3,494,865
LIGNITE PRODUCTS AND COMPOSITIONS THEREOF
3,494,865
褐煤产品及其组合物
Robert S. Andrews, Jr., and William C. McDaniels, Houston, Tex., assignors to National Lead Com pany, New York, N.Y., a corporation of New Jersey
德克萨斯州休斯顿市的小罗伯特-S-安德鲁斯和威廉-C-麦克丹尼尔斯，新泽西州纽约市国家铅业公司的转让人
德克萨斯州休斯顿市的小罗伯特-S-安德鲁斯和威廉-C-麦克丹尼尔斯，新泽西州纽约市国家铅业公司的转让人
Int. CI. C10m 11/00; E21b 3/02
Int.CI.C10m 11/00；E21b 3/02
U.S. Cl. 252-8.5 《美国法典》第 252-8.5 条
12 Claims 12 索赔
Int.CI.C10m 11/00；E21b 3/02
U.S. Cl. 252-8.5 《美国法典》第 252-8.5 条
12 Claims 12 索赔
Abstract 摘要
OF THE DISCLOSURE Reaction products of humic acid with long-chain fatty acid partial amide of a polyalkylene polyamine, and oil base well-working fluids containing the same, and compositions comprising the same together with a dispersing additive. The humic acid optionally may be in part reacted with a long-chain alkyl ammonium cation.
公开内容 腐植酸与聚亚烷基多胺的长链脂肪酸部分酰胺的反应产物，以及含有腐植酸的油基加工液和由腐植酸与分散添加剂组成的组合物。腐植酸还可与长链烷基铵阳离子发生部分反应。
This invention relates to derivatives of humic acid, as obtained, for example, from lignite, and useful compositions thereof, particularly including oil-base fluids for use in well-working operations such as drilling, fracturing, packing, and the like and including processes of drilling with such compositions.
本发明涉及腐植酸衍生物（例如从褐煤中获得）及其有用的组合物，特别包括用于钻井、压裂、填料等油井作业的油基流体，还包括使用此类组合物的钻井工艺。
The present invention represents an enlargement and an improvement over certain of the inventive subject matter set forth in United States Patent 3,168,475 which issued Feb. 2, 1965, to a common assignee, and the patent is hereby incorporated herein by reference.
本发明是对 1965 年 2 月 2 日颁发给共同受让人的美国专利 3,168,475 号中某些创造性主题的扩充和改进，现将该专利并入本文作为参考。
本发明涉及腐植酸衍生物（例如从褐煤中获得）及其有用的组合物，特别包括用于钻井、压裂、填料等油井作业的油基流体，还包括使用此类组合物的钻井工艺。
The present invention represents an enlargement and an improvement over certain of the inventive subject matter set forth in United States Patent 3,168,475 which issued Feb. 2, 1965, to a common assignee, and the patent is hereby incorporated herein by reference.
本发明是对 1965 年 2 月 2 日颁发给共同受让人的美国专利 3,168,475 号中某些创造性主题的扩充和改进，现将该专利并入本文作为参考。
In the rotary drilling of wells for oil and gas, drilling fluids are used which are circulated in such a manner as to remove cuttings and to support the walls of the hole. Most commonly such fluids are water base, comprising, for example, clay dispersed in water, but in recent years extensive use has been made of fluids having oil as the base, i.e., the continuous liquid vehicle.
在石油和天然气井的旋转钻探过程中，需要使用钻井液，这些钻井液在循环过程中可以清除切屑并支撑井壁。最常见的钻井液是以水为基质的，例如由分散在水中的粘土组成，但近年来已广泛使用以油为基质的钻井液，即连续液体载体。
在石油和天然气井的旋转钻探过程中，需要使用钻井液，这些钻井液在循环过程中可以清除切屑并支撑井壁。最常见的钻井液是以水为基质的，例如由分散在水中的粘土组成，但近年来已广泛使用以油为基质的钻井液，即连续液体载体。
The oily vehicle is converted into a well-working fluid suitable for the purpose at hand, such as a drilling fluid, by adding various materials thereto for a number of purposes. Thus, thickening agents may be added, so that the fluid will support cuttings and finely-divided solid additives. Again, weighting materials such as ground barite or calcite may be added to increase the density of the fluid. Also, and of great importance, substances may be added which serve to reduce the filtration of the fluid, as takes place when the fluid is in contact with permeable formations. These oil-base fluids may also contain water in the form of water-in-oil emulsion, so that the continuous phase of the fluid is still oil.
通过添加各种材料，油性载体被转化为适合手头用途的良好工作流体，例如钻井液。因此，可以添加增稠剂，使液体能够支撑切屑和细小的固体添加剂。此外，还可添加重晶石或方解石等加重材料，以增加钻井液的密度。另外，非常重要的一点是，可以添加一些物质来减少流体的过滤性，当流体与渗透性地层接触时就会发生这种情况。这些油基流体还可能含有油包水型乳化液形式的水，因此流体的连续相仍然是油。
In the earlier development of oil-base fluids of the types described, primary attention was given to providing thickening additives. Many were found and have been used at various times, including carbon black; soaps of fatty acids, rosin, tall oil, and the like organic acids; asphalts of various kinds; and so forth. In recent years, however, it has become apparent that a low fluid loss is the most important characteristic of these fluids to be sought for, and that thickening to whatever degree desired can generally be readily accomplished by any of several means, provided that the fluid loss is maintained at a very small value, by reducing the ability of the fluid to undergo filtration.
