[75] Inventor: Roy F. House, Lafayette, La.
[75] 发明者罗伊-F.-豪斯，拉法叶市
[73] Assignee: Venture Innovations, Inc., Lafayette, La.
[73] Assignee：Venture Innovations, Inc.
[21] Appl. No.: 574,379 [21] 申请号：574,379
[22] Filed: Jan. 27, 1984
[22] 归档：1984年1月27日
[51] Int. Cl. 4 C07C 91/26; C09F 7/14
[51] Int.Cl.4 C07C 91/26; C09F 7/14
52] U.S. Cl 260/501.15; 260/501.11; 260/404.5
52]U.S. Cl 260/501.15；260/501.11；260/404.5
[58] Field of Search 260/501.15, 501.11 260/404.5 PA
[260/501.15, 501.11 260/404.5 PA

3,494,865 2/1970 Andrews, Jr. et al. ......... 252/8.5 M
3,671,427 6/1972 Andrews, Jr. et al. .......... 260/404.5
3,671,428 6/1972 Kim ............................... 252/8.5 M
3,775,447 11/1973 Andrews et al. .......... 260/404.5 PA
Primary Examiner-Glennon H. Hollrah Assistant Examiner-Raymond Covington
主审查员--格伦农-H-霍拉赫 助理审查员--雷蒙德-考文顿
[57]
ABSTRACT 摘要
The invention provides a novel process of preparing organophilic humate derivatives wherein: an aqueous solution of a humic acid-containing material is prepared with an alkali metal or ammonium base; an amine containing at least 16 carbon atoms and at least one functional group per molecule selected from the group consisting of primary amino, secondary amino, quaternary ammonium, and mixtures thereof, is mixed with the humate solution; an acid is mixed with the amine-containing humate solution in an amount at least sufficient to neutralize all of the alkali metal or ammonium base used to prepare the humate solution; and thereafter the organophilic substituted ammonium humate derivative is recovered.
本发明提供了一种制备亲有机腐植酸衍生物的新工艺，其中包括用碱金属或铵碱制备含腐植酸材料的水溶液；将至少含有 16 个碳原子且每个分子至少含有一个官能团的胺与腐植酸溶液混合，该官能团选自伯氨基、仲氨基、季铵及其混合物组成的组；将一种酸与含胺腐植酸盐溶液混合，其用量至少足以中和所有用于制备腐植酸盐溶液的碱金属或铵碱，然后回收亲有机取代的腐植酸铵衍生物。
9 Claims, No Drawings 9 项索赔，无图纸

The invention relates to methods for the manufacture of organophilic amine derivatives of complex phenolic compounds.
本发明涉及复杂酚类化合物的亲有机胺衍生物的制造方法。

In the drilling of wells for oil and gas by the rotary method, it is common to use a circulating fluid which is pumped down to the bottom of the well through a drill pipe, where the fluid emerges through ports in the drilling bit. The fluid rises to the surface in the annular space between the drill pipe and the walls of the hole, and at the surface it is treated to remove cuttings and the like and to prepare it for recirculation into the drill pipe. The circulation is substantially continuous while the drill pipe is rotated.
在用旋转法钻探石油和天然气井时，通常使用循环流体，通过钻杆将流体泵送到井底，流体从钻头的孔口流出。流体在钻杆和井壁之间的环形空间内上升到地面，在地面经过处理，除去切屑等，准备再循环到钻杆中。当钻杆旋转时，循环基本上是连续的。
An important feature of oil base well working fluids of the class described is their ability to resist filtration. In most instances when they are in actual use, whether as drilling fluids, packer fluids, fracturing or completion fluids, the well working fluid is in contact with a more or less permeable formation, such as, for example, sandstone, sandy shale and the like, with an effective balance of pressure such that the fluid tends to be forced into the permeable formation. When a well working fluid is deficient in its ability to resist filtration, then the solids in the fluid are held back by the permeable formation and build up as a filter cake or sludge on its surfaces, while the liquid per se of the well working fluid filters into the permeable formation. The filter cake or sludge thus formed is generally very undesirable. Moreover, the loss of oil to the formation is very expensive, not only because of the cost of the oil itself, but also due to the cost of maintaining the properties and composition of the fluid.
所述类别的油基油井工作液的一个重要特点是具有抗过滤能力。在实际使用中，无论是作为钻井液、封隔器液、压裂液还是完井液，在大多数情况下，油井工作液都会与或多或少具有渗透性的地层接触，例如砂岩、砂页岩等，压力的有效平衡使得油井工作液倾向于被迫进入渗透性地层。当油井工作流体的抗过滤能力不足时，流体中的固体就会被渗透地层阻挡，并在其表面形成滤饼或淤泥，而油井工作流体中的液体本身则会过滤到渗透地层中。这样形成的滤饼或淤泥通常是非常不理想的。此外，地层中石油的损失是非常昂贵的，这不仅是因为石油本身的成本，还因为维持液体特性和成分的成本。
Various additives have been used or suggested for use as fluid loss additives to prevent or decrease this loss of fluid by filtration from oil base muds. Some of the first materials used for this purpose were asphalt and various modified asphaltic materials. The following U.S. patents all disclose various amine derivatives of various polyphenolic compounds for use as fluid loss additives (hereinafter sometimes referred to as FLA) for oil base muds: Jordan et al. U.S. Pat. No. 3,168,475; Jordan et al. U.S. Pat. No. 3,281,458; Beasley et al. U.S. Pat. No 3,379,650; Cowan et al. U.S. Pat. No. 3,232,870; Cowan et al. U.S. Pat. No. 3,425,953; Andrews et al. U.S. Pat. No. 3,494,865; Andrews et al. U.S. Pat. No. 3,671,427; Andrews et al. U.S. Pat. No. 3,775,447; Kim U.S. Pat. No. 3,538,071; and Kim U.S. Pat. No. 3,671,428. These patents are incorporated herein by reference for all purposes.
人们使用或建议使用各种添加剂作为流体损失添加剂，以防止或减少油基泥浆中流体的过滤损失。最早用于此目的的一些材料是沥青和各种改性沥青材料。以下美国专利都公开了各种多酚化合物的各种胺衍生物，可用作油基泥浆的流体流失添加剂（以下有时称为 FLA）：Jordan et al.No. 3,168,475; Jordan et al.No. 3,281,458; Beasley et al.No 3,379,650; Cowan et al.No. 3,232,870; Cowan et al.3,425,953; Andrews et al.No. 3,494,865; Andrews et al.No. 3,671,427; Andrews et al.No. 3,775,447; Kim U.S. Pat.No. 3,538,071；以及 Kim U.S. Pat.第 3,671,428 号。为所有目的，这些专利通过引用并入本文。
Jordan et al. U.S. Pat. No. and U.S. Pat No. disclose certain substituted ammonium salts of humic acid. Compounds useful in the practice of their invention can be represented by the formula
Jordan et al. 号和美国专利 号公开了腐植酸的某些取代铵盐。在其发明实践中有用的化合物可由式表示

