在1与50μm之间，并且-D10 is comprised between 1 and 50 µm, and
-D90是包括在50与500μm之间。(REV 5)-D90 is comprised between 50 and 500 μm. (REV 5)
在本发明的范围内，颗粒的尺寸可以通过从现有技术中已知的任何合适的平均值来测量。Within the scope of the present invention, the size of the particles may be measured by any suitable mean value known from the prior art.
在优选的实施例中，颗粒的尺寸分布是鉴于在ISO 13320：2009(E)中规定的原则和基本规则，通过干分散的激光衍射的平均值测量的。In a preferred embodiment, the size distribution of the particles is measured by means of dry dispersed laser diffraction in view of the principles and ground rules specified in ISO 13320:2009(E).
实际上，使用Helos H1302激光衍射传感器(Sympatec，德国)进行分析。选择检测器焦距，使得其通带覆盖有待分析的含碳材料颗粒的尺寸范围。例如，当分析研磨的经焙烧的生物质时，R4检测器(0.5μm至350μm)特别好地适合。Actually, analysis was performed using a Helos H1302 laser diffraction sensor (Sympatec, Germany). The detector focal length is chosen such that its passband covers the size range of the carbonaceous material particles to be analyzed. For example, the R4 detector (0.5 μm to 350 μm) is particularly well suited when analyzing ground torrefied biomass.
使用干燥分散单元(Rodos，德国新帕泰克)将含碳材料颗粒在压力下分散在干燥氮气流中。Carbonaceous material particles were dispersed under pressure in a dry nitrogen stream using a dry dispersion unit (Rodos, Sipatec, Germany).
实验上寻求最佳操作条件以获得良好的颗粒分散体，而不会在喷射器中破碎。在实践中，当分析呈碾磨的经焙烧的生物质形式的含碳材料颗粒时，氮气压力是约100kPa(1巴)并且低压(depression)代表约4kPa(40毫巴)。Optimum operating conditions were sought experimentally to obtain a good particle dispersion without breaking up in the injector. In practice, when analyzing particles of carbonaceous material in the form of ground torrefied biomass, the nitrogen pressure is about 100 kPa (1 bar) and the depression represents about 4 kPa (40 mbar).
含碳材料颗粒使用振动槽进料。调节进料速率以获得在2％与10％之间的光学浓度。在实践中，含有有待分析的含碳材料颗粒的样品的总质量是在从约1g至约10g的范围，优选约5g。Carbonaceous material pellets are fed using a vibrating trough. The feed rate was adjusted to obtain an optical concentration between 2% and 10%. In practice, the total mass of the sample containing particles of carbonaceous material to be analyzed ranges from about 1 g to about 10 g, preferably about 5 g.
使用Windox 5软件(德国新帕泰克)获取并且分析激光衍射数据。Laser diffraction data were acquired and analyzed using Windox 5 software (Sypatec, Germany).
在一个实施例中，含碳材料颗粒代表按重量计在5％与50％之间的该悬浮液的总重量。(REV 6)In one embodiment, the carbonaceous material particles represent between 5% and 50% by weight of the total weight of the suspension. (REV 6)
非离子表面活性剂nonionic surfactant
在本发明的范围内，非离子表面活性剂可以选自下组，该组包含醚基非离子表面活性剂、酯基非离子表面活性剂、胺基或酰胺基非离子表面活性剂和氟表面活性剂。(REV7)Within the scope of the present invention, nonionic surfactants may be selected from the group consisting of ether-based nonionic surfactants, ester-based nonionic surfactants, amine-based or amide-based nonionic surfactants, and fluorosurfactants active agent. (REV7)
a)醚基非离子表面活性剂a) ether-based nonionic surfactant
在醚基非离子表面活性剂中，人们可以列举羧酸基非离子表面活性剂、醇基非离子表面活性剂、糖苷(oside)基非离子表面活性剂、脂肪醇基非离子表面活性剂和硅氧烷非离子表面活性剂的醚。Among the ether-based nonionic surfactants, one can cite carboxylic acid-based nonionic surfactants, alcohol-based nonionic surfactants, glycoside (oside)-based nonionic surfactants, fatty alcohol-based nonionic surfactants, and Ether of silicone nonionic surfactant.
根据本发明有意义的非离子乳化剂可以由具有如下式(1)的羧酸的醚表示：Nonionic emulsifiers of interest according to the invention can be represented by ethers of carboxylic acids having the following formula (1):
R1-O-(R2-O)y-CH2-COOH(1)，R1-O-(R2-O)y-CH2-COOH(1),
其中R1是C8-C20烷基、C8-C20烷基苯基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R1 is C8-C20 alkyl, C8-C20 alkylphenyl or C8-C20 alkenyl, R2 is C2-C10 alkylene, such as -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, And the range of y is from 2 to 50.
在某些实施例中，羧酸的醚由具有式(1)的化合物表示，其中R2是C2或C3亚烷基。In certain embodiments, ethers of carboxylic acids are represented by compounds having formula (1), wherein R2 is C2 or C3 alkylene.
特别地，羧酸基非离子表面活性剂的醚优选由聚氧亚乙基非离子表面活性剂(-(CH2-CH2-O)-)、聚氧亚丙基非离子表面活性剂(-(CH2-CH2-CH2-O)-)、聚氧亚乙基-聚氧亚丙基非离子表面活性剂表示。Particularly, the ether of carboxylic acid base nonionic surfactant is preferably made of polyoxyethylene nonionic surfactant (-(CH2-CH2-O)-), polyoxypropylene nonionic surfactant (-( CH2-CH2-CH2-O)-), polyoxyethylene-polyoxypropylene nonionic surfactant representation.
聚氧亚乙基非离子表面活性剂可以包含聚氧亚乙基烷基醚、聚氧亚乙基烷基苯基醚、聚氧亚乙基聚氧亚丙基烷基醚。The polyoxyethylene nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether.
在聚氧亚乙基烷基醚中，人们可以列举诸如聚氧亚乙基十六烷基醚、聚氧亚乙基月桂醚、聚氧亚乙基辛醚、聚氧亚乙基油烯基醚、聚氧亚乙基硬脂醚、聚氧亚乙基异硬脂醚的化合物。Among the polyoxyethylene alkyl ethers, one may cite examples such as polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene oleyl Ether, polyoxyethylene stearyl ether, polyoxyethylene isostearyl ether compounds.
在聚氧亚乙基烷基苯基醚中，人们可以列举诸如聚氧亚乙基辛基苯基醚、聚氧亚乙基壬基苯基醚和二烷基苯氧基聚(亚乙基氧基)乙醇的化合物。Among the polyoxyethylene alkylphenyl ethers, one may cite such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and dialkylphenoxypoly(ethylene oxy)ethanol compounds.
在聚氧亚乙基聚氧亚丙基烷基醚中，人们可以列举诸如聚氧亚乙基聚氧亚丙基十六烷基醚、聚氧亚乙基聚氧亚丙基癸基十四烷基醚的化合物。Among the polyoxyethylene polyoxypropylene alkyl ethers, one may cite examples such as polyoxyethylene polyoxypropylene hexadecyl ether, polyoxyethylene polyoxypropylene decyltetradecyl ether, polyoxyethylene polyoxypropylene decyltetradecyl Alkyl ether compounds.
根据本发明有意义的醇基非离子表面活性剂可以由烷氧基化醇表示。Alcohol-based nonionic surfactants of interest according to the invention may be represented by alkoxylated alcohols.
在本发明的范围内，术语“烷氧基化的”取决于氧亚烷基单元的存在，其中这些单元的总数总体上是在从2至50、优选从3至25、优选从4至12、优选从2至10、最优选从2至6、或优选从10至50、最优选从10至35的范围。Within the scope of the present invention, the term "alkoxylated" depends on the presence of oxyalkylene units, wherein the total number of these units is generally in the range from 2 to 50, preferably from 3 to 25, preferably from 4 to 12 , preferably from 2 to 10, most preferably from 2 to 6, or preferably from 10 to 50, most preferably from 10 to 35.
有意义的烷氧基化醇可以由具有如下通式(2)的化合物表示：Interesting alkoxylated alcohols can be represented by compounds having the general formula (2):
R1-O-(R2-O)y-H(2)R1-O-(R2-O)y-H(2)
其中R1是C6-C30烃基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。wherein R1 is a C6-C30 hydrocarbon group, R2 is a C2-C10 alkylene group, such as -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.