在早期开发所述类型的油基流体时，主要关注的是提供增稠添加剂。在不同时期，人们发现并使用了许多添加剂，包括炭黑；脂肪酸皂、松香、妥尔油和类似的有机酸；各种沥青等等。然而，近年来人们发现，低流体损耗是这些流体需要追求的最重要的特性，只要通过降低流体的过滤能力，将流体损耗保持在一个非常小的值，那么无论需要何种程度的增稠，一般都可以通过几种方法中的任何一种轻松实现。
The technique set forth in the aforesaid Patent
上述专利
通过添加各种材料，油性载体被转化为适合手头用途的良好工作流体，例如钻井液。因此，可以添加增稠剂，使液体能够支撑切屑和细小的固体添加剂。此外，还可添加重晶石或方解石等加重材料，以增加钻井液的密度。另外，非常重要的一点是，可以添加一些物质来减少流体的过滤性，当流体与渗透性地层接触时就会发生这种情况。这些油基流体还可能含有油包水型乳化液形式的水，因此流体的连续相仍然是油。
In the earlier development of oil-base fluids of the types described, primary attention was given to providing thickening additives. Many were found and have been used at various times, including carbon black; soaps of fatty acids, rosin, tall oil, and the like organic acids; asphalts of various kinds; and so forth. In recent years, however, it has become apparent that a low fluid loss is the most important characteristic of these fluids to be sought for, and that thickening to whatever degree desired can generally be readily accomplished by any of several means, provided that the fluid loss is maintained at a very small value, by reducing the ability of the fluid to undergo filtration.
在早期开发所述类型的油基流体时，主要关注的是提供增稠添加剂。在不同时期，人们发现并使用了许多添加剂，包括炭黑；脂肪酸皂、松香、妥尔油和类似的有机酸；各种沥青等等。然而，近年来人们发现，低流体损耗是这些流体需要追求的最重要的特性，只要通过降低流体的过滤能力，将流体损耗保持在一个非常小的值，那么无论需要何种程度的增稠，一般都可以通过几种方法中的任何一种轻松实现。
The technique set forth in the aforesaid Patent
上述专利
An object of the present invention, accordingly, is to 5 provide a novel derivative of humic acid having broad utility.
因此，本发明的目的是提供一种具有广泛用途的新型腐植酸衍生物。
因此，本发明的目的是提供一种具有广泛用途的新型腐植酸衍生物。
Another object of the invention is to provide well working fluid compositions containing the said derivative, which exhibit improved filter-loss-reducing properties as 10 compared to those of United States Patent 3,168,475 under extreme conditions of temperature.
本发明的另一个目的是提供含有上述衍生物的油井工作液组合物，与美国专利 3,168,475 的组合物相比，该组合物在极端温度条件下具有更好的降低过滤损耗的性能。
本发明的另一个目的是提供含有上述衍生物的油井工作液组合物，与美国专利 3,168,475 的组合物相比，该组合物在极端温度条件下具有更好的降低过滤损耗的性能。
Other objects of the invention will appear as the description thereof proceeds.
本发明的其他目的将随着描述的深入而显现出来。
本发明的其他目的将随着描述的深入而显现出来。
Generally speaking and in accordance with illustrative 15 embodiments of our invention, we react humic acid with from about
一般来说，根据本发明的 15 个示例性实施方案，我们将腐植酸（其碱结合能力约为
20 oil but which may also be any available crude oil, topped or untopped or various fractions of crude oil, including kerosene, fuel oil, and the like, with the aforementioned humic acid derivative; and, optionally, we may add thereto any of the commonly employed additives for oil-base comprises ground minerals, such as barite, celestite, calcium carbonate, spent refinery clays, and the like; soaps, blown asphalts, carbon black, organophilic clays, and the like; water, and other known materials.
20 油，但也可以是任何现有的原油，带顶或不带顶的原油或原油的各种馏分，包括煤油、燃料油等，并添加上述腐植酸衍生物；另外，我们还可以添加任何常用的油基添加剂，包括重晶石、天青石、碳酸钙、废炼油厂粘土等磨碎的矿物；肥皂、吹沥青、炭黑、亲有机粘土等；水和其他已知材料。
一般来说，根据本发明的 15 个示例性实施方案，我们将腐植酸（其碱结合能力约为
20 oil but which may also be any available crude oil, topped or untopped or various fractions of crude oil, including kerosene, fuel oil, and the like, with the aforementioned humic acid derivative; and, optionally, we may add thereto any of the commonly employed additives for oil-base comprises ground minerals, such as barite, celestite, calcium carbonate, spent refinery clays, and the like; soaps, blown asphalts, carbon black, organophilic clays, and the like; water, and other known materials.