wherein at least one of the R's is an alkyl radical having from 12 to 22 carbon atoms in a straight chain, and in which those R's which do not have from 12 to 22 carbon atoms in a straight chain are chosen from the group consisting of hydrogen, alkyl radicals having fewer than
其中至少有一个 R 是直链上有 12 至 22 个碳原子的烷基，而直链上没有 12 至 22 个碳原子的 R 选自以下组别：氢、直链上的碳原子数少于 12 的烷基、直链上的碳原子数少于 22 的烷基、直链上的碳原子数少于 12 的烷基、直链上的碳原子数少于 22 的烷基、直链上的碳原子数少于 12 的烷基。
12 carbon atoms, phenyl, and benzyl; wherein Hu - is the anion of humic acid; wherein the term "alkyl" includes unsaturated alkyl chains, such as, for example, oleyl as well as stearyl; and wherein at least one of the
其中 Hu - 是腐植酸的阴离子；其中术语 "烷基 "包括不饱和烷基链，例如油基和硬脂基；其中至少一个 "烷基 "是腐植酸的阴离子。
5 alkyl radicals having from 12 to 22 carbon atoms may be attached to the nitrogen atom indirectly through an intermediate linkage, most generally a heterocylic carbon-nitrogen ring
5 个具有 12 至 22 个碳原子的烷基可通过中间连接间接连接到氮原子，最常见的是杂环碳氮环
Beasley et al. U.S. Pat. No. 3,379,650 discloses vari10 ous additives (dispersants) which facilitate the dispersion of long chain alkyl ammonium humates in organic liquids. Such humates are more readily dispersible in some organic liquids than in others. The dispersibility of these humates is also dependent to some extent on their long chain alkyl ammonium humates decreases their dispersibility.
Beasley et al.第 3,379,650 号专利公开了 10 种不同的添加剂（分散剂），它们有助于长链烷基腐植酸铵在有机液体中的分散。这些腐植酸盐在某些有机液体中比在其他有机液体中更容易分散。这些腐植酸盐的分散性在一定程度上还取决于它们的长链烷基腐植酸铵是否会降低其分散性。
Andrews et al. U.S. Pat. No. 3,494,865 discloses an adduct prepared by reacting humic acid with from about to about of its base-combining capacity, with certain fatty acid partial amides of a polyalkylene polyamine. As stated therein at column 3, lines 10-12. "The adduct as described and wherein the partial amide is present to the extent of about of the base-combining capacity of the humic acid probably represents salt formation for , the remaining being adsorption, although in view of the complicated nature of the constituents, exact structural analysis is difficult and somewhat undertain. Also, depending on the drying temperature, where heat is used for such a step, the adduct may undergo a certain extent of amidification where the amine groups of the polyamines are combined with the carboxyl groups of the humic acid." well working fluids and further discloses certain dispersants which are desirable to expedite the dispersion of the adducts without depending on down-hole circulation of the well working fluids.
Andrews et al.3,494,865号专利公开了一种加合物，该加合物是由腐植酸（其碱结合能力约为 至 ）与聚亚烷基多胺的某些脂肪酸部分酰胺反应制备而成。如其中第 3 栏第 10-12 行所述。"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 ，可能代表 的盐形成，其余的 为吸附，但鉴于成分的复杂性，精确的结构分析很难，而且有些不充分。此外，根据干燥温度的不同（如果在这一步骤中使用了热量），加合物可能会发生一定程度的酰胺化，此时多胺的胺基团与腐植酸的羧基结合。

Andrews et al. U.S. Pat. No. 3,671,427 discloses certain adducts of humic acid and a fatty acyl partial amide of a polyalkylene polyamine wherein the partial amide is linked to the humic acid by an amide linkage.
Andrews et al.第 3,671,427 号专利公开了腐植酸与聚烯多胺的脂肪酰部分酰胺的某些加合物，其中部分酰胺通过酰胺连接与腐植酸相连。
Beasley et al. U.S. Pat. No. 3,325,537 discloses certain zation of at least by weight and at the same time obtain a resulting pH within the limits of 5.2 to 7.5 . Such lignite solutions are disclosed to be useful in preparing long chain alkyl ammonium humates.
Beasley et al.3,325,537号公开了按重量计至少 的某些zation，同时得到的pH值在5.2至7.5的范围内。这种褐煤溶液可用于制备长链烷基腐植酸铵。