优选地，烷氧基化醇可以由具有如下通式(3)的化合物表示：Preferably, the alkoxylated alcohol may be represented by a compound having the following general formula (3):
R3-O-(R2-O)y-H(3)R3-O-(R2-O)y-H(3)
其中R3是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50，或者Wherein R3 is C8-C20 alkyl or C8-C20 alkenyl, R2 is C2-C10 alkylene, such as -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and the range of y is from 2 to 50, or
可替代地，烷氧基化醇具有如下式(4)：Alternatively, the alkoxylated alcohol has the following formula (4):
其中R4是C4-C20烷基，特别地，R4是辛基(C8)或壬基(C9)，是对亚苯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R4 is C4-C20 alkyl, particularly, R4 is octyl (C8) or nonyl (C9), is p-phenylene, R2 is C2-C10 alkylene, such as -CH2-CH2-, -CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.
类似的醇可以通过用[2，4-6-三-(叔丁基)]-苯基替换上式(4)中的获得。Similar alcohols can be replaced by [2,4-6-tri-(tert-butyl)]-phenyl in the above formula (4) get.
根据本发明，适合作为非离子表面活性剂的烷氧基化醇的实例是(i)从2至50摩尔的至少一种C2-C3环氧烷，诸如环氧乙烷与(ii)一摩尔的烯键式饱和或不饱和的脂肪醇，尤其选自月桂醇、肉豆蔻醇、棕榈醇、硬脂醇、油醇、亚油醇、亚麻醇、羰基合成醇及其混合物的C8-C20醇的缩合产物。Examples of alkoxylated alcohols suitable as nonionic surfactants according to the invention are (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide with (ii) one mole Ethylenically saturated or unsaturated fatty alcohols, especially C8-C20 alcohols selected from the group consisting of lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, oxo alcohols and mixtures thereof condensation products.
根据本发明，适合作为非离子表面活性剂的烷氧基化醇的其他实例是(i)从2至50摩尔的至少一种C2-C3环氧烷诸如环氧乙烷与一摩尔的正辛基苯酚、正壬基苯酚及其混合物的缩合产物。Further examples of alkoxylated alcohols suitable as nonionic surfactants according to the invention are (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide such as ethylene oxide with one mole of n-octyl Condensation products of phenol, n-nonylphenol and mixtures thereof.
烷氧基化醇可以是以商品名(阿特拉斯化工公司(Atlas Chemical Co.))、(科莱恩公司(Clariant))和(巴斯夫公司(BASF))可商购的。Alkoxylated alcohols are available under the trade name (Atlas Chemical Co.), (Clariant) and (BASF) is commercially available.
糖苷基非离子表面活性剂可以包含长链烷基聚葡糖苷，其通过a)含有从约6至约25个碳原子的长链醇与b)葡萄糖或含葡萄糖的聚合物缩合而获得。实际上，这种化合物可以是烷基多糖苷和烷基多糖，诸如癸基葡糖苷、辛基葡糖苷或癸基麦芽糖苷。Glycoside-based nonionic surfactants may comprise long chain alkyl polyglucosides obtained by condensation of a) long chain alcohols containing from about 6 to about 25 carbon atoms with b) glucose or glucose-containing polymers. Indeed, such compounds may be alkyl polyglycosides and alkyl polysaccharides, such as decyl glucoside, octyl glucoside or decyl maltoside.
在某些实施例中，醚基非离子表面活性剂是烷氧基化的酚表面活性剂。(REV 8)In certain embodiments, the ether-based nonionic surfactant is an alkoxylated phenolic surfactant. (REV 8)
在某些实施例中，该烷氧基化的酚表面活性剂选自下组，该组包含烷氧基化的烷基酚、烷氧基化的烷基芳基酚、烷氧基化的硫酸化的和/或磷酸盐烷基酚以及烷氧基化的硫酸化和/或磷酸盐烷基芳基酚。(REV 9)In certain embodiments, the alkoxylated phenolic surfactant is selected from the group consisting of alkoxylated alkylphenols, alkoxylated alkylarylphenols, alkoxylated Sulfated and/or phosphated alkylphenols and alkoxylated sulfated and/or phosphated alkylarylphenols. (REV 9)
合适的烷氧基化的酚化合物包含氧亚烷基基团，该氧亚烷基基团可以是例如氧亚乙基基团、氧亚丙基基团、或氧亚乙基/氧亚丙基基团(即，乙氧基-丙氧基化的基团)。Suitable alkoxylated phenolic compounds contain an oxyalkylene group which may be, for example, an oxyethylene group, an oxypropylene group, or an oxyethylene/oxypropylene group A radical group (ie, an ethoxy-propoxylated group).
在烷氧基化的酚化合物中的氧亚烷基单元数，如氧亚乙基(OE)单元和/或氧亚丙基(OP)单元数，通常取决于所希望的HLB(亲水/亲油平衡)是在2与100之间。更特别地，OE和/或OP单元数包括在2与50之间。优选地，OE和/或OP单元数包括在5与50之间。The number of oxyalkylene units in the alkoxylated phenolic compound, such as the number of oxyethylene (OE) units and/or oxypropylene (OP) units, generally depends on the desired HLB (hydrophilic/ lipophilic balance) is between 2 and 100. More particularly, the number of OE and/or OP units is comprised between 2 and 50. Preferably, the number of OE and/or OP units is comprised between 5 and 50.
适合于本发明的烷氧基化的酚化合物可以包含一个、两个、或三个直链的或支链的连接到该酚基团上的烃基，这种或这些烃基优选包含从4至50个碳原子、更优选地包含从4至12个碳原子。这种烃基优选是选自由以下各项组成的组的烃基：烷基，诸如叔丁基、丁基、或异丁基，芳基，烷基芳基，和芳基烷基，其可以包含杂原子，诸如N、O或S。烷基芳基或芳基烷基的烷基部分可以是C1-C6烷基部分。烃基可以值得注意地由苯基或苯乙基表示。Alkoxylated phenolic compounds suitable for the present invention may contain one, two, or three linear or branched hydrocarbyl groups attached to the phenolic group, the hydrocarbyl group(s) preferably containing from 4 to 50 carbon atoms, more preferably from 4 to 12 carbon atoms. Such hydrocarbyl groups are preferably hydrocarbyl groups selected from the group consisting of alkyl groups such as tert-butyl, butyl, or isobutyl, aryl, alkylaryl, and arylalkyl groups, which may contain hetero Atoms such as N, O or S. The alkyl moiety of the alkylaryl or arylalkyl group may be a C1-C6 alkyl moiety. Hydrocarbyl groups may notably be represented by phenyl or phenethyl groups.
烷氧基化的酚化合物还可以包含连接到烷氧基化的链上的官能团，诸如磷酸盐(PO4-M+)、硫酸盐(SO4-M+)、磺酸盐(SO3-M+)或羧酸盐(COO-M+)。M+可以是阳离子，包括但不限于H+、Na+、NH4+、K+、或Li+。Alkoxylated phenolic compounds may also contain functional groups attached to the alkoxylated chain, such as phosphate (PO4-M+), sulfate (SO4-M+), sulfonate (SO3-M+) or carboxylic acid Salt (COO-M+). M+ can be a cation, including but not limited to H+, Na+, NH4+, K+, or Li+.
合适的盐是，例如，金属盐，诸如碱金属或碱土金属的盐，例如钠、钾、钙或镁的盐；或者具有氨或有机胺的盐，诸如吗啉，哌啶，吡咯烷，单-、双-或三-低级烷基胺，例如乙基-、二乙基-、三乙基-或二甲基-丙胺，或单-、二-或三-羟基-低级烷基胺，例如单-、二-或三-乙醇胺。Suitable salts are, for example, metal salts, such as salts of alkali metals or alkaline earth metals, for example sodium, potassium, calcium or magnesium; or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono -, di- or tri-lower alkylamines, such as ethyl-, diethyl-, triethyl- or dimethyl-propylamine, or mono-, di- or tri-hydroxy-lower alkylamines, such as Mono-, di- or tri-ethanolamine.