20 油，但也可以是任何现有的原油，带顶或不带顶的原油或原油的各种馏分，包括煤油、燃料油等，并添加上述腐植酸衍生物；另外，我们还可以添加任何常用的油基添加剂，包括重晶石、天青石、碳酸钙、废炼油厂粘土等磨碎的矿物；肥皂、吹沥青、炭黑、亲有机粘土等；水和其他已知材料。
Humic acid is a material of wide distribution and is present in soils, peat, and coals, particularly lignite or brown coal. It is an acid in which carboxyl and phenolic hydroxyl groups contribute base-combining ability. It is soluble in alkalies, such as caustic soda and sodium car5 bonate, has a deep brown color, and is readily soluble in water when converted to its alkali metal salt, which may be then termed an alkali metal humate, the commonest example of which is sodium humate
腐植酸是一种分布广泛的物质，存在于土壤、泥炭和煤炭中，尤其是褐煤。它是一种羧基和酚羟基具有碱结合能力的酸。它可溶于碱（如烧碱和碳酸钠），呈深褐色，转化为碱金属盐后易溶于水，可称为碱金属腐植酸盐，最常见的例子是腐植酸钠。
腐植酸是一种分布广泛的物质，存在于土壤、泥炭和煤炭中，尤其是褐煤。它是一种羧基和酚羟基具有碱结合能力的酸。它可溶于碱（如烧碱和碳酸钠），呈深褐色，转化为碱金属盐后易溶于水，可称为碱金属腐植酸盐，最常见的例子是腐植酸钠。
While humic acid is present in soils and peat, and may be extracted from them, for example, with dilute aqueous alkali, we prefer to obtain humic acid for the purposes of this invention in the form of lignite of high alkali solubility, of which vast deposits are found throughout the world, including, particularly, the United States, for example, in North Dakota, Texas, New Mexico, and Cali fornia. While we do not mean to limit ourselves thereby, we prefer a lignite having a solubility in dilute aqueous sodium hydroxide of at least
虽然腐植酸存在于土壤和泥炭中，并且可以通过稀碱水溶液等方式从土壤和泥炭中提取，但为了本发明的目的，我们更倾向于以高碱溶解度褐煤的形式获取腐植酸，全世界都有大量的褐煤矿藏，尤其是美国，例如北达科他州、德克萨斯州、新墨西哥州和加利福尼亚州。虽然我们无意因此而限制自己，但我们更倾向于使用在稀氢氧化钠水溶液中的溶解度至少为
虽然腐植酸存在于土壤和泥炭中，并且可以通过稀碱水溶液等方式从土壤和泥炭中提取，但为了本发明的目的，我们更倾向于以高碱溶解度褐煤的形式获取腐植酸，全世界都有大量的褐煤矿藏，尤其是美国，例如北达科他州、德克萨斯州、新墨西哥州和加利福尼亚州。虽然我们无意因此而限制自己，但我们更倾向于使用在稀氢氧化钠水溶液中的溶解度至少为
The fatty acid partial amide is an amdie of a fatty acid having from 12 to 22 carbon atoms, and which may be saturated or unsaturated, and of a polyalkylene polyamine having from three to seven amino groups, and thus in cluding tri-amines such as di-ethylene tri-amine, tetramines such as tri-ethylene tetramine, pentamines such as tetraethylene pentamine, and higher analogs of these, up to and including seven amino groups. The amide is only partial, that is, it is such that from about one-third to two-thirds of the nitrogen atoms are present in the form of a fatty acid amide, the balance being in the form of free amino groups, except that, of course, the latter are in the pentavalent state in combination with the humic acid to form a humate. We prefer fatty acids within the broad atoms and saturated and mono- and di-unsaturated, which of course includes the very common myristic, palmitic stearic, oleic, and linoleic acids. These are conveniently obtainable commercially as tallow fatty acids; corn; cottonseed, and soya fatty acids; and tall oil fatty acids, all of which may be natural or hydrogenated. Of these, we
脂肪酸部分酰胺是具有 12 至 22 个碳原子（可以是饱和或不饱和）的脂肪酸与具有 3 至 7 个氨基的聚烯烃多胺的酰胺，因此包括三胺（如二乙烯三胺）、四胺（如三乙烯四胺）、五胺（如四乙烯五胺）以及这些胺的高级类似物，最高包括 7 个氨基。酰胺只是部分的，也就是说，大约有三分之一到三分之二的氮原子以脂肪酸酰胺的形式存在，其余的以游离氨基的形式存在，当然，后者与腐植酸结合形成腐植酸盐的五价状态除外。我们更喜欢广义原子内的脂肪酸、饱和脂肪酸、单不饱和脂肪酸和双不饱和脂肪酸，其中当然包括非常常见的肉豆蔻酸、棕榈硬脂酸、油酸和亚油酸。这些都可以通过商业途径方便地获得，如牛油脂肪酸、玉米、棉籽和大豆脂肪酸以及妥尔油脂肪酸，所有这些都可能是天然的或氢化的。其中，我们
prefer tall oil fatty acids. As the polyamine, we prefer tetraethylene pentamine. The adduct as described and wherein the partial amide is present to the extent of about
首选妥尔油脂肪酸。作为多胺，我们倾向于使用四乙烯五胺。如上所述的加合物，其中部分酰胺的含量约为腐植酸碱结合能力的
脂肪酸部分酰胺是具有 12 至 22 个碳原子（可以是饱和或不饱和）的脂肪酸与具有 3 至 7 个氨基的聚烯烃多胺的酰胺，因此包括三胺（如二乙烯三胺）、四胺（如三乙烯四胺）、五胺（如四乙烯五胺）以及这些胺的高级类似物，最高包括 7 个氨基。酰胺只是部分的，也就是说，大约有三分之一到三分之二的氮原子以脂肪酸酰胺的形式存在，其余的以游离氨基的形式存在，当然，后者与腐植酸结合形成腐植酸盐的五价状态除外。我们更喜欢广义原子内的脂肪酸、饱和脂肪酸、单不饱和脂肪酸和双不饱和脂肪酸，其中当然包括非常常见的肉豆蔻酸、棕榈硬脂酸、油酸和亚油酸。这些都可以通过商业途径方便地获得，如牛油脂肪酸、玉米、棉籽和大豆脂肪酸以及妥尔油脂肪酸，所有这些都可能是天然的或氢化的。其中，我们
prefer tall oil fatty acids. As the polyamine, we prefer tetraethylene pentamine. The adduct as described and wherein the partial amide is present to the extent of about
首选妥尔油脂肪酸。作为多胺，我们倾向于使用四乙烯五胺。如上所述的加合物，其中部分酰胺的含量约为腐植酸碱结合能力的
Generally speaking, the adducts for use in our invention may be produced by bringing together humic acid and the partial amide compound in its base form. The base and the acid neutralize each other with salt formation, so as to produce the desired adduct in accordance with this aspect of the invention. Another general method of preparation is to convert the humic acid to a simple salt by reaction with an alkali, so as to produce sodium humate, potassium humate, ammonium humate, and the like, by reaction with sodium hydroxide, potassium hydroxide, or ammonium hydroxide, respectively. The partial amide compound is caused to be present in the form of a simple salt. Thus, the free amine groups of the partial amide may be reacted with a simple acid such as hydrochloric, acetic, and the like to give the corresponding partially amidated polyalkylene polyamine chloride or acetate, respectively. This method of procedure has the advantage that such onium salts, and the simple humates as described, are both water soluble, so that solutions of each reactant may be made, and the reaction completed by mixing solutions thereof together. Water, or mixtures of water with methanol, ethanol, isopropanol, acetone, and the like may also be used.