Generally speaking, the substituted ammonium humates disclosed in these prior art patents may be produced by bringing together humic acid and the substituted ammonium compound in its base form. The base and the acid neturalize each other with salt formation to produce the desired humate derivative. Another general method of preparation disclosed 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 alkali metal or ammonium bases, respectively. The substituted ammonium compound is caused to be present in the form of a simple salt or in quaternary ammonium form. Thus the free amine groups may be reacted with a simple acid such as hydrochloric, acetic, and the like to 5 give the corresponding substituted ammonium chloride or acetate, respectively. This method of procedure is stated to have the advantage that the substituted ammonium salts and quaternary ammonium salts, and the
一般来说，这些现有技术专利中公开的取代铵腐植酸盐可以通过将腐植酸和取代铵化合物以碱的形式结合在一起来生产。碱和酸通过盐的形成相互净化，生成所需的腐植酸衍生物。公开的另一种一般制备方法是通过与碱反应将腐植酸转化为简单的盐，从而通过与碱金属或铵碱反应分别生成腐植酸钠、腐植酸钾、腐植酸铵等。取代的铵化合物会以单盐或季铵的形式存在。因此，游离胺基团可与盐酸、醋酸等单酸反应，分别生成相应的取代氯化铵或醋酸铵。据说这种方法的优点是取代铵盐和季铵盐，以及
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. Mixtures of water with methanol, ethanol, isopropanol, acetone, and the like may be needed for some substituted ammonium salts and quaternary ammonium salts.
所述的简单腐殖酸盐均可溶于水，因此可以配制每种反应物的溶液，并通过将其溶液混合在一起完成反应。某些取代铵盐和季铵盐可能需要水与甲醇、乙醇、异丙醇、丙酮等的混合物。
I have found that the prior art method for preparing organophilic humate derivatives wherein the humic acid containing material and the substituted ammonium compound in base form are reacted together produces organophilic humate derivatives which are inefficient high temperature fluid loss control additives for oil base drilling fluids. The amount of substituted ammonium compound which can be reacted with the humic acid under these conditions is insufficient to react with all of the acidic functional groups of the humic acid.
我发现，现有技术中制备嗜有机腐植酸衍生物的方法是将含腐植酸的材料和碱形式的取代铵化合物反应在一起，生成的嗜有机腐植酸衍生物是一种低效的油基钻井液高温流体损失控制添加剂。在这些条件下能与腐植酸反应的取代铵化合物的量不足以与腐植酸的所有酸性官能团反应。
I have further found that the prior art method for preparing organophilic humate derivatives wherein the humic acid containing material is converted to a water soluble or colloidally dispersible humate salt and subsequently reacted with a substituted ammonium compound in the form of an acid salt or quaternary ammonium salt suffers from several disadvantages, i.e., (a) many substituted ammonium salts are not water soluble and a polar organic solvent such as an alcohol, ketone, and the like must be added to the salt in order for the substituted ammonium salt to properly react with the humate salt. The use of such solvents is expensive and creates disposal problems when it is removed from the product, as by filtration, drying, and the like; (b) as noted in Beasley et al. U.S. Pat. No. 3,325,537, an excessive amount of substituted ammonium salt must be used to precipitate the humate salt when the pH of the humate solution is greater than 7.5 ; (c) the humate salt and the substituted ammonium salt commence reaction as soon as the substituted ammonium salt is mixed with the humate solution. As the precipitation of the organophilic humate derivative proceeds, some of the reactive sites on the humate become unavailable for reaction resulting in a sorption of the substituted ammonium salt onto the reacted ammonium humate derivative; and (d) filtration of the precipitated organophilic humate derivative is poor when utilizing as the substituted ammonium salt an amino-amide compound of the types disclosed in Andrews et al. U.S. Pat. Nos. 3,494,865; ; and .
我还发现，现有技术中用于制备亲有机腐植酸衍生物的方法存在几个缺点，即先将含腐植酸的材料转化为水溶性或胶体分散性腐植酸盐，然后再与酸盐或季铵盐形式的取代铵化合物反应、(a) 许多取代铵盐不溶于水，必须在盐中加入极性有机溶剂，如醇、酮等，才能使取代铵盐与腐植酸盐正常反应。使用这类溶剂价格昂贵，而且在通过过滤、干燥等方法从产品中去除时会产生处理问题；（b）如 Beasley et al.3,325,537 号中指出，当腐植酸盐溶液的 pH 值大于 7.5 时，必须使用过量的取代铵盐来沉淀腐植酸盐；(c) 当取代铵盐与腐植酸盐溶液混合后，腐植酸盐和取代铵盐立即开始反应。随着亲有机腐植酸盐衍生物沉淀的进行，腐植酸盐上的一些反应位点无法进行反应，导致取代铵盐吸附在反应后的腐植酸铵衍生物上；以及 (d) 当使用 Andrews et al. U.S. Pat.Nos.3,494,865； ；和 。

I have now found a process for the preparation of organophilic humate derivatives which overcomes the disadvantages of the prior art processes and which produces efficient fluid loss control additives in oil base drilling fluids. These additives impart excellent high temperature filtration control characteristics to oil base drilling fluids.
我现在已经找到了一种制备亲有机腐殖酸衍生物的工艺，它克服了现有工艺的缺点，并能在油基钻井液中生产出高效的流体流失控制添加剂。这些添加剂可为油基钻井液提供出色的高温过滤控制特性。

The process of my invention comprises: preparing an aqueous humate solution; mixing with the humate solution an amine containing at least one functional group per molecule selected from the group consisting of primary amino ( ), secondary amino ( ), quaternary ammonium
本发明的工艺包括：制备腐植酸水溶液；与腐植酸水溶液混合的胺，其每个分子至少含有一个官能团，该官能团选自由伯氨基（ ）、仲氨基（ ）、季铵组成的组。

5
or mixtures thereof; mixing with this amine containing humate solution an acid in an amount sufficient to at least neutralize all of the base used in preparing the 0 aqueous humate solution; and thereafter recovering an organophilic ammonium humate; wherein the temperature of the amine containing humate, solution is at least about . .).
或其混合物；与该含腐植酸胺溶液混合一种酸，其量至少足以中和制备0腐植酸水溶液时使用的所有碱；然后回收一种嗜有机腐植酸铵；其中含腐植酸胺溶液的温度至少约为 . )。

Accordingly, it is an object of this invention to pro15 vide an improved process for the preparation of organophilic humate derivatives which are useful as additives to control the fluid loss from oil base drilling fluids.
因此，本发明的目的是提供15 一种改进的亲有机腐殖酸衍生物的制备工艺，这种衍生物可用作添加剂来控制油基钻井液的流体损失。
It is another object of this invention to provide a process for the preparation of organophilic ammonium humate derivatives in which the humic acid and the ammonium compound are more uniformly reacted.
本发明的另一个目的是提供一种制备亲有机腐殖酸铵衍生物的工艺，其中腐殖酸和铵化合物的反应更加均匀。
It is yet another object of this invention to provide a process for the preparation of organophilic ammonium humates which requires no polar organic solvents.
本发明的另一个目的是提供一种无需极性有机溶剂的亲有机腐植酸铵制备工艺。

These and other objects of this invention will be apparent to one skilled in the art upon reading this specification and the appended claims.
本领域技术人员在阅读本说明书和所附权利要求书后，就会明白本发明的上述和其他目的。