烷氧基化的酚化合物值得注意地可以是具有如下式(5)的化合物：The alkoxylated phenolic compound may notably be a compound having the following formula (5):
其中：in:
-R1、R2和R3，彼此独立地，是氢或直链的或支链的烃基，该烃基优选包含从4至50个碳原子、优选包含从4至12个碳原子；-R1, R2 and R3, independently of each other, are hydrogen or a straight-chain or branched hydrocarbon radical, preferably comprising from 4 to 50 carbon atoms, preferably comprising from 4 to 12 carbon atoms;
-R4是包含从2至8个碳原子、优选2或3个碳原子的二价的直链或支链的亚烷基；R4可以是几种不同亚烷基的混合物；-R4 is a divalent linear or branched alkylene group comprising from 2 to 8 carbon atoms, preferably 2 or 3 carbon atoms; R4 can be a mixture of several different alkylene groups;
-n是包括在2与100之间、优选包括在2与50之间的整数；- n is an integer comprised between 2 and 100, preferably comprised between 2 and 50;
-R5是H、OH、烷氧基、磷酸盐(PO4-M+)、硫酸盐(SO4-M+)、磺酸盐(SO3-M+)或羧酸盐(COO-M+)；M+如果存在的话是阳离子，包括但不限于H+、Na+、NH4+、K+、或Li+。-R5 is H, OH, alkoxy, phosphate (PO4- M+ ), sulfate (SO4- M+ ), sulfonate (SO3- M+ ) or carboxylate (COO- M+ ); M+ , if present, is a cation, including but not limited to H+ , Na+ ,NH4+ , K+ , or Li+ .
如在式(5)中表示的，R1、R2和R3是连接至该苯基结构上的氢或直链或支链的烃基。R1、R2和R3，彼此独立地，可以是烷基，诸如叔丁基、丁基、或异丁基，芳基，烷基芳基，或芳基烷基，可以包含杂原子，诸如N、O或S。烷基芳基或芳基烷基的烷基部分可以是C1-C6烷基部分。R1、R2和R3可以彼此独立地尤其是苯基或苯乙基。As represented in formula (5), R1, R2, and R3 are hydrogen or a linear or branched hydrocarbon group attached to the phenyl structure. R1, R2 and R3, independently of each other, can be alkyl, such as tert-butyl, butyl, or isobutyl, aryl, alkylaryl, or arylalkyl, and can contain heteroatoms, such as N, O or S. The alkyl moiety of the alkylaryl or arylalkyl group may be a C1-C6 alkyl moiety. R1, R2 and R3 may independently of one another be especially phenyl or phenethyl.
当R5为烷氧基时，可以是例如C1-C6烷氧基，诸如-OCH3、-OC2H5、-OC3H7、-OC4H9、-OC5H11、或-OC6H13。When R5 is alkoxy, it may be, for example, C1-C6 alkoxy, such as -OCH3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, or -OC6H13.
合适的烷氧基化的酚化合物可以尤其选自由以下各项组成的组：Suitable alkoxylated phenolic compounds may especially be selected from the group consisting of:
-烷氧基化的烷基酚，其可以是例如C6-C16-烷醇，如烷氧基化的辛基酚、烷氧基化的月桂基酚和烷氧基化的壬基酚，诸如聚乙氧基化的辛基酚和聚乙氧基化的壬基酚；- alkoxylated alkylphenols, which may be, for example, C6 -C16 -alkanols, such as alkoxylated octylphenol, alkoxylated laurylphenol and alkoxylated nonylphenol , such as polyethoxylated octylphenol and polyethoxylated nonylphenol;
-烷氧基化的烷基芳基酚，其可以是例如烷氧基化的单-、二-或三苯乙烯基酚，诸如聚乙氧基化的三苯乙烯基酚；- alkoxylated alkylarylphenols, which may be, for example, alkoxylated mono-, di- or tristyrylphenols, such as polyethoxylated tristyrylphenols;
-烷氧基化的硫酸化和/或磷酸盐烷基酚；以及- alkoxylated sulfated and/or phosphated alkylphenols; and
-烷氧基化的硫酸化和/或磷酸盐烷基芳基酚，诸如乙氧基化的和/或丙氧基化的、硫酸化和/或磷酸化单-、二-或三苯乙烯基酚，乙氧基化的聚芳基酚醚磷酸盐。- alkoxylated sulfated and/or phosphated alkylarylphenols, such as ethoxylated and/or propoxylated, sulfated and/or phosphorylated mono-, di- or triphenylethylenes phenolic, ethoxylated polyarylphenol ether phosphates.
用于其他用途的三苯乙烯基酚乙氧基化物例如通过美国专利号6,146,570、公开的PCT专利申请号WO 98/012921和WO 98/045212中披露，这些专利通过援引的方式并入本申请中。Tristyrylphenol ethoxylates for other uses are disclosed, for example, in U.S. Patent No. 6,146,570, Published PCT Patent Application Nos. WO 98/012921 and WO 98/045212, which are incorporated herein by reference .
本发明的烷氧基化的酚化合物可以尤其选自由以下各项组成的组：用2个OE单元乙氧基化的壬基酚；用4个OE单元乙氧基化的壬基酚；用6个OE单元乙氧基化的壬基酚；用9个OE单元乙氧基化的壬基酚；用25个OE+OP单元乙氧基-丙氧基化的壬基酚；用30个OE+OP单元乙氧基-丙氧基化的壬基酚；用40个OE+OP单元乙氧基-丙氧基化的壬基酚；用55个OE+OP单元乙氧基-丙氧基化的壬基酚；用80个OE+OP单元乙氧基-丙氧基化的壬基酚；用5个OE单元乙氧基化的二(1-苯乙基)酚；用7个OE单元乙氧基化的二(1-苯乙基)酚；用10个OE单元乙氧基化的二(1-苯乙基)酚；用8个OE单元乙氧基化的三(1-苯乙基)酚；用16个OE单元乙氧基化的三(1-苯乙基)酚；用20个OE单元乙氧基化的三(1-苯乙基)酚；用25个OE单元乙氧基化的三(1-苯乙基)酚；用40个OE单元乙氧基化的三(1-苯乙基)酚；用25个OE+OP单元乙氧基-丙氧基化的三(1-苯乙基)酚；包含5个OE单元的乙氧基化并且硫酸化的二(1-苯乙基)酚；包含7个OE单元的乙氧基化并且硫酸化的二(1-苯乙基)酚；包含15个OE单元的乙氧基化并且硫酸化的二(1-苯乙基)酚；包含16个OE单元的乙氧基化并且硫酸化的二(1-苯乙基)酚；包含16个OE单元的乙氧基化并且硫酸化的三(1-苯乙基)酚；以及包含16个OE单元的乙氧基化并且磷酸化的三(1-苯乙基)酚。The alkoxylated phenolic compounds of the present invention may especially be selected from the group consisting of: nonylphenol ethoxylated with 2 OE units; nonylphenol ethoxylated with 4 OE units; Nonylphenol ethoxylated with 6 OE units; Nonylphenol ethoxylated with 9 OE units; Nonylphenol ethoxy-propoxylated with 25 OE+OP units; Nonylphenol ethoxylated with 30 Nonylphenol ethoxy-propoxylated with OE+OP units; nonylphenol ethoxy-propoxylated with 40 OE+OP units; ethoxy-propoxylated with 55 OE+OP units nonylphenol ethoxylated with 80 OE+OP units; nonylphenol ethoxylated with 80 OE+OP units; bis(1-phenethyl)phenol ethoxylated with 5 OE units; Bis(1-phenethyl)phenols ethoxylated with OE units; bis(1-phenethyl)phenols ethoxylated with 10 OE units; tris(1-phenethyl)phenols ethoxylated with 8 OE units -phenethyl)phenol; tris(1-phenethyl)phenol ethoxylated with 16 OE units; tris(1-phenethyl)phenol ethoxylated with 20 OE units; tris(1-phenethyl)phenol ethoxylated with 25 OE units Tris(1-phenethyl)phenol ethoxylated with OE units; Tris(1-phenethyl)phenol ethoxylated with 40 OE units; Ethoxy-propoxylated with 25 OE+OP units oxylated tris(1-phenethyl)phenol; ethoxylated and sulfated bis(1-phenethyl)phenol containing 5 OE units; ethoxylated and sulfated containing 7 OE units ethoxylated and sulfated bis(1-phenethyl)phenol containing 15 OE units; ethoxylated and sulfated bis(1-phenethyl)phenol containing 16 OE units (1-phenethyl)phenol; ethoxylated and sulfated tris(1-phenethyl)phenol containing 16 OE units; and ethoxylated and phosphorylated tris(1-phenylethyl)phenol containing 16 OE units 1-Phenylethyl)phenol.