一般来说，本发明中使用的加合物可以通过将腐植酸和部分酰胺化合物以碱的形式结合在一起来生产。碱和酸相互中和，形成盐，从而根据本发明的这一方面生产出所需的加合物。另一种一般的制备方法是通过与碱反应将腐植酸转化为简单的盐，从而分别与氢氧化钠、氢氧化钾或氢氧化铵反应生成腐植酸钠、腐植酸钾、腐植酸铵等。部分酰胺化合物以单盐的形式存在。因此，部分酰胺的游离胺基团可与盐酸、醋酸等单酸反应，分别得到相应的部分酰胺化聚烯烃多胺氯化物或醋酸盐。这种操作方法的优点是这种鎓盐和所述的单腐植酸盐都是水溶性的，因此可以制得每种反应物的溶液，并通过将其溶液混合在一起完成反应。也可以使用水或水与甲醇、乙醇、异丙醇、丙酮等的混合物。
一般来说，本发明中使用的加合物可以通过将腐植酸和部分酰胺化合物以碱的形式结合在一起来生产。碱和酸相互中和，形成盐，从而根据本发明的这一方面生产出所需的加合物。另一种一般的制备方法是通过与碱反应将腐植酸转化为简单的盐，从而分别与氢氧化钠、氢氧化钾或氢氧化铵反应生成腐植酸钠、腐植酸钾、腐植酸铵等。部分酰胺化合物以单盐的形式存在。因此，部分酰胺的游离胺基团可与盐酸、醋酸等单酸反应，分别得到相应的部分酰胺化聚烯烃多胺氯化物或醋酸盐。这种操作方法的优点是这种鎓盐和所述的单腐植酸盐都是水溶性的，因此可以制得每种反应物的溶液，并通过将其溶液混合在一起完成反应。也可以使用水或水与甲醇、乙醇、异丙醇、丙酮等的混合物。
For the purposes of the invention, the preparation of the adducts as just described may be carried out without necessarily having all of the reactants in solution. That is, the humic acid and the partial amide compound can be mixed together in a pug mill or like apparatus, conveniently with enough moisture to facilitate the mechanical handling of the mixture and to speed up the reaction. This method can also be employed where the partial amide compound is in a salt form, as, for example, the hydrochloride; and indeed, the alkali necessary to convert the humic acid to its simple salt form such as sodium humate may be included in the mixture fed to the pug mill. Thus, a mixture in suitable proportions of weathered lignite, an alkali such as sodium hydroxide or borax or a mixture thereof, and the selected partial amide salt, with or without added water (or aqueous lower alcohol or ketone) may be passed through a pug mill to produce the inventive product. Where a long-chain alkyl ammonium cation is also incorporated as explained hereinbelow, this may be added along with the mixture of reactants fed to the pug mill at the same time.
就本发明而言，制备上述加合物时，不一定要将所有反应物都置于溶液中。也就是说，可以将腐植酸和部分酰胺化合物一起在一台球磨机或类似设备中混合，并加入足够的水分，以方便混合物的机械处理并加快反应速度。如果部分酰胺化合物是盐的形式，例如盐酸盐，也可以采用这种方法；事实上，将腐植酸转化为其简单盐形式（如腐植酸钠）所需的碱也可以包含在送入球磨机的混合物中。因此，风化褐煤、碱（如氢氧化钠或硼砂）或它们的混合物以及选定的部分酰胺盐的适当比例的混合物，无论是否添加了水（或含水低级醇或酮），都可以通过球磨机来生产本发明的产品。如果还加入了下文所述的长链烷基铵阳离子，则可将其与反应物混合物一起同时加入到球磨机中。
就本发明而言，制备上述加合物时，不一定要将所有反应物都置于溶液中。也就是说，可以将腐植酸和部分酰胺化合物一起在一台球磨机或类似设备中混合，并加入足够的水分，以方便混合物的机械处理并加快反应速度。如果部分酰胺化合物是盐的形式，例如盐酸盐，也可以采用这种方法；事实上，将腐植酸转化为其简单盐形式（如腐植酸钠）所需的碱也可以包含在送入球磨机的混合物中。因此，风化褐煤、碱（如氢氧化钠或硼砂）或它们的混合物以及选定的部分酰胺盐的适当比例的混合物，无论是否添加了水（或含水低级醇或酮），都可以通过球磨机来生产本发明的产品。如果还加入了下文所述的长链烷基铵阳离子，则可将其与反应物混合物一起同时加入到球磨机中。
Subsequent to the production of the adduct, it may be used as such, or it may be dried, with or without subsequent grinding. Where drying is carried out, it may be at relatively low temperatures, such as
在生产加合物之后，可以将其作为加合物使用，也可以将其干燥，无论是否进行后续研磨。在进行干燥时，可以在相对较低的温度下进行，例如
Where the full base-combining capacity of the humic acid has not been utilized, that is, when the partial amide has been combined with the humic acid in an equivalent proportion of less than
当腐植酸的全部碱结合能力未被利用时，也就是说，当部分酰胺与腐植酸的结合比例小于
Our inventive adducts, whether or not containing the 5 alkyl ammonium cations just referred to, may be used as produced, and preferably after drying and grinding for inclusion in well-working fluids of the type already described. A certain amount of agitation, particularly at elevated temperatures, is generally necessary to effect 0 good dispersion of our inventive adducts in such fluids. Generally, means will be present at the well site for obtaining such agitation and heat; and even when these are lacking, subsequent use of the well-working fluids, particularly where circulation at high bottom-hole tempera5 tures is involved, will bring about the desired dispersion. Generally, where the base fluid has some aromatic content, as is the case with crude oils in certain oil fields, dispersion will be rapid indeed.