While the invention is susceptible of various modifi30 cations and alternative forms, specific embodiments thereof will hereinafter be described in detail and shown by way of example. It should be understood, however, that it is not intended to limit the invention to the particular forms disclosed, but, on the contrary, the invention is to cover all modifications and alternatives falling within the spirit and scope of the invention as expressed in the appended claims.
虽然本发明可以有各种修改30 和替代形式，但下文将详细描述其具体实施例，并以举例的方式加以说明。然而，应当理解的是，本发明无意限制于所公开的特定形式，相反，本发明涵盖了在所附权利要求书所表达的本发明精神和范围内的所有修改和替代形式。
The compositions can comprise, consist essentially of, or consist of the stated materials. The method can comprise, consist essentially of, or consist of the stated steps with the stated materials.
组合物可以包括、主要包括或包括所述材料。该方法可以包括、主要包括或包括使用所述材料的所述步骤。

The novel process of my invention for preparing organophilic humate derivatives comprises: (a) dispersing a humic acid-containing material in water with an alkali metal or ammonium base to produce a humate solution; (b) mixing with the humate solution an amine containing at least sixteen carbon atoms and at least one functional group per molecule selected from the group consisting of primary amino, secondary amino, quater nary ammonium, or mixtures thereof; (c) mixing with said amine containing humate solution an acid in an amount sufficient to at least neutralize all of the alkali metal or ammonium base; and (d) thereafter recovering the organophilic ammonium humate; wherein the temperature of the amine containing humate solution is above about . ( .).
本发明制备亲有机腐植酸衍生物的新工艺包括(a) 将含腐植酸的材料与碱金属或铵盐分散在水中，生成腐植酸盐溶液； (b) 与腐植酸盐溶液混合一种胺，该胺至少含有 16 个碳原子，每个分子至少含有一个官能团，该官能团选自由伯氨基、仲氨基、季铵或它们的混合物组成的组；(c) 与所述含腐植酸胺溶液混合一种酸，其用量足以至少中和所有碱金属或铵碱；以及 (d) 随后回收嗜有机腐植酸铵；其中，含腐植酸胺溶液的温度高于约 。( 。)。
Humic acid is a material of wide distribution and is present in soils, peat, and coals, particularly lignite or brown coal, and most particularly in the soft brown coal known as a leonardite. Humic acids are complex organic molecules that are formed by the breakdown of organic matter. Their exact structures are unknown and they are extremely variable. The principal organic groups present are phenolic and carboxylic OH , aliphatic CH, carbonyl, conjugated carbonyl or aromatic
腐植酸是一种分布广泛的物质，存在于土壤、泥炭和煤炭中，特别是褐煤或褐煤，尤其是被称为褐铁矿的软褐煤中。腐植酸是有机物质分解后形成的复杂有机分子。它们的确切结构尚不清楚，而且极其易变。存在的主要有机基团是酚基和羧基 OH、脂肪族 CH、羰基、共轭羰基或芳香基。
or or ionic carboxyl, and possibly others. The average molecular weight of the humic acids is between 5,000 and 50,000 . They have no -ray or electron diffraction patterns and are therefore presumably amorphous.
或 或离子羧基，可能还有其他。腐植酸的平均分子量在 5,000 到 50,000 之间。它们没有 射线或电子衍射图，因此可能是无定形的。

The humic acids have a large cation exchange capacity which varies from 200 to 500 milliequivalents per 100 grams at pH 7 depending on the humus source. Humic acids are colloids. When the cation exchange sites on the humic molecule are filled predominantly with other than hydrogen, the material is called humate. The humates of monovalent inorganic and ammonium ions are soluble in water, but the humates of multivalent cations are insoluble.
腐殖酸具有很大的阳离子交换容量，根据腐殖质来源的不同，在 pH 值为 7 时，每 100 克腐殖酸的阳离子交换容量从 200 毫当量到 500 毫当量不等。腐殖酸是胶体。当腐殖酸分子上的阳离子交换位点主要由氢以外的元素填充时，这种物质就被称为腐殖酸盐。单价无机离子和铵离子的腐殖酸盐可溶于水，但多价阳离子的腐殖酸盐则不溶于水。
The term humic acid is used herein to include all of the colloidal acids derived from humus, including humic acid, ulmic acid and fulvic acid. Humic acid is soluble in alkali but insoluble in acid, methyl ethyl ketone, and methyl alcohol. Ulmic acid is soluble in alkali and methyl etyl ketone but insoluble in methyl alcohol. Fulvic acid is soluble in alkali, methyl ethyl ketone and methyl alcohol. The term humic acid is also intended to mean humic acids which have been further oxidized to increase their carboxyl content. See for example, "Chemistry of Brown Coals. IV. Action of Oxygen in Presence of Alkali", R. A. Durie and S. Sternhill, Australian Journal of Applied Science, 9, No. 4, 360-369, 1958.
这里所说的腐植酸包括从腐殖质中提取的所有胶体酸，包括腐植酸、溃疡酸和富勒酸。腐植酸可溶于碱，但不溶于酸、甲乙酮和甲醇。腐植酸可溶于碱和甲乙酮，但不溶于甲醇。富里酸可溶于碱、甲乙酮和甲醇。腐植酸一词也指经过进一步氧化以增加其羧基含量的腐植酸。例如，参见 "褐煤的化学"。IV.IV. 氧气在碱存在下的作用"，R. A. Durie 和 S. Sternhill，《澳大利亚应用科学杂志》，9，第 4 期，360-369，1958 年。

While humic acid is present in soils and peat, and may be extracted from them, for example, with dilute aqueous alkali, it is preferred 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, Montana, Texas, New Mexico, and California. While I do not mean to be limited thereby, I prefer a humic acid source having a solubility in dilute, aqueous sodium hydroxide of at least by dry weight, preferably at least as this provides a reasonable compromise between cost and efficacy in the final product.
虽然腐植酸存在于土壤和泥炭中，并且可以从它们中提取，例如用稀碱水溶液提取，但为了本发明的目的，最好以高碱溶解度的褐煤的形式获得腐植酸，全世界都有大量的褐煤矿藏，特别是美国，例如在北达科他州、蒙大拿州、得克萨斯州、新墨西哥州和加利福尼亚州。虽然我无意因此而受到限制，但我更倾向于使用在稀氢氧化钠水溶液中的溶解度至少为 （以干重计），最好至少为 的腐植酸源，因为这样可以在最终产品的成本和功效之间达成合理的折衷。