实际上，根据本发明的烷氧基化的酚表面活性剂可以选自：Indeed, the alkoxylated phenolic surfactants according to the invention may be selected from:
-三苯乙烯基苯酚的乙氧基化物，诸如可商购产品BSU；CY8；S25(苏威公司(Solvay))；- ethoxylates of tristyrylphenol, such as commercially available products BSU; CY8; S25 (Solvay);
-醇的乙氧基化物，诸如可商购产品LA 12/80；LA12；BC 720；BC 630；BC 639(罗地亚公司(Rhodia))；- ethoxylates of alcohols, such as commercially available products LA 12/80; LA12; BC 720; BC 630; BC 639 (Rhodia);
-烷基酚的乙氧基化物，诸如可商购产品RC 630；DM 530；RC 620：CO 610；CO 630；CO 660；CO 710；CO 710(苏威公司)。- ethoxylates of alkylphenols, such as commercially available products RC 630; DM 530; RC620: CO 610; CO 630; CO 660; CO 710; CO 710 (Solvay).
在实践中，硅氧烷表面活性剂包括在一个或多个侧链、一个末端、两个末端及其组合上改性的聚二甲基硅氧烷。作为改性的实例，该聚二甲基硅氧烷可以被聚醚基团改性，诸如聚氧亚乙基基团或聚氧亚乙基聚氧亚丙基基团。In practice, silicone surfactants include polydimethylsiloxanes modified at one or more side chains, at one end, at both ends, and combinations thereof. As an example of modification, the polydimethylsiloxane may be modified with polyether groups, such as polyoxyethylene groups or polyoxyethylenepolyoxypropylene groups.
b)酯基非离子表面活性剂b) Ester-based nonionic surfactants
在感兴趣的酯基非离子乳化剂中，人们可以列举烷氧基化的油和脂肪。这些化合物包括羊毛脂(lanolin)(羊毛脂(wool fat))或蓖麻油的乙氧基化和/或丙氧基化的衍生物。羊毛脂是含有高分子量醇和脂肪酸的酯和聚酯的混合物的蜡的通用名称。蓖麻油是脂肪酸的甘油三酯的混合物。Among the ester-based nonionic emulsifiers of interest, one may cite alkoxylated oils and fats. These compounds include ethoxylated and/or propoxylated derivatives of lanolin (wool fat) or castor oil. Lanolin is the common name for waxes containing a mixture of esters and polyesters of high molecular weight alcohols and fatty acids. Castor oil is a mixture of triglycerides of fatty acids.
酯基非离子乳化剂的其他实例可以由烷氧基化的酸表示，诸如由单酯和二酯表示的化合物。Other examples of ester-based nonionic emulsifiers may be represented by alkoxylated acids, such as compounds represented by monoesters and diesters.
有意义的单酯可以由具有如下通式(6)的化合物表示：Interesting monoesters can be represented by compounds having the general formula (6):
其中R1是C6-C30烃基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。wherein R1 is a C6 -C30 hydrocarbon group, R2 is a C2 -C10 alkylene group such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or a mixture thereof, and y ranges from 2 to 50.
优选地，单酯可以由具有如下通式(7)的化合物表示：Preferably, the monoester can be represented by a compound having the following general formula (7):
其中R3是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R3 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or mixtures thereof, and y ranges from 2 to 50.
烷氧基化的酸单酯的实例是从2至50摩尔(特别是从4至16摩尔)的环氧烷(诸如环氧乙烷)与一摩尔的饱和或不饱和脂肪酸的缩合产物，该饱和或不饱和脂肪酸选自月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、亚油酸和亚麻酸。An example of an alkoxylated acid monoester is the condensation product of from 2 to 50 moles (in particular from 4 to 16 moles) of alkylene oxide (such as ethylene oxide) with one mole of saturated or unsaturated fatty acid, which Saturated or unsaturated fatty acids are selected from lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acids.
其实例是产品，其是约4-5mol的氧亚乙基单元与月桂酸和/或肉豆蔻酸的缩合物(德国科宁公司(Cognis))。相应的丙氧基化和/或丁基化的脂肪酸也可以包括在有意义的烷氧基化酸单酯中。An example of this is The product is a condensation product of about 4-5 mol of oxyethylene units with lauric and/or myristic acid (Cognis). Correspondingly propoxylated and/or butylated fatty acids may also be included in the alkoxylated acid monoesters of interest.
有意义的二酯可以由具有如下通式(8)的化合物表示：Diesters of interest can be represented by compounds having the general formula (8):
其中R1和R3独立地是C6-C30烃基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。优选地，感兴趣的二酯可以由具有如下通式(9)的化合物表示：wherein R1 and R3 are independently C6 -C30 hydrocarbyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or a mixture thereof, and y The range is from 2 to 50. Preferably, the diester of interest may be represented by a compound having the following general formula (9):
其中R4和R5独立地是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R4 and R5 are independently C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 - CH2- or a mixture thereof, and y ranges from2 to 50.
有意义的酯基非离子乳化剂的其他实例可以由烷氧基化二醇诸如烷氧基化乙二醇酯和烷氧基化丙二醇酯表示。Further examples of interesting ester-based nonionic emulsifiers may be represented by alkoxylated glycols such as alkoxylated ethylene glycol esters and alkoxylated propylene glycol esters.
烷氧基化乙二醇酯可以由具有如下通式(10)的化合物表示：Alkoxylated glycol esters can be represented by compounds having the general formula (10):
其中R1是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R1 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or mixtures thereof, and y ranges from 2 to 50.
烷氧基化丙二醇酯可以由具有如下通式(11)的化合物表示：Alkoxylated propylene glycol esters can be represented by compounds having the following general formula (11):
其中R1是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R1 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or mixtures thereof, and y ranges from 2 to 50.
甘油单酯的烷氧基化酯，甘油二酯的二烷氧基化酯和甘油三酯的三烷氧基化酯也可以是有意义的化合物，所述酯是甘油或其衍生物之一与包含从8至20个碳原子并且包含共计从6至60个氧亚烷基单元的羧酸的反应产物。Alkoxylated esters of monoglycerides, dialkoxylated esters of diglycerides and trialkoxylated esters of triglycerides may also be compounds of interest, said ester being glycerol or one of its derivatives Reaction products with carboxylic acids containing from 8 to 20 carbon atoms and containing a total of from 6 to 60 oxyalkylene units.
在非限制性的酯基非离子表面活性剂中，人们可以列举聚氧亚乙基烷基酯、聚氧亚乙基甘油脂肪酸酯、聚氧亚乙基蓖麻油、氢化蓖麻油、聚氧亚乙基山梨糖醇脂肪酸酯、聚乙二醇脂肪酸酯、脂肪酸单甘油酯、聚甘油脂肪酸酯、脱水山梨醇脂肪酸酯、聚氧亚乙基脱水山梨醇脂肪酸酯、丙二醇脂肪酸酯、蔗糖脂肪酸酯、聚乙二醇脂肪酸酯、脱水山梨醇脂肪酸酯、聚氧亚乙基脱水山梨醇脂肪酸酯、聚氧亚乙基山梨糖醇脂肪酸酯、甘油脂肪酸酯、聚氧亚乙基甘油脂肪酸酯、聚甘油脂肪酸酯、丙二醇脂肪酸酯、聚氧亚乙基蓖麻油、聚氧亚乙基固化蓖麻油、聚氧亚乙基固化蓖麻油脂肪酸酯、蔗糖脂肪酸酯、聚氧亚烷基化脂肪酸酯、氧亚烷基化的烷基多糖苷、烷基葡糖苷酯。Among non-limiting ester-based nonionic surfactants, one may cite polyoxyethylene alkyl esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene Ethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglyceryl fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, propylene glycol fat Ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid Esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene cured castor oil, polyoxyethylene cured castor oil fatty acids Esters, sucrose fatty acid esters, polyoxyalkylenated fatty acid esters, oxyalkylenated alkyl polyglycosides, alkyl glucoside esters.