本发明的加合物，无论是否含有刚才提到的 5 烷基铵阳离子，都可以在生产出来后使用，最好是在干燥和研磨后，加入到上述类型的良好加工液中。为了使本发明的加合物在此类液体中达到良好的分散效果，通常需要进行一定的搅拌，特别是在温度较高的情况下。一般情况下，井场会有获得这种搅拌和加热的手段；即使缺乏这些手段，随后使用油井作业液，特别是在井底温度较高的情况下进行循环，也会获得所需的分散效果。一般来说，如果基础油中含有一些芳烃成分，如某些油田的原油，分散速度确实很快。
In many cases it will be desirable to expedite the dis30 persion of our inventive adducts in the well-working fluids, without depending upon down-in-the-hole circulation. This is particularly desirable where the base oil of the well-working fluid is essentially paraffinic in nature. In that case, any of several dispersant additives may be in55 cluded with our adduct, such as any of the dispersing additives described and presently claimed in application Ser. No. 332,279, filed Dec. 20, 1963, now Patent No. 3,379,650, issued Apr. 23, 1968, and assigned to a common assignee. The contents of that application are incorporated herein by reference. Thereby disclosed herein (and in that application) are, particularly, nonyl phenol, octyl phenol, phenol, alkyl phenols generally from methyl through dodecyl, pentachlorophenol, salicyclic acid, benzoic acid, phthalic acid, and the like. Of these, we prefer nonyl phenol, as it is effective, easily handled, and widely obtainable commercially. As is well-known in organic chemistry, the alkyl groups methyl, octyl, nonyl, and dodecyl each contain respectively
在许多情况下，我们希望能够加快本发明加成物在油井工作液中的扩散速度，而不依赖于井下循环。当井下作业流体的基础油本质上是石蜡油时，这种情况尤为理想。在这种情况下，可以在我们的加成物中加入几种分散剂添加剂中的任何一种，例如 1963 年 12 月 20 日提交的第 332,279 号专利申请（现为第 3,379,650 号专利，1968 年 4 月 23 日颁发，已转让给共同受让人）中描述的和目前要求的任何一种分散添加剂。该申请的内容并入本文作为参考。本文（以及该申请中）特别公开了壬基酚、辛基酚、苯酚、一般从甲基到十二烷基的烷基酚、五氯苯酚、水杨酸、苯甲酸、邻苯二甲酸等。在这些烷基酚中，我们更倾向于壬基酚，因为它有效、易于处理，并且可以从市场上广泛获得。众所周知，在有机化学中，烷基甲基、辛基、壬基和十二烷基分别含有
Where such a dispersing additive is used, it may be present in any amount which is lesser than the amount of the inventive adduct. A range which has been found practical, balancing cost against benefits received, is from about
在使用这种分散添加剂时，其用量可以小于本发明加合物的用量。在平衡成本与收益的基础上，我们发现一个实用的范围是按加合物的重量计，从
We now give some examples showing the practice of our invention:
现在我们举几个例子来说明本发明的实际应用：
在生产加合物之后，可以将其作为加合物使用，也可以将其干燥，无论是否进行后续研磨。在进行干燥时，可以在相对较低的温度下进行，例如
Where the full base-combining capacity of the humic acid has not been utilized, that is, when the partial amide has been combined with the humic acid in an equivalent proportion of less than
当腐植酸的全部碱结合能力未被利用时，也就是说，当部分酰胺与腐植酸的结合比例小于
Our inventive adducts, whether or not containing the 5 alkyl ammonium cations just referred to, may be used as produced, and preferably after drying and grinding for inclusion in well-working fluids of the type already described. A certain amount of agitation, particularly at elevated temperatures, is generally necessary to effect 0 good dispersion of our inventive adducts in such fluids. Generally, means will be present at the well site for obtaining such agitation and heat; and even when these are lacking, subsequent use of the well-working fluids, particularly where circulation at high bottom-hole tempera5 tures is involved, will bring about the desired dispersion. Generally, where the base fluid has some aromatic content, as is the case with crude oils in certain oil fields, dispersion will be rapid indeed.
本发明的加合物，无论是否含有刚才提到的 5 烷基铵阳离子，都可以在生产出来后使用，最好是在干燥和研磨后，加入到上述类型的良好加工液中。为了使本发明的加合物在此类液体中达到良好的分散效果，通常需要进行一定的搅拌，特别是在温度较高的情况下。一般情况下，井场会有获得这种搅拌和加热的手段；即使缺乏这些手段，随后使用油井作业液，特别是在井底温度较高的情况下进行循环，也会获得所需的分散效果。一般来说，如果基础油中含有一些芳烃成分，如某些油田的原油，分散速度确实很快。
In many cases it will be desirable to expedite the dis30 persion of our inventive adducts in the well-working fluids, without depending upon down-in-the-hole circulation. This is particularly desirable where the base oil of the well-working fluid is essentially paraffinic in nature. In that case, any of several dispersant additives may be in55 cluded with our adduct, such as any of the dispersing additives described and presently claimed in application Ser. No. 332,279, filed Dec. 20, 1963, now Patent No. 3,379,650, issued Apr. 23, 1968, and assigned to a common assignee. The contents of that application are incorporated herein by reference. Thereby disclosed herein (and in that application) are, particularly, nonyl phenol, octyl phenol, phenol, alkyl phenols generally from methyl through dodecyl, pentachlorophenol, salicyclic acid, benzoic acid, phthalic acid, and the like. Of these, we prefer nonyl phenol, as it is effective, easily handled, and widely obtainable commercially. As is well-known in organic chemistry, the alkyl groups methyl, octyl, nonyl, and dodecyl each contain respectively