The amino compounds which may be used in this invention include polyamines or polyamidoamines which contain at least one primary or secondary amine 45 group per molecule and at least 16 carbon atoms selected from the group consisting of (I), (II), (III), and mixtures thereof:
本发明中可使用的氨基化合物包括多胺或多氨基胺，它们每个分子至少含有一个伯胺或仲胺 45 基团，至少含有 16 个碳原子，这些碳原子选自由（I）、（II）、（III）及其混合物组成的组：

where is an aliphatic group containing from 12 to 30 carbon atoms; is selected from the group consisting of H and , and mix- 60 tures thereof; is an aliphatic group containing from 11 to 29 carbon atoms; and wherein at least one of the groups are H
其中 是含有 12 至 30 个碳原子的脂肪族基团； 选自 H 和 组成的组，以及它们的混合物； 是含有 11 至 29 个碳原子的脂肪族基团；其中 基团中至少有一个是 H

The amine compound may also be a quaternary am monium compound obtained by quaternizing the above 65 compounds such that the H atoms are replaced with an alkyl group containing 1 to 3 carbon atoms, a benzyl group, or mixtures thereof, and excess of the quaterniz- ing reagent is used sufficient to effect the quaternization of the amino group.
胺化合物也可以是一种季铵化合物，通过对上述 65 种化合物进行季铵化处理，使 H 原子被含有 1 至 3 个碳原子的烷基、苄基或它们的混合物所取代，并使用过量的季铵化试剂来实现氨基的季铵化。

Preferably in the compounds represented by formula and in the compounds represented by
优选式 代表的化合物中的 和式 代表的化合物中的 。
5 formulas II and III. Preferably is an alkyl group containing from 12 to 22 carbon atoms, and is an alkyl group containing from 11 to 21 carbon atoms. Most preferably at least of the aliphatic radicals represented by R contain 18 carbon atoms, and at least of the aliphatic groups represented by contain 17 carbon atoms. Still more preferably the R" group is derived from tall oil fatty acid.
5 式 II 和 III。最好 是含有 12 至 22 个碳原子的烷基， 是含有 11 至 21 个碳原子的烷基。最优选的是，由 R 代表的脂肪族基团中至少 含有 18 个碳原子，而由 代表的脂肪族基团中至少 含有 17 个碳原子。更优选的是，R "基团来自妥尔油脂肪酸。

The amino compound may also be a quaternary ammonium compound having the molecular formula (IV), and mixtures thereof with compounds (I), (II), and (III).
氨基化合物也可以是分子式为(IV)的季铵盐化合物及其与化合物(I)、(II)和(III)的混合物。

where , and are independently selected 20 from the group consisting of H , lower alkyl groups containing from one to three carbon atoms, and higher aliphatic groups containing from 12 to 30 carbon atoms; and where is a charge balancing anion of valence .
其中 和 分别独立地从 H、含有 1 至 3 个碳原子的低级烷基和含有 12 至 30 个碳原子的高级脂肪族基团组成的组中选出；且 是价数 的电荷平衡阴离子。
Preferably at least two of the , and
最好是 和 中的至少两个
5 groups contain at least 16 carbon atoms, and the anion is chloride.
5 个基团含有至少 16 个碳原子，阴离子为氯化物。
In the foregoing as well as elsewhere in this specification and the claims which follow, the term aliphatic is to be understood as including unsaturated as well as saturated (alkyl) straight carbon chain radicals, and straight carbon chain radicals which contain one or more hydroxyl or amino groups substituted therein.
在上文以及本说明书的其它地方和后面的权利要求中，术语脂肪族应理解为包括不饱和以及饱和（烷基）直碳链基，以及含有一个或多个羟基或氨基取代的直碳链基。
By way of further explanation of the nature and types of the amino compounds utilized in the present invention are some typical members of the series in the following table, although these are merely illustrative and not at all by way of limitation.
为了进一步说明本发明中使用的氨基化合物的性质和类型，下表中列出了该系列中的一些典型成员，但这些仅仅是说明性的，完全不是限制性的。

-

where is the imidazoline group
其中 为咪唑啉基团

The preferred amino compounds for use in this invention are the fatty acyl partial amides, which may also be called fatty acid amido amines, from Group II which result from the reaction of fatty acids with polyalkylene polyamines. The preferred fatty acids contain from 12 to 22 carbon atoms, preferably from 14 to 18 carbon atoms. The preferred polyalkylene polyamines are polyethylene polyamines having from 3 to about 9 amino groups, and thus includes tri-amines such as diethylene triamine, tetra-amines such as triethylene tetramine, pentamines such as tetraethylene pentamine, and higher analogs of these, up to nine and more amino groups. The amide is only partial, that is, it is such that from about one-fourth to about three-fourths of the nitrogen atoms are present in the form of a fatty acid amide, the balance being in the form of free amino groups.
用于本发明的优选氨基化合物是由脂肪酸与聚亚烷基多胺反应生成的第二类脂肪酰基部分酰胺，也可称为脂肪酸氨基胺。优选的脂肪酸含有 12 至 22 个碳原子，最好是 14 至 18 个碳原子。优选的聚亚烷基多胺是具有 3 至约 9 个氨基的聚乙烯多胺，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）以及这些胺的更高类似物，多达 9 个或更多的氨基。酰胺仅是部分的，即大约四分之一到四分之三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。

Most preferably the fatty acid is selected from the group consisting of tall oil fatty acid, hydrogenated tallow fatty acid, and mixtures thereof. The preferred fatty acyl partial amides of Group II have an average equivalent weight per amino group in the range from about 235 to about 850 .
最优选的脂肪酸选自妥尔油脂肪酸、氢化牛脂脂肪酸及其混合物组成的组。优选的第 II 组脂肪酰基部分酰胺的每个氨基的平均当量重量在约 235 至约 850 之间。