特别是在聚氧亚乙基甘油脂肪酸酯中，人们可以列举聚氧亚乙基氢化蓖麻油、聚氧亚乙基蓖麻油、聚氧亚乙基甘油单硬脂酸酯、聚氧亚乙基甘油单油酸酯、以及聚氧亚乙基甘油单异硬脂酸酯。In particular among polyoxyethylene glycerin fatty acid esters, one may cite polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene glycerol monostearate, polyoxyethylene Glyceryl monooleate, and polyoxyethylene glycerol monoisostearate.
在聚氧亚乙基脱水山梨醇脂肪酸酯中，人们可以列举聚氧亚乙基脱水山梨醇单硬脂酸酯和聚氧亚乙基脱水山梨醇单油酸酯。Among the polyoxyethylene sorbitan fatty acid esters, one may cite polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate.
在聚氧亚乙基山梨糖醇脂肪酸酯中，人们可以列举聚氧亚乙基山梨糖醇单月桂酸酯。Among polyoxyethylene sorbitan fatty acid esters, one may cite polyoxyethylene sorbitan monolaurate.
在聚乙二醇脂肪酸酯中，人们可以列举聚乙二醇单硬脂酸酯、聚乙二醇单油酸酯和聚乙二醇单月桂酸酯。Among polyethylene glycol fatty acid esters, one may cite polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol monolaurate.
c)胺基或酰胺基非离子表面活性剂c) Amine-based or amido-based nonionic surfactants
胺基非离子表面活性剂的实例可以是具有如下通式(11)的氧化胺表面活性剂：An example of an amine-based nonionic surfactant may be an amine oxide surfactant having the following general formula (11):
其中箭头是半极性键(N+-O-)的常规表示；并且，R1、R2、和R3可以是脂肪族、芳香族、杂环、脂环族或其组合。实际上，R1为C8至C24的烷基；R2和R3是C1至C3的烷基或羟烷基或其混合物；R2和R3可以例如通过氧或氮原子彼此连接以形成环状结构。where the arrow is a conventional representation of a semipolar bond (N+ —O− ); and, R1, R2, and R3 may be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof.In practice, R1 is C8 toC24 alkyl; R2 andR3 areC1 to C3 alkyl or hydroxyalkyl or a mixture thereof; R2 and R3 may be linked to each other, for example via an oxygen or nitrogen atom, to form a ring structure.
在某些实施例中，R1选自下组，该组包含辛基、癸基、十二烷基、异十二烷基、椰子油和牛油烷基二-(低级烷基)基团。In certain embodiments, R1 is selected from the group consisting of octyl, decyl, dodecyl, isododecyl, coconut oil and tallow alkyl di-(lower alkyl) groups.
实际上，这些化合物称为辛基二甲基氧化胺、壬基二甲基氧化胺、癸基二甲基氧化胺、十一烷基二甲基氧化胺、十二烷基二甲基氧化胺、异十二烷基二甲基氧化胺、十三烷基二甲基氧化胺、十四烷基二甲基氧化胺、十五烷基二甲基氧化胺、十六烷基二甲基氧化胺、十七烷基二甲基氧化胺、十八烷基二甲基氧化胺、十二烷基二丙基氧化胺、十四烷基二丙基氧化胺、十六烷基二丙基氧化胺、十四烷基二丁基氧化胺、十八烷基二丁基氧化胺、双(2-羟乙基)十二烷基氧化胺、双(2-羟乙基)-3-十二烷基氧基-1-羟丙基氧化胺、二甲基-(2-羟基十二烷基)氧化胺、3，6，9-三(十八烷基)二甲基氧化胺和3-十二烷基氧基-2-羟丙基二-(2-羟乙基)氧化胺。In fact, these compounds are called octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide , Isododecyl dimethyl amine oxide, Tridecyl dimethyl amine oxide, Tetradecyl dimethyl amine oxide, Pentadecyl dimethyl amine oxide, Hexadecyl dimethyl amine oxide Amine, Heptadecyl Dimethyl Amine Oxide, Octadecyl Dimethyl Amine Oxide, Dodecyl Dipropyl Amine Oxide, Tetradecyl Dipropyl Amine Oxide, Hexadecyl Dipropyl Amine Oxide Amine, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, bis(2-hydroxyethyl) dodecyl amine oxide, bis(2-hydroxyethyl)-3-dodecyl Alkyloxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-tris(octadecyl)dimethylamine oxide and 3- Dodecyloxy-2-hydroxypropyl bis-(2-hydroxyethyl)amine oxide.
根据本发明有意义的胺基非离子乳化剂的其他实例可以由烷氧基化胺表示，诸如二烷氧基化伯胺和单烷氧基化仲胺。Further examples of amine-based nonionic emulsifiers of interest according to the invention may be represented by alkoxylated amines, such as dialkoxylated primary amines and monoalkoxylated secondary amines.
有意义的二烷氧基化伯胺可以由具有如下的式(12)的化合物表示：Dialkoxylated primary amines of interest can be represented by compounds having the formula (12):
其中R1是C8-C20烷基或C8-C20烯基，R2和R3独立地是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y和y’的范围独立地是从2至50；Wherein R1 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 and R3 are independently C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 - CH2 - or a mixture thereof, and y and y' independently range from 2 to 50;
单烷氧基化叔胺可以由具有如下通式(13)的化合物表示：Monoalkoxylated tertiary amines can be represented by compounds having the general formula (13):
其中R1和R3独立地是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R1 and R3 are independently C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 - CH2- or a mixture thereof, and y ranges from2 to 50.
在酰胺基非离子表面活性剂中，人们可以列举醛缩二酰胺(aldobionamide)、脂肪酸烷醇酰胺、聚氧亚乙基烷基酰胺、聚氧亚乙基脂肪酸酰胺。Among the amide-based nonionic surfactants, one may cite aldobionamide, fatty acid alkanolamide, polyoxyethylene alkylamide, polyoxyethylene fatty acid amide.
在一些实施例中，烷醇酰胺表面活性剂包括但不限于椰油酰胺DEA、月桂基二乙醇酰胺、月桂酰胺DEA、椰油酰胺DEA、月桂酰胺DEA。In some embodiments, alkanolamide surfactants include, but are not limited to, cocamide DEA, lauryldiethanolamide, lauramide DEA, cocamide DEA, lauramide DEA.
根据本发明感兴趣的酰胺基非离子乳化剂的其他实例可以由烷氧基化烷醇酰胺表示，诸如烷氧基化单烷醇胺和二烷氧基化二烷醇胺。Further examples of amido-based nonionic emulsifiers of interest according to the invention may be represented by alkoxylated alkanolamides, such as alkoxylated monoalkanolamines and dialkoxylated dialkanolamines.
烷氧基化单烷醇酰胺可以由具有如下的式(14)的化合物表示：Alkoxylated monoalkanolamides can be represented by compounds having the following formula (14):
其中R1是C8-C20烷基或C8-C20烯基，R2是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y的范围是从2至50。Wherein R1 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 is C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 -CH2 - or mixtures thereof, and y ranges from 2 to 50.
二烷氧基化二烷醇酰胺可以由具有如下的式(15)的化合物表示：Dialkoxylated dialkanolamides can be represented by compounds having the following formula (15):
其中R1是C8-C20烷基或C8-C20烯基，R2和R3独立地是C2-C10亚烷基，例如-CH2-CH2-、-CH2-CH2-CH2-或其混合物，并且y和y’的范围彼此独立地是从2至50。Wherein R1 is C8 -C20 alkyl or C8 -C20 alkenyl, R2 and R3 are independently C2 -C10 alkylene, such as -CH2 -CH2 -, -CH2 -CH2 - CH2- or a mixture thereof, and y and y' range from2 to 50 independently of each other.
d)氟表面活性剂d) Fluorosurfactant
总体上，氟表面活性剂可以通过在分子中氟的含量来表征，这可能是由部分或完全氟化的环氧烷与非氟化的环氧烷的共聚产生的，或者通过含氟反应物与聚(环氧烷)的反应产生，从而为端基提供氟含量。In general, fluorosurfactants can be characterized by the amount of fluorine in the molecule, which may result from the copolymerization of partially or fully fluorinated alkylene oxides with non-fluorinated alkylene oxides, or by the The reaction with poly(alkylene oxide) produces, thereby providing the fluorine content to the end groups.