在许多情况下，我们希望能够加快本发明加成物在油井工作液中的扩散速度，而不依赖于井下循环。当井下作业流体的基础油本质上是石蜡油时，这种情况尤为理想。在这种情况下，可以在我们的加成物中加入几种分散剂添加剂中的任何一种，例如 1963 年 12 月 20 日提交的第 332,279 号专利申请（现为第 3,379,650 号专利，1968 年 4 月 23 日颁发，已转让给共同受让人）中描述的和目前要求的任何一种分散添加剂。该申请的内容并入本文作为参考。本文（以及该申请中）特别公开了壬基酚、辛基酚、苯酚、一般从甲基到十二烷基的烷基酚、五氯苯酚、水杨酸、苯甲酸、邻苯二甲酸等。在这些烷基酚中，我们更倾向于壬基酚，因为它有效、易于处理，并且可以从市场上广泛获得。众所周知，在有机化学中，烷基甲基、辛基、壬基和十二烷基分别含有
Where such a dispersing additive is used, it may be present in any amount which is lesser than the amount of the inventive adduct. A range which has been found practical, balancing cost against benefits received, is from about
在使用这种分散添加剂时，其用量可以小于本发明加合物的用量。在平衡成本与收益的基础上，我们发现一个实用的范围是按加合物的重量计，从
We now give some examples showing the practice of our invention:
现在我们举几个例子来说明本发明的实际应用：
Example 1 示例 1
950.4 grams of commercial tall oil fatty acid was mixed with 249.6 grams of commercial tetraethylene pentamine (thus, 3.25 and 6.50 gram equivalents respectively, so that about half of the amino groups of the tetraethylene pentamine were neutralized) and the mixture heated 55 to
将 950.4 克商品妥尔油脂肪酸与 249.6 克商品四乙烯五胺混合（因此，分别为 3.25 克和 6.50 克当量，这样四乙烯五胺中约一半的氨基被中和），并将混合物加热 55 至
将 950.4 克商品妥尔油脂肪酸与 249.6 克商品四乙烯五胺混合（因此，分别为 3.25 克和 6.50 克当量，这样四乙烯五胺中约一半的氨基被中和），并将混合物加热 55 至
Example 2 示例 2
To 350 ml . of diesel oil, 30 grams of the product of Example 1 was added, and the mixture stirred. Thus, the final composition was about 380 ml . diesel oil and 15 grams of the adduct proper. This was tested as a wellworking fluid for filtration loss in accordance with the Americal Petroleum Institute testing procedure, and gave a fluid loss of 2.5 ml . in thirty minutes.
在 350 毫升柴油中加入 30 克实施例 1 的产品，并搅拌混合物。因此，最终成分为约 380 毫升柴油和 15 克适当的加成物。按照美国石油学会的测试程序，将其作为井工液进行了过滤损失测试，结果表明在 30 分钟内的液体损失为 2.5 毫升。
在 350 毫升柴油中加入 30 克实施例 1 的产品，并搅拌混合物。因此，最终成分为约 380 毫升柴油和 15 克适当的加成物。按照美国石油学会的测试程序，将其作为井工液进行了过滤损失测试，结果表明在 30 分钟内的液体损失为 2.5 毫升。
Example 3 示例 3
A well-working fluid of the weighted type was prepared by mixing together 192 ml . diesel oil, 30 grams of the product of Example 1 (and thus containing 15 grams of the inventive adduct), 6 grams of dimethyldioctadecylammonium attapulgite, and 470 grams of 325 -mesh barite, giving a total volume of 350 ml . This was tested as de scribed in Example 2, and gave a fluid loss of 0.5 ml .
将 192 毫升柴油、30 克实施例 1 的产品（因此含有 15 克本发明的加合物）、6 克二甲基双 十八烷基铵阿塔波耳石和 470 克 325 目重晶石混合在一起，制备出总体积为 350 毫升的加权型 良好工作流体。按照实施例 2 所述方法进行测试，结果显示液体损失为 0.5 毫升。
将 192 毫升柴油、30 克实施例 1 的产品（因此含有 15 克本发明的加合物）、6 克二甲基双 十八烷基铵阿塔波耳石和 470 克 325 目重晶石混合在一起，制备出总体积为 350 毫升的加权型 良好工作流体。按照实施例 2 所述方法进行测试，结果显示液体损失为 0.5 毫升。
Example 4 示例 4
A production-size pug mill was fed continuously with the following materials at the rates specified:
在一台生产规模的碾磨机中，以规定的速率连续喂入以下材料：
Lignite,
褐煤，
lbs./min- 4.2
Tall oil fatty acid half amide of tetraethylene pentamine, as described in the first sentence of Example 1 Ibs.
四乙烯五胺的妥尔油脂肪酸半酰胺，如实施例 1 Ibs 第一句所述。
Water
Nonyl phenol lbs./min_- 0.3
壬基酚 磅/分钟_- 0.3
The lignite and the half amide, preheated to
预热至
When one gram of the product was dispersed in 350 ml . diesel oil so as to produce a well-working fluid, an A.P.I. fluid loss of less than 2.0 ml . was obtained.
将一克该产品分散在 350 毫升柴油中以产生良好的工作流体时，A.P.I. 流体损耗小于 2.0 毫升。
在一台生产规模的碾磨机中，以规定的速率连续喂入以下材料：
Lignite,
褐煤，
lbs./min- 4.2
Tall oil fatty acid half amide of tetraethylene pentamine, as described in the first sentence of Example 1 Ibs.
四乙烯五胺的妥尔油脂肪酸半酰胺，如实施例 1 Ibs 第一句所述。
Water
Nonyl phenol lbs./min_- 0.3
壬基酚 磅/分钟_- 0.3
The lignite and the half amide, preheated to
预热至
When one gram of the product was dispersed in 350 ml . diesel oil so as to produce a well-working fluid, an A.P.I. fluid loss of less than 2.0 ml . was obtained.
将一克该产品分散在 350 毫升柴油中以产生良好的工作流体时，A.P.I. 流体损耗小于 2.0 毫升。
Example 5 示例 5
An adduct in accordance with the invention was prepared, in which a minor proportion of the acid sites of the lignite was occupied by a long-chain ammonium cation, as set forth hereinabove.