Mixtures of one or more of the amino compounds 60 from Group I, Group II, or Group III with one or more quaternary ammonium compounds from Group IV are very desirable organophilic humate derivatives for use in oil base drilling fluids.
第 I 组、第 II 组或第 III 组中的一种或多种氨基化合物 60 与第 IV 组中的一种或多种季铵盐化合物的混合物是非常理想的亲有机腐殖酸衍生物，可用于油基钻井液中。
The base used to prepare the aqueous humate solution 65 must be an alkali metal or ammonium base as all other metallic humate salts are insoluble and non-colloidal. The term "solution" as used herein to describe the "hu- mate solution" is intended to mean not only completely solubilized humate but also colloidally dispersed humate. The preferred bases for use in the present invention are sodium bases, most preferably sodium hydrox-
用于制备腐植酸水溶液 65 的碱必须是碱金属碱或铵碱，因为所有其他金属腐植酸盐都是不溶性和非胶体的。此处用于描述 "腐殖酸盐溶液 "的术语 "溶液 "不仅指完全溶解的腐殖酸盐，也指胶体分散的腐殖酸盐。用于本发明的优选碱是钠碱，最优选的是氢氧化钠。
5 ide, sodium tetraborate (borax), and mixtures thereof. Other bases which may be used include sodium carbonate, sodium silicate, the various sodium phosphates, the various condensed sodium phosphates, potassium hydroxide, potassium carbonate, ammonium hydroxide,
5 ide、四硼酸钠（硼砂）以及它们的混合物。其他可使用的碱包括碳酸钠、硅酸钠、各种磷酸钠、各种缩合磷酸钠、氢氧化钾、碳酸钾、氢氧化铵、
10 and mixtures thereof with one another and with sodium hydroxide and/or sodium tetraborate.
10 以及它们与氢氧化钠和/或四硼酸钠的混合物。

The acids useful in the practice of my invention are preferably inorganic acids, most preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and mixtures theor. The most partic ularly preferred acids are hydrochloric acid and sulfuric acid. Other acids which may be used include acetic acid, hydroxy acetic acid, and the like.
用于本发明的酸最好是无机酸，最好选自盐酸、硫酸、硝酸及其混合物。最特别优选的酸是盐酸和硫酸。其他可使用的酸包括乙酸、羟基乙酸等。

The amount of amine added to the aqueous humate solution to react with and precipitate the humate on addition of the acid must be sufficient to produce an organophilic humate derivative after drying which is an effective fluid loss additive in oil base drilling fluids Generally, an amount of amine in the range from about to about by weight of the humic acid (i.e., from about to about by weight of the humic acid-containing material) must be used, preferably from about to about by weight of the humic acid (i.e. from about to about by weight of the humic acid-containing material).
添加到腐植酸水溶液中以在添加酸时与腐植酸反应并沉淀腐植酸的胺的量必须足以在干燥后产生嗜有机腐植酸衍生物，该衍生物是油基钻井液中有效的流体流失添加剂 一般来说，按腐植酸重量计，胺的用量必须在约 至约 的范围内（即必须使用按腐植酸重量计约 至约 的胺，最好按腐植酸重量计约 至约 的胺（即按含腐植酸材料重量计约 至约 ）。

In the process of my invention the humic acid or humic acid-containing material is first solublized or dispersed in water with the alkali metal or ammonium base is used to provide a pH in the range from about 7.0 to about 12.0 , preferably greater than about 7.5 . Gener ally the humic acid-containing material is ground to a fine particle size, preferably less than 60 mesh, and mixed with water to which the base has been added. The order of addition of the water, humic acid, and base does not appear to be critical, although more foaming is noted if the lignite and base are first reacted before addition of the water. The concentration of humic acidcontaining material is not critical in this step as long as the humate solution can be easily mixed. However, upon addition of the acid to the amine containing humate solution in a subsequent step of this process, the solution becomes very viscous. A solid, gummy mass is 0 obtained if the concentration of humic acid-containing material is greater than about by weight in the humate solution.
在本发明的工艺中，首先将腐植酸或含腐植酸的材料溶解或分散在水中，并使用碱金属或铵碱，使 pH 值在约 7.0 至约 12.0 之间，最好大于约 7.5。一般情况下，将含腐植酸的材料研磨成细颗粒，最好小于 60 目，然后与加入碱的水混合。加入水、腐植酸和碱的顺序似乎并不重要，但如果在加入水之前先让褐煤和碱发生反应，则会产生更多的泡沫。在这一步骤中，只要腐植酸溶液易于混合，含腐植酸材料的浓度并不重要。但是，在该工艺的后续步骤中，向含有胺的腐植酸溶液中加入酸后，溶液会变得非常粘稠。如果腐植酸溶液中含腐植酸材料的浓度大于约 （按重量计），就会产生固体胶状物。

The humate solution can be prepared at ambient temperature or above. However, the time required to effec55 tively solublize the humic acid is decreased as the temperature is increased. Inasmuch as the temperature of the amine containing humate solution must be at least . in a subsequent step, it is desirable to raise the temperature of the humate solution to at least . ), preferably from about .) to about .). At this temperature a mixing time of 15 to 30 minutes is sufficient to solublize the humic acid although longer heating time has no detrimental effect
腐植酸溶液可在常温或更高温度下制备。但是，随着温度的升高，有效溶解腐植酸所需的时间会缩短。由于在后续步骤中，含胺腐植酸溶液的温度必须至少达到 . )，最好从大约 .) 到大约 .) 。在此温度下，15 至 30 分钟的混合时间足以使腐植酸溶解，但更长的加热时间不会产生不利影响。

Once the humate solution is formed, the amino com pound is then added. If the amino compound is selected from Group I, II, and III and it contains no quaternary ammonium radicals, no particular reaction is noted. The
腐殖酸溶液形成后，再加入氨基化合物。如果氨基化合物选自第 I、II 和 III 组，且不含季铵基，则无需特别注意反应。反应
amino compound and humic acid (or humic acid-containing material) form a smooth, somewhat more viscous slurry in which the amino compound and humic acid are initimately and homogeneously mixed. The amino compound is most probably sorbed onto the humic acid at this stage of the process. If a quaternary ammonium compound is added at this stage, a reaction is evident as the humate solution becomes grainy and flocculent.
氨基化合物和腐植酸（或含腐植酸的材料）形成一种光滑的、略微粘稠的浆液，氨基化合物和腐植酸在浆液中初步均匀混合。在这一阶段，氨基化合物很可能吸附在腐植酸上。如果在这一阶段加入季铵化合物，腐殖酸溶液会变得颗粒状和絮状，从而明显产生反应。