在第一种情况下，低聚物或聚合物除了氧亚烷基基团之外还包含一定量的具有一个或多个氟原子的相应基团，即在作为环氧烷烃的环氧乙烷的情况下，这些化合物包含-(CH2-CH2-O)-单元和-(CH2-aXa-CH2-bXb-O)-单元，其中X表示氟，并且a或b中的至少一个表示至少为1的整数。In the first case, the oligomer or polymer contains, in addition to the oxyalkylene groups, a certain amount of corresponding groups with one or more fluorine atoms, i.e. in the case of ethylene oxide as alkylene oxide In the case of , these compounds comprise -(CH2-CH2-O)-units and -(CH2-aXa-CH2-bXb-O)-units, where X represents fluorine and at least one of a or b represents at least 1 an integer of .
在某些情况下，氟表面活性剂可以由具有如下通式(16)的化合物表示：In some cases, fluorosurfactants can be represented by compounds having the following general formula (16):
F(CF2-CF2)x-CH2-CH2-O-(CH2-CH2-O)y-R (16)F(CF2 -CF2 )x -CH2 -CH2 -O-(CH2 -CH2 -O)y -R (16)
其中R为H或烷氧基，并且x和y具有在从1至50范围内、优选在从1至30范围内的值并且特别优选x和y高达20。wherein R is H or alkoxy, and x and y have values in the range from 1 to 50, preferably in the range from 1 to 30 and particularly preferably x and y up to 20.
具有高达2000、优选高达1500并且甚至更优选高达1000的重均分子量的这种类型的产物是特别有意义的。x与y(x/y)的比率不受特定限制，并且可以在宽范围内选择。许多这种类型的氟表面活性剂是从杜邦公司(DuPont)以商品名可获得的。Products of this type having a weight-average molecular weight of up to 2000, preferably up to 1500 and even more preferably up to 1000 are of particular interest. The ratio of x to y (x/y) is not particularly limited and can be selected within a wide range. Many fluorosurfactants of this type are available from DuPont under the tradename available.
另一组氟表面活性剂包括具有六个或更少基团CF2的短链分子，并且在一端用氟封端，并且结合到如从杜邦公司以商品名可商购的递送系统诸如聚合物或表面活性剂上。Another group of fluorosurfactants consists of short- chain molecules with six or fewer groups CF and terminated at one end with fluorine, and bonded to fluorosurfactants such as those available from DuPont under the tradename Commercially available delivery systems such as polymers or surfactants.
在某些实施例中，该非离子表面活性剂代表按重量计从0.1％至5％的悬浮液的总重量。(REV 10)In certain embodiments, the nonionic surfactant represents from 0.1% to 5% by weight of the total weight of the suspension. (REV 10)
在某些实施例中，该非离子表面活性剂具有包括在约10与约14之间的HLB、优选约12的HLB。(REV 11)In certain embodiments, the nonionic surfactant has an HLB comprised between about 10 and about 14, preferably an HLB of about 12. (REV 11)
具有范围从约10至约14的HLB的非离子表面活性剂是亲水的，即容易分散在水相中。水相Nonionic surfactants having an HLB ranging from about 10 to about 14 are hydrophilic, ie, readily disperse in an aqueous phase. water box
在一个具体实施例中，该水相由水组成。In a particular embodiment, the aqueous phase consists of water.
在某些实施例中，该水相包含水和至少一种亲水添加剂。In certain embodiments, the aqueous phase comprises water and at least one hydrophilic additive.
合适的亲水添加剂可以包括但不限于具有2至8个碳原子的单醇，诸如乙醇和异丙醇，以及多元醇，诸如甘油、二醇类、戊二醇、丙二醇、丁二醇、异戊二醇和聚乙二醇诸如PEG-8。Suitable hydrophilic additives may include, but are not limited to, monoalcohols having 2 to 8 carbon atoms, such as ethanol and isopropanol, and polyalcohols, such as glycerol, glycols, pentanediol, propylene glycol, butylene glycol, isopropanol, Pentylene glycol and polyethylene glycols such as PEG-8.
在某些实施例中，该至少一种亲水添加剂可以代表按重量计从0.01％至10％、优选从0.1％至1％的该悬浮液的总重量。In certain embodiments, the at least one hydrophilic additive may represent from 0.01% to 10%, preferably from 0.1% to 1% by weight, of the total weight of the suspension.
如与煤/水浆料(CWS)相比，该悬浮液中含有的较低量的水相减少了相对于燃烧是惰性的材料(即水)的量。The lower amount of aqueous phase contained in the suspension reduces the amount of material that is inert to combustion (ie water) as compared to a coal/water slurry (CWS).
在某些实施例中，该水相代表按重量计在10％至30％之间的该悬浮液的总重量。(REV 12)In certain embodiments, the aqueous phase represents between 10% and 30% by weight of the total weight of the suspension. (REV 12)
有机相The organic phase
在某些实施例中，该有机相选自下组，该组包含化石基液体或其衍生物、生物质基液体、合成有机液体或其衍生物、及其混合物。(REV 13)In certain embodiments, the organic phase is selected from the group consisting of fossil-based liquids or derivatives thereof, biomass-based liquids, synthetic organic liquids or derivatives thereof, and mixtures thereof. (REV 13)
在某些实施例中，该化石基液体是石油基液体或其衍生物。(REV 14)In certain embodiments, the fossil-based fluid is a petroleum-based fluid or a derivative thereof. (REV 14)
在某些实施例中，根据本发明的化石基液体可以是原油石油和例如由炼油厂从其过程产生的原油石油衍生物产物。作为来自炼油厂的产物的实例，人们可以列举柴油燃料、燃料油、炉燃料油(FFO)、汽油、重质燃料油(HFO)、中等燃料油(IFO)、喷气燃料、船用柴油(MDO)、船用燃料油(MFO)、船用汽油(MGO)、海军特级燃料油(NSFO)及其混合物。In certain embodiments, the fossil-based liquids according to the present invention may be crude petroleum and crude petroleum derivative products produced, for example, by refineries from their processes. As examples of products from refineries, one may cite diesel fuel, fuel oil, furnace fuel oil (FFO), gasoline, heavy fuel oil (HFO), intermediate fuel oil (IFO), jet fuel, marine diesel oil (MDO) , Marine Fuel Oil (MFO), Marine Gasoline (MGO), Naval Special Fuel Oil (NSFO) and mixtures thereof.
在某些实施例中，根据本发明的生物质基液体可以是藻类生物燃料、生物乙醇、生物柴油、生物燃料汽油、生物甲醇、椰子油、绿色柴油、棕榈油、植物油及其混合物。In certain embodiments, the biomass-based liquid according to the present invention may be algal biofuel, bioethanol, biodiesel, biofuel gasoline, biomethanol, coconut oil, green diesel, palm oil, vegetable oil, and mixtures thereof.
在某些实施例中，适用于本发明的生物柴油可以包括棕榈油，即马来西亚生物柴油或LOF生物柴油，后者已经在在此的实例中使用。所述马来西亚液体生物柴油组合物包含衍生自棕榈硬脂精的生物柴油组合物，衍生自棕榈油甲酯的生物柴油组合物以及衍生自废弃烹调油的生物柴油组合物。In certain embodiments, biodiesel suitable for use in the present invention may include palm oil, Malaysian biodiesel or LOF biodiesel, the latter of which has been used in the examples herein. The Malaysian liquid biodiesel composition comprises a biodiesel composition derived from palm stearin, a biodiesel composition derived from palm oil methyl ester, and a biodiesel composition derived from waste cooking oil.
在某些实施例中，该有机相包含值得注意地由生物质和/或化石试剂获得的合成燃料。In certain embodiments, the organic phase comprises synthetic fuels, notably derived from biomass and/or fossil reagents.