根据本发明制备了一种加合物，其中褐煤酸位点的一小部分被上文所述的长链铵阳离子占据。
The following materials were put in a reaction vessel fitted with an agitator and with heating means, and mixed at
将下列材料放入装有搅拌器和加热装置的反应容器中，在
根据本发明制备了一种加合物，其中褐煤酸位点的一小部分被上文所述的长链铵阳离子占据。
The following materials were put in a reaction vessel fitted with an agitator and with heating means, and mixed at
将下列材料放入装有搅拌器和加热装置的反应容器中，在
The following long-chain onium salt was then added, and agitation continued for about one hour:
然后加入以下长链鎓盐，继续搅拌约一小时：
Dimethyl-di-hydrogenated tall oil fatty ammonium chloride
二甲基二氢化妥尔油脂肪氯化铵
二甲基二氢化妥尔油脂肪氯化铵
A mixture of the following components was prepared, added to the rest in the vessel, and allowed to react for 15 minutes:
制备以下成分的混合物，加入容器中的其余成分，并让其反应 15 分钟：
制备以下成分的混合物，加入容器中的其余成分，并让其反应 15 分钟：
Tall oil fatty acid half amide as in Example 4
实施例 4 中的妥尔油脂肪酸半酰胺
实施例 4 中的妥尔油脂肪酸半酰胺
The following materials were then added and allowed to mix for 10 minutes; the kaolin was a grinding aid:
然后加入以下材料并搅拌 10 分钟；高岭土是研磨助剂：
然后加入以下材料并搅拌 10 分钟；高岭土是研磨助剂：
Pounds 英镑
Kaolin 300 高岭土 300
Nonyl phenol 450 壬基酚 450
The solids, which consisted of the inventive adduct intermixed with the kaolin, were filtered off, dried in a rotary dryer, and ground.
过滤掉由本发明加合物和高岭土混合而成的固体，在旋转干燥器中干燥，然后研磨。
Kaolin 300 高岭土 300
Nonyl phenol 450 壬基酚 450
The solids, which consisted of the inventive adduct intermixed with the kaolin, were filtered off, dried in a rotary dryer, and ground.
过滤掉由本发明加合物和高岭土混合而成的固体，在旋转干燥器中干燥，然后研磨。
Example 6 例 6
s used in this control. It thus corresponded to the inventive product of U.S.在此控制中使用。因此，它与美国
The test muds were compounded of 228 ml . diesel 15 oil; 15 grams of a commercial mud invert-emulsifier which was essentially a calcium tall oil soap; 2 grams of dimethyldioctadecylammonium attapulgite; 122 ml . water; 500 grams barite; and 10 grams of either the product of Example 5 or the control as already described, to give a 00 total volume per sample of 350 ml .
试验泥浆由 228 毫升 15 号柴油、15 克商用泥浆反相乳化剂（基本上是一种妥尔油钙皂）、2 克二甲基双十八烷基铵阿塔波尔格石、122 毫升水、500 克重晶石和 10 克实施例 5 的产品或前述对照品混合而成，每个样品的总体积为 350 毫升。
试验泥浆由 228 毫升 15 号柴油、15 克商用泥浆反相乳化剂（基本上是一种妥尔油钙皂）、2 克二甲基双十八烷基铵阿塔波尔格石、122 毫升水、500 克重晶石和 10 克实施例 5 的产品或前述对照品混合而成，每个样品的总体积为 350 毫升。
The mud samples were treated and tested as shown in the following tabulation:
泥浆样本的处理和测试结果如下表所示：
泥浆样本的处理和测试结果如下表所示：
| Ex. 5 Ex.5 | Control 控制 | |||
和在 温度下热轧 16 小时 .:
|
||||
| 48 | ||||
| Filtrate, A.P.I., mal. 滤液，A.P.I.，mal. | 0 | |||
| Filtrate at
和 500 p.s.i. 时的滤液，毫升。 |
2.0 | 3.0 | ||
十六小时： Filtrate, A.P.I., mil........................
|
||||
| Filtrate at
在 |
12.8 | 27.2 | ||
1 Regular 30-minute test.
1 30 分钟常规测试。
wave invention by the use of specific ingredients, reaction conditions, and the like, it will be understood that numerous variations, equivalents, and alternatives may be employed in its practice, all within the scope of the claims which follow.
在本发明中使用了特定的成分、反应条件等，不言而喻，在实践中还可以使用许多变体、等价物和替代品，这些都在后面的权利要求书的范围之内。
1 30 分钟常规测试。
wave invention by the use of specific ingredients, reaction conditions, and the like, it will be understood that numerous variations, equivalents, and alternatives may be employed in its practice, all within the scope of the claims which follow.
在本发明中使用了特定的成分、反应条件等，不言而喻，在实践中还可以使用许多变体、等价物和替代品，这些都在后面的权利要求书的范围之内。
Having described our invention, we claim:
在描述了我们的发明之后，我们声称
在描述了我们的发明之后，我们声称
- A composition of matter consisting essentially of a salt of humic acid and a fatty acyl partial amide of a polyalkylene polyamine having from 3 to 7 amino groups, in which said partial amide has fatty acyl to the extent of 5 between one third and two thirds of the nitrogen atoms of said polyamine and wherein said fatty acyl radical has from 12 to 22 carbon atoms and said partial amide is present from about 50 to about 110 percent of the base combining capacity of said humic acid, together with an effective dispersing amount but less than that of said salt of a dispersing additive selected from the group consisting of phenol, alkyl phenols in which said alkyl group has from 1 to 12 carbon atoms, pentachlorophenol, salicylic acid, benzoic acid, and phthalic acid.
一种物质组合物，主要由腐植酸盐和具有 3 至 7 个氨基的聚烯烃多胺的脂肪酰基部分酰胺组成，其中所述部分酰胺的脂肪酰基占所述多胺氮原子的三分之一至三分之二，所述脂肪酰基具有 12 至 22 个碳原子，所述部分酰胺的含量约为所述腐植酸碱结合能力的 50%至 110%、与有效分散量但少于所述盐的分散添加剂一起使用，所述分散添加剂选自苯酚、烷基酚（其中所述烷基具有 1 至 12 个碳原子）、五氯苯酚、水杨酸、苯甲酸和邻苯二甲酸。 - The composition in accordance with claim 1 in which said dispersing additive is nonyl phenol.