The temperature of the amine-containing humate solution must be at least .), preferably in the range from about .) to about . .)
含胺腐殖酸盐溶液的温度必须至少为 .)，最好在约 .)至约 . 。）
Thereafter an acid is added to the amine-containing humate solution to decrease the pH causing an in-situ reaction to occur between the humate and the amine. As the acid is slowly added, the viscosity of the mixture slowly increases until a maximum viscosity is obtained when about by weight of the theoretical amount of acid required to neutralize the base used to solublize the humic acid is added. Thereafter the viscosity decreases as the remainder of the acid is added. The a mount of acid added must be sufficient to at least neutralize all of the base used to solublize the humic acid. The pH of the substituted ammonium humate slurry will generally be in the range from 4.0 to 6.0 when the amount of acid is the theoretical amount required to neutralize the base.
然后向含胺腐植酸盐溶液中加入酸，降低 pH 值，使腐植酸盐和胺发生原位反应。随着酸的缓慢加入，混合物的粘度缓慢增加，直到加入中和用于溶解腐植酸的碱所需的理论酸量的约 （按重量计）时，粘度达到最大值。此后，随着剩余酸量的加入，粘度逐渐降低。加入的酸必须至少足以中和所有用于增溶腐植酸的碱。当酸的用量为中和碱所需的理论用量时，替代腐植酸铵浆料的 pH 值一般在 4.0 到 6.0 之间。
Upon completion of the addition of the acid, the substituted ammonium humate must be recovered for use. Recovery procedures vary depending on the characteristics of the substituted ammonium humate produced. Generally the aqueous phase is removed by filtration and drying, and the organophilic humate derivative is then finely ground.
加酸完成后，必须回收取代的腐植酸铵以备使用。回收程序因所生产的取代腐植酸铵的特性而异。一般来说，通过过滤和干燥去除水相，然后将嗜有机腐植酸衍生物磨细。
When sodium hydroxide or potassium hydroxide has been used to prepare the humate solution and the substituted ammonium humate derivative is prepared utilizing high shear mixing, the substituted ammonium humate obtained is of very fine particle size and difficult to filter to remove the major proportion of the aqueous phase before drying. This results in long filtration times, low filter cake solids, and, hence, extra processing expenses. Thus it is desirable to spray dry or otherwise directly dry this substituted ammonium humate slurry. The organophilic ammonium humate derivative obtained is a very fine powder which imparts excellent fluid loss control at high temperatures in oil base drilling fluids.
当使用氢氧化钠或氢氧化钾制备腐植酸溶液，并利用高剪切混合法制备取代腐植酸铵衍生物时，得到的取代腐植酸铵粒度非常细，很难在干燥前进行过滤以去除大部分水相。这就导致过滤时间长、滤饼固体含量低，从而产生额外的加工费用。因此，最好是喷雾干燥或直接干燥这种取代的腐植酸铵浆料。所得到的嗜有机腐植酸铵衍生物是一种非常细的粉末，在石油基钻井液的高温条件下具有极佳的流体流失控制效果。
When less basic materials are used to prepare the humate solution, such as sodium tetraborate, or the 50 substituted ammonium humate derivative is prepared utilizing low shear mixing, the substituted ammonium humate slurry may be filtered prior to drying and grinding to recover the organophilic humate derivative.
如果使用四硼酸钠等碱性较低的材料制备腐植酸盐溶液，或利用低剪切力混合制备 50 种取代的腐植酸铵衍生物，则可在干燥和研磨之前过滤取代的腐植酸铵浆液，以回收亲有机腐植酸衍生物。
The rate of filtration is dependent on many variables 55 such as the ratio of the amine to humic acid, the amount of base and the type of base used to prepare the humate solution, and the amount of acid added to the amine containing humate solution.
过滤速度取决于许多变量，例如胺与腐殖酸的比例、制备腐殖酸溶液时使用的碱的量和类型，以及添加到含腐殖酸胺溶液中的酸的量。
I have found, however, that the rate of filtration and 60 the percent filter cake solids can be increased by adding more acid to decrease the pH to less than about 4.0 , preferably in the range from about 2.0 to about 3.5 . Decreasing the pH of the amine containing humate solution to this pH provides a larger particle size prod- 65 uct which is more readily filterable.
但我发现，通过添加更多的酸，将 pH 值降至 4.0 以下，最好在 2.0 到 3.5 之间，可以提高过滤速度和滤饼固体百分比。将含腐植酸胺溶液的 pH 值降至这一 pH 值，可获得粒径更大、更易过滤的产品。
In another embodiment of this invention, I have found that the pH of the acidified solution can be raised by the addition of lime without adversely effecting the rate of filtration. Indeed, in some cases the rate of filtration is favorably increased. The lime produces an organophilic humate derivative which has better initial dispersibility in diesel oil (the basic oil used in the preparation of oil base drilling fluids). Cowan in U.S. Pat. No. , incorporated herein by reference, discloses a complex salt of a amino compound, humic acid, and a polyvalent metallic cation such as calcium as a fluid loss additive in oil base drilling fluids. It is possible that a complex of this type containing a higher concentration of substituted ammonium compound can be prepared by the process of this invention. An amount of lime sufficient to raise the pH to is preferred.
在本发明的另一个实施方案中，我发现可以通过添加石灰来提高酸化溶液的 pH 值，而不会对过滤速度产生不利影响。事实上，在某些情况下，过滤速度会得到有利的提高。石灰产生的亲有机腐殖酸衍生物在柴油（用于制备油基钻井液的基础油）中的初始分散性更好。Cowan 在 U.S. Pat. 号（并入本文作为参考）中公开了一种氨基化合物、腐植酸和多价金属阳离子（如钙）的复盐，作为油基钻井液中的流体损失添加剂。通过本发明的工艺，有可能制备出含有更高浓度取代铵化合物的此类复盐。石灰的用量最好足以将pH值提高到 。