在本发明的范围内，该有机相可以包含脂肪烃，例如像己烷、庚烷、辛烷或壬烷；惰性脂环族烃，诸如环己烷、环戊烷或环庚烷；芳香烃，诸如苯、甲苯、乙苯、二甲苯、或液体环烷烃；醇诸如丁醇、乙醇、甲醇或丙醇；以及其混合物。Within the scope of the present invention, the organic phase may comprise aliphatic hydrocarbons, such as, for example, hexane, heptane, octane or nonane; inert cycloaliphatic hydrocarbons, such as cyclohexane, cyclopentane or cycloheptane; aromatic hydrocarbons , such as benzene, toluene, ethylbenzene, xylene, or liquid naphthenes; alcohols such as butanol, ethanol, methanol, or propanol; and mixtures thereof.
如与煤/水浆料(CWS)相比，该悬浮液中含有的有机相的存在增加了易于燃烧的材料的量。因此，根据本发明的浆料悬浮液提供优异的燃烧特性，特别是良好的总热值。The presence of an organic phase contained in the suspension increases the amount of readily combustible material as compared to a coal/water slurry (CWS). Therefore, the slurry suspension according to the invention provides excellent combustion characteristics, in particular a good gross calorific value.
在某个实施例中，该有机相代表按重量计在50％与75％之间的该悬浮液的总重量。(REV 15)In a certain embodiment, the organic phase represents between 50% and 75% by weight of the total weight of the suspension. (REV 15)
乳液lotion
在本发明的一个方面，该浆料悬浮液可以呈乳液的形式，即水包油(O/W)乳液或油包水(W/O)乳液。In one aspect of the invention, the slurry suspension may be in the form of an emulsion, ie an oil-in-water (O/W) emulsion or a water-in-oil (W/O) emulsion.
可以根据现有技术中已知的常识来制备乳液。在实践中，乳液的制备可以包括分别制备均相水相和均相有机相。Emulsions can be prepared according to general knowledge known in the art. In practice, the preparation of the emulsion may involve the separate preparation of a homogeneous aqueous phase and a homogeneous organic phase.
在某些实施例中，将具有范围从约10至约14的HLB的非离子表面活性剂分散在水相中。In certain embodiments, a nonionic surfactant having an HLB ranging from about 10 to about 14 is dispersed in the aqueous phase.
在这个阶段，可以通过在搅拌下将有机相引入连续水相中来制备直接的水包油(O/W)乳液。因此获得直接的O/W乳液，并且表示分散在连续水相中的不连续的有机相。At this stage, direct oil-in-water (O/W) emulsions can be prepared by introducing the organic phase into the continuous aqueous phase with stirring. A direct O/W emulsion is thus obtained and represents a discontinuous organic phase dispersed in a continuous aqueous phase.
相反地，通过经由搅拌将水相引入有机相中获得油包水(W/O)乳液。在该方法结束时，反相W/O乳液因此由分散在连续有机相中的不连续水相表示。也可以使用其他已知的具体的制备方法。Conversely, water-in-oil (W/O) emulsions are obtained by introducing the aqueous phase into the organic phase by stirring. At the end of the process, the inverse W/O emulsion is thus represented by a discontinuous aqueous phase dispersed in a continuous organic phase. Other known specific preparation methods may also be used.
在某些实施例中，所述悬浮液是水包油乳液。(REV 2)In certain embodiments, the suspension is an oil-in-water emulsion. (REV 2)
在某些实施例中，该水相与该有机相的重量比率是在从1/7.5的比率至1/1.65的比率、优选从1/4的比率至1/2的比率的范围内。In certain embodiments, the weight ratio of the aqueous phase to the organic phase ranges from a ratio of 1/7.5 to a ratio of 1/1.65, preferably from a ratio of 1/4 to 1/2.
在某些实施例中，当将该非离子表面活性剂混合在该水相中时，该非离子表面活性剂与该水相的重量比率是在从1/100的比率至1/7的比率、优选1/25的比率至1/8的比率的范围内。In certain embodiments, when the nonionic surfactant is mixed in the aqueous phase, the weight ratio of the nonionic surfactant to the aqueous phase is from a ratio of 1/100 to a ratio of 1/7 , preferably in the range of a ratio of 1/25 to a ratio of 1/8.
这些比率特别适用于提供稳定的乳液，并且有效且均匀地将含碳材料颗粒分散在水相中。These ratios are particularly useful in providing a stable emulsion and effectively and uniformly dispersing the carbonaceous material particles in the aqueous phase.
一种或多种额外的成分one or more additional ingredients
本发明的悬浮液还可以包含一种或多种额外的成分，诸如本领域已知的常规成分。这些成分的非限制性实例可以是保湿剂、润湿剂、流变添加剂、碱、腐蚀抑制剂、泡沫抑制剂、稳定剂和杀生物防腐剂。The suspensions of the present invention may also contain one or more additional ingredients, such as conventional ingredients known in the art. Non-limiting examples of these ingredients may be humectants, wetting agents, rheology additives, bases, corrosion inhibitors, foam inhibitors, stabilizers and biocidal preservatives.
当存在于悬浮液中时，所述额外的成分代表按重量计从0.001％至5％、优选从0.01％至1％的该悬浮液的总重量。When present in a suspension, said additional ingredients represent from 0.001% to 5% by weight, preferably from 0.01% to 1%, of the total weight of the suspension.
方法method
在另一方面，本发明涉及一种用于制备根据本发明的浆料悬浮液的方法，该方法包括以下步骤：In another aspect, the present invention relates to a method for preparing a slurry suspension according to the present invention, the method comprising the steps of:
i.至少混合成分(b)、(c)和(d)以形成乳液；i. mixing at least ingredients (b), (c) and (d) to form an emulsion;
ii.将成分(a)与步骤i.中获得的乳液混合以形成浆料悬浮液。(REV 16)ii. Mixing ingredient (a) with the emulsion obtained in step i. to form a slurry suspension. (REV 16)
在某些实施例中，所述乳液是水包油乳液。(REV 17)In certain embodiments, the emulsion is an oil-in-water emulsion. (REV 17)
在某些实施例中，用于制备根据本发明的浆料悬浮液的所述方法包括以下步骤：In certain embodiments, the method for preparing a slurry suspension according to the present invention comprises the steps of:
i1.至少混合该非离子表面活性剂(b)和该水相(c)；il. mixing at least the nonionic surfactant (b) and the aqueous phase (c);
i2.将该有机相(d)混合到步骤i1.中获得的混合物中以形成水包油乳液；i2. mixing the organic phase (d) into the mixture obtained in step ii. to form an oil-in-water emulsion;
iii.将含碳材料颗粒(a)与步骤i2.中获得的水包油乳液混合以形成浆料悬浮液。iii. Mixing the carbonaceous material particles (a) with the oil-in-water emulsion obtained in step i2. to form a slurry suspension.
在这些实施例中，将该非离子表面活性剂优选在形成乳液之前加入到水相中，因为具有从约10至约14的范围的HLB的非离子表面活性剂容易分散在水相中。In these embodiments, the nonionic surfactant is preferably added to the aqueous phase prior to forming the emulsion, since nonionic surfactants having an HLB ranging from about 10 to about 14 are readily dispersed in the aqueous phase.
此外，观察到非离子表面活性剂的存在促进了含碳材料颗粒在水相中的分散。Furthermore, it was observed that the presence of nonionic surfactants facilitated the dispersion of carbonaceous material particles in the aqueous phase.
在某些实施例中，获得如以上描述的水包油乳液，并且将这些含碳材料颗粒分散在有机相液滴之间的连续水相中。In certain embodiments, an oil-in-water emulsion as described above is obtained and the carbonaceous material particles are dispersed in the continuous aqueous phase between the droplets of the organic phase.
不希望受理论的束缚，在水包油(O/W)乳液的情况下，非离子表面活性剂的亲油部分可以有利地形成与含碳材料颗粒的疏水表面的相互作用，而非离子表面活性剂的亲水部分将使得连续水相中的分散变得容易。因此，这些含碳材料颗粒被均匀地分散到连续的水相中，并且它们在乳液中的沉淀显著延迟。Without wishing to be bound by theory, in the case of oil-in-water (O/W) emulsions, the lipophilic portion of the nonionic surfactant may advantageously form interactions with the hydrophobic surface of the carbonaceous material particles, rather than the nonionic surface The hydrophilic portion of the active agent will facilitate dispersion in the continuous aqueous phase. Consequently, these carbonaceous material particles are uniformly dispersed into the continuous aqueous phase, and their precipitation in the emulsion is significantly delayed.