根据权利要求 1 所述的组合物，其中所述的分散添加剂为壬基酚。 - A composition of matter in accordance with claim 1 in which said percentage is less than
, and the remainder of said base-combining capacity is neutralized with an alkyl-substituted ammonium cation in which at least one alkyl thereof has between 12 and 22 carbon atoms.
2.一种符合权利要求 1 的物质组合物，其中所述百分比小于，并且所述碱结合能力的剩余部分用烷基取代的铵阳离子中和，其中至少一个烷基具有 12 到 22 个碳原子。 - The composition in accordance with claim 3 in which said dispersing additive is nonyl phenol.
4.根据权利要求 3 所述的组合物，其中所述分散添加剂为壬基酚。 - An oil base well-working fluid consisting essentially of a major proportion of oil and a minor proportion but sufficient to substantially lower the filter loss of a salt of humic acid and a fatty acyl partial amide of a polyalkylene polyamine having from 3 to 7 amino groups, 70 in which said partial amide has fatty acyl to the exten of between one third and two thirds of the nitrogen atoms of said polyamine and wherein said fatty acyl radical has from 12 to 22 carbon atoms and said partial amide is present at from about 50 to about 110 percent of the base 75 combining capacity of said humic acid.
一种油基加工液，其主要成分是油和少量的腐植酸盐以及具有 3 至 7 个氨基的聚烯烃多胺的脂肪酰部分酰胺，但这些成分足以大大降低过滤损失、70 其中所述部分酰胺的脂肪酰基占所述多胺氮原子的三分之一至三分之二，所述脂肪酰基具有 12 至 22 个碳原子，所述部分酰胺的含量约为所述腐植酸碱 75 结合能力的 50%至 110%。
- An oil base-well working fluid in accordance with claim 5 in which said percentage is less than
, and the remainder of said base-combining capacity is neutralized with an alkyl-substituted ammonium cation in which at least one alkyl thereof has between 12 and 22 carbon atoms.
6.根据权利要求5所述的一种油基井工作液，其中所述百分比小于，并且所述碱结合能力的剩余部分用烷基取代的铵阳离子中和，其中至少一个烷基具有12到22个碳原子。 - A fluid in accordance with claim 5 in which a dispersing additive selected from the group consisting of phenol, alkyl phenols in which said alkyl group has from 1 to 12 carbon atoms, pentachlorophenol, salicyclic acid, benzoic acid, and phthalic acid is present in an effective dispersing amount but less than that of said salt.
6.一种符合权利要求 5 的流体，其中的分散添加剂选自由苯酚、烷基酚（其中所述烷基具有 1 至 12 个碳原子）、五氯苯酚、水杨酸、苯甲酸和邻苯二甲酸组成的组，其有效分散量低于所述盐的有效分散量。 - A fluid in accordance with claim 7 in which said dispersing additive is nonyl phenol
根据权利要求 7 的流体，其中所述分散添加剂为壬基酚 - A fluid in accordance with claim 6 in which a dis- 15 persing additive selected from the group consisting of phenol, alkyl phenols in which said alkyl group has from 1 to 12 carbon atoms, pentachlorophenol, salicyclic acid, benzoic acid, and phthalic acid is present in an effective dispersing amount but less than that of said salt.
7.根据权利要求 6 的一种流体，其中的分散添加剂选自苯酚、烷基酚（其中所述烷基具有 1 至 12 个碳原子）、五氯苯酚、水杨酸、苯甲酸和邻苯二甲酸组成的组，其有效分散量小于所述盐的有效分散量。 - A fluid in accordance with claim 9 in which said dispersing additive in nonyl phenol.
10. 根据权利要求 9 的一种流体，其中所述分散添加剂为壬基酚。 - In a process for drilling a well wherein there is circulated in the well an oil-base drilling fluid subject to filtration into permeable formations penetrated by the well, the method of maintaining said filtration at a selected low value during said drilling which comprises ad- mixing with said drilling fluid a salt of humic acid and a fatty acyl partial amide of a polyalkylene polyamine having from 3 to 7 amino groups, in which said partial amide has fatty acyl to the extent of between one third and two thirds of the nitrogen atoms of said polyamine and wherein said fatty acyl radical has from 12 to 22 carbon atoms and said partial amide is present at from about 50 to about 110 percent of the base-combining capacity of said humic acid.
在一种钻井过程中，油基钻井液在井中循环，钻井液被过滤到钻井所穿透的渗透地层中，在钻井过程中将所述过滤保持在选定的低值的方法包括将腐植酸盐和具有3至7个氨基的聚烯多胺的脂肪酰基部分酰胺与所述钻井液混合、其中，所述部分酰胺的脂肪酰基占所述多胺氮原子的三分之一至三分之二，所述脂肪酰基具有 12 至 22 个碳原子，所述部分酰胺的含量约为所述腐植酸碱结合能力的 50%至 110%。 - The process in accordance with claim 11 in which said percentage is less than
, and the remainder of said base-combining capacity is neutralized with an alkylsubstituted ammonium cation in which at least one alkyl thereof has between 12 and 22 carbon atoms.
12.根据权利要求 11 所述的工艺，其中所述百分比小于，并且所述碱结合能力的剩余部分用烷基取代的铵阳离子中和，其中至少一个烷基具有 12 到 22 个碳原子。
UNITED STATES PATENTS 美国专利
| 2,5 | 5/1952 | Blair -..-.-- 布莱尔 |
| 2/1965 |
|
|
| 4/1968 | Be 是 |
HERBERT B. GUYNN, Primary Examiner
主审查员 HERBERT B. GUYNN
U.S. Cl. X.R. U.S. Cl.X.R.
主审查员 HERBERT B. GUYNN
U.S. Cl. X.R. U.S. Cl.X.R.