此外，这些含碳材料颗粒分散在有机相的液滴之间，这会产生表面张力，该表面张力将有机相的液滴保持均匀地分散到连续水相中In addition, these carbonaceous material particles are dispersed between the droplets of the organic phase, which creates surface tension that keeps the droplets of the organic phase dispersed evenly into the continuous aqueous phase
由于这些原因，这些含碳材料颗粒可以表现得如同表面活性剂，因为它们保持液滴均匀分散到连续水相中，并且有机相的聚结显著延迟。For these reasons, these carbonaceous material particles can behave like surfactants in that they keep the droplets dispersed evenly into the continuous aqueous phase and the coalescence of the organic phase is significantly delayed.
在另一方面，本发明涉及一种用于发电的方法，该方法包括燃烧根据本发明的浆料悬浮液(REV 18)。In another aspect, the invention relates to a method for generating electricity, the method comprising combusting a slurry suspension (REV 18) according to the invention.
用途use
在另一方面，本发明还涉及非离子表面活性剂用来稳定包含具有包括在0.1μm与200μm之间的平均直径D50的含碳材料颗粒的乳液的用途。(REV 19)In another aspect, the invention also relates to the use of a nonionic surfactant to stabilize an emulsion comprising particles of carbonaceous material having a mean diameter D50 comprised between 0.1 μm and 200 μm. (REV 19)
在某些实施例中，所述乳液是水包油乳液。(REV 20)In certain embodiments, the emulsion is an oil-in-water emulsion. (REV 20)
诸位发明人已经观察到，根据本发明的悬浮液能够形成稳定的乳液(例如水包油乳液)持续至少2周的时间段。The inventors have observed that suspensions according to the invention are capable of forming stable emulsions (eg oil-in-water emulsions) for a period of at least 2 weeks.
然而，在较长时间段之后，呈乳液形式的悬浮液可能返回到非乳液悬浮液的状态，即在水相和有机相的沉降和/或分离已经发生之后的状态。可以以形成持续至少2周的另一个时间段的稳定乳液的方式进一步操作悬浮液。However, after a longer period of time, the suspension in the form of an emulsion may return to the state of a non-emulsion suspension, ie after settling and/or separation of the aqueous and organic phases has occurred. The suspension may be further manipulated in such a way as to form a stable emulsion for another period of at least 2 weeks.
根据本发明的稳定乳液可以有利地用于已经可得的内燃机中，或者只需稍微改变这些现有发动机。The stable emulsions according to the invention can advantageously be used in already available internal combustion engines, or these existing engines need only be slightly modified.
实例example
实例1：经焙烧的木材颗粒的制备Example 1: Preparation of Roasted Wood Pellets
经焙烧的木片通过焙烧获得，并且小片具有厘米尺寸的平均尺寸。根据干式碾磨方案研磨经焙烧的木片，以得到具有300μm至1mm的平均尺寸的颗粒。呈粉末形式的这些颗粒随后通过使用具有以下特征的Retsch ZM200干研磨机进行干燥研磨：栅格120μm、速度18000rpm、25℃、氮气吹扫、在10min内每批80g。在研磨过程结束时，颗粒显示出用新帕泰克激光衍射传感器测量的如下粒径分布：D10＝6μm；D50＝23μm；D90＝60μm。Roasted wood chips are obtained by firing, and the chips have an average size of centimeter size. The calcined wood chips were ground according to a dry milling protocol to obtain particles with an average size of 300 μm to 1 mm. These granules in powder form were then dry milled by using a Retsch ZM200 dry mill with the following characteristics: grid 120 μm, speed 18000 rpm, 25° C., nitrogen purge, batches of 80 g in 10 min. At the end of the milling process, the particles showed the following particle size distribution measured with a Synpatek laser diffraction sensor: D10 =6 μm; D50 =23 μm; D90 =60 μm.
实例2：包含水/柴油/经焙烧的木材颗粒的浆料悬浮液Example 2: Slurry suspension comprising water/diesel/torrified wood particles
通过首先混合20％wt的水、63％的柴油(Shell V-Power Diesel CAS号：68334-30-5)和2％wt的BSU(非离子表面活性剂)在室温下制备稳定的水包油(O/W)乳液。将表面活性剂(Soprophor BSU；HLB＝12)加入水中，它容易地润湿木材颗粒。By first mixing 20% wt of water, 63% of diesel oil (Shell V-Power Diesel CAS No.: 68334-30-5) and 2% wt of BSU (nonionic surfactant) prepares stable oil-in-water (O/W) emulsions at room temperature. A surfactant (Soprophor BSU; HLB=12) was added to the water, which readily wets the wood particles.
然后加入15％wt的根据实例1的经焙烧的木材颗粒(25μm)，并且与该第一混合物混合以获得稳定的分散体。用位于连续相中经焙烧的木材颗粒获得水包油(o/w)乳液。可以观察到，经焙烧的木材颗粒被捕获在连续相中的液滴之间，这防止它们沉降。同时，经焙烧的木材颗粒看起来充当乳化剂，从而防止这些液滴的聚结。Then 15% wt of calcined wood particles (25 μm) according to example 1 were added and mixed with this first mixture to obtain a stable dispersion. Oil-in-water (o/w) emulsions were obtained with calcined wood particles in the continuous phase. It can be observed that the torrefied wood particles are trapped between the droplets in the continuous phase, which prevents them from settling. At the same time, the roasted wood particles appear to act as emulsifiers, preventing coalescence of these droplets.
通过每天一次目视检查每个样品来确定直到乳液不稳定的天数。乳液基浆料被称为不稳定，如果：The number of days until emulsion instability was determined by visual inspection of each sample once a day. Emulsion-based slurries are said to be unstable if:
-聚结导致在浆料顶部形成油层。-Coalescence leads to the formation of an oil layer on top of the slurry.
-乳油化(creaming)导致相分离，从而在容器底部形成木材和水层。-creaming leads to phase separation resulting in a wood and water layer at the bottom of the vessel.
-沉淀导致在容器底部的固体层。- Precipitation results in a solid layer at the bottom of the vessel.
在这种情况下，用15％的经焙烧的木材、20％的水和2％的Soprophor BSU，乳液长期保持稳定。说明性地，所述浆料乳液在两周或更长时间的储存时间段后保持稳定。In this case, with 15% roasted wood, 20% water and 2% Soprophor BSU, the emulsion remained stable for a long time. Illustratively, the slurry emulsion remained stable after a storage period of two weeks or more.
因此，用非离子表面活性剂稳定的由经焙烧的木材、水和柴油制成的乳液的配制品是可行的。Thus, formulations of emulsions from roasted wood, water and diesel stabilized with nonionic surfactants are feasible.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910976787.8ACN111303952A (en) | 2014-12-23 | 2014-12-23 | Pulp suspension comprising calcined wood particles |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2014/094571WO2016101113A1 (en) | 2014-12-23 | 2014-12-23 | Slurry suspension comprising torrefied wood particles |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910976787.8ADivisionCN111303952A (en) | 2014-12-23 | 2014-12-23 | Pulp suspension comprising calcined wood particles |
| Publication Number | Publication Date |
|---|---|
| CN107207980Atrue CN107207980A (en) | 2017-09-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910976787.8APendingCN111303952A (en) | 2014-12-23 | 2014-12-23 | Pulp suspension comprising calcined wood particles |
| CN201480084351.3APendingCN107207980A (en) | 2014-12-23 | 2014-12-23 | Slurry suspension comprising torrefied wood particles |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910976787.8APendingCN111303952A (en) | 2014-12-23 | 2014-12-23 | Pulp suspension comprising calcined wood particles |
| Country | Link |
|---|---|
| US (1) | US20170349848A1 (en) |
| EP (1) | EP3237586A4 (en) |
| CN (2) | CN111303952A (en) |
| WO (1) | WO2016101113A1 (en) |
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| CN1354227A (en)* | 2000-11-20 | 2002-06-19 | 中国科学院理化技术研究所 | Oil-based ternary mixed fuel composed of coal, water and oil |
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| Date | Code | Title | Description |
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20170926 | |
| RJ01 | Rejection of invention patent application after publication |