The following non-limiting examples illustrate the results and benefits obtainable utilizing this process for the preparation of organophilic humate derivatives. In the examples, all percentages are by weight unless otherwise indicated. The amido-amines (partial amides) which were evaluated were obtained by reacting tall oil fatty acid, containing rosin acids, with a polyamine at a temperature of . for one hour. The number of equivalents of tall oil fatty acid per equivalent of amine is indicated by the numerical fraction, i.e., Partial Amide 0.7 indicates that this partial amide contains 0.7 equivalents of tall oil fatty acid per equivalent of amine.
以下非限制性示例说明了利用该工艺制备亲有机腐植酸衍生物可获得的结果和益处。在示例中，除非另有说明，所有百分比均为重量百分比。通过在 .温度下使含有 松香酸的妥尔油脂肪酸与多胺反应一小时，可获得所评估的氨基胺（部分酰胺）。每个胺当量所含妥尔油脂肪酸的数量用数字分数表示，例如，部分酰胺 0.7 表示该部分酰胺每个胺当量含有 0.7 个妥尔油脂肪酸当量。

50 parts of lignite, dry basis ( 66.8 parts as received) were mixed with 150 parts of hot water and 7.5 parts of sodium hydroxide in a Waring Blendor for five minutes. Thereafter 55 parts of Partial Amide 0.7 prepared from tetraethylene-pentamine were added and mixed for 2 minutes. 18.5 parts of concentrated hydrochloric acid
在 Waring Blendor 中将 50 份干基褐煤（收到时为 66.8 份）与 150 份热水和 7.5 份氢氧化钠混合 5 分钟。然后加入 55 份由四乙烯五胺制备的 0.7 部分酰胺，混合 2 分钟。18.5 份浓盐酸
were then added followed by 130 parts of additional hot water and mixed for 5 minutes at . .). 2.5 parts of hydrated lime were added and mixed for two minutes. This fine particle size fluid sample obtained before drying contained substituted 0 ammonium lignite. The slurry was then dried at . and the organophilic lignite ground to a fine powder.
，然后再加入 130 份热水，在 下搅拌 5 分钟。 ）。加入 2.5 份熟石灰并混合两分钟。干燥前获得的这种细粒度流体样品含有 取代的 0 氨褐煤。然后在 条件下对浆液进行干燥，并将有机褐煤研磨成细粉。

The procedure of Example 1 was repeated except 45 5 parts of the Partial Amide 0.7 were used.
除使用 5 份部分酰胺 0.7 外，重复例 1 的步骤。

The procedure of Example 1 was repeated except 35 parts of the Partial Amide 0.7 were used
除了使用 35 份部分酰胺 0.7 之外，重复例 1 的步骤

The procedure of Example 2 was repeated except that the sodium hydroxide and hydrochloric acid were deleted. Thus this process is as described in the prior art wherein the humic acid-containing material is reacted with the substituted ammonium compound in its base form. As the mixing continued following the addition of the 130 parts of hot water, the slurry became a semisolid mass which completely stopped the Blendor. After drying at . a gummy solid was obtained which could not be ground.
除去氢氧化钠和盐酸外，重复例 2 的步骤。因此，该过程与现有技术中所述的含腐植酸材料与碱形式的取代铵化合物反应的过程相同。在加入 130 份热水后继续搅拌，浆液变成了半固体状，完全停止了 Blendor。在 条件下干燥后，得到了无法研磨的胶状固体。

The procedure of Example 3 was repeated except that the sodium hydroxide and hydrochloric acid were deleted, as in Comparative Example 2. As the mixing continued following the addition of the 130 parts of hot water, the solids began to clump and very poor mixing
与比较例 2 一样，重复例 3 的步骤，只是去掉氢氧化钠和盐酸。在加入 130 份热水后继续搅拌，固体开始结块，搅拌效果非常差。
resulted. After drying at F. a gummy solid was obtained which could not be ground.
结果。在 华氏温度下干燥后，会得到无法研磨的胶状固体。

The procedure of Comparative Example 2 was re- 5 peated except that a low shear mixer was used instead of a Waring Blendor. A sticky, semi-solid material was obtained which was dried at . A gummy solid was obtained which could not be ground.
除了使用低剪切力混合器而不是 Waring Blendor 外，对比实施例 2 的步骤重新进行。得到一种粘性半固体材料，在 下干燥。得到的胶状固体无法研磨。

The procedure of Example 1 was repeated except that 11.25 parts of glacial acetic acid were used instead of the hydrochloric acid.
除了用 11.25 份冰醋酸代替盐酸外，重复了例 1 的步骤。

50 parts of humate, dry basis, as described in Firth U.S. Pat. No. ( 270 parts as received at solids) was used as a substitute for lignite in the procedure of Example 1.
Firth U.S. Pat. 中所述的腐植酸盐（270 份，以 固体含量计）在实施例 1 的过程中用作褐煤的替代物。

The procedure of Example 1 was repeated except that 75 parts of the Partial Amide 0.7 were used and the lime was omitted.
除了使用 75 份部分酰胺 0.7 和省略石灰外，重复例 1 的步骤。

The procedure of Example 1 was repeated except that the lime was omitted.
除省略石灰外，重复例 1 的步骤。

50 parts of lignite, dry basis ( 66.8 parts as received) were mixed with 150 parts hot water and 7.5 parts sodium hydroxide in a Waring Blendor for five minutes. In a separate Waring Blendor jar there were mixed 130 parts of hot water, 18.5 parts of concentrated hydro chloric acid ( ) and 55 parts the Partial Amide 0.7 . The lignite solution was added to the Blendor jar containing the HCl and Partial Amide 0.7 and mixed 7 minutes. The slurry was then dried at . and the 40 organophilic lignite ground to a fine powder.
在 Waring Blendor 中，将 50 份干燥的褐煤（66.8 份收货时的褐煤）与 150 份热水和 7.5 份氢氧化钠混合五分钟。在另一个 Waring Blendor 瓶中混合 130 份热水、18.5 份浓氯酸（ ）和 55 份 0.7 部分酰胺。将褐煤溶液加入装有盐酸和部分酰胺 0.7 的 Blendor 瓶中，混合 7 分钟。然后在 条件下将浆液干燥，并将 40 份嗜有机褐煤研磨成细粉。
This process is as described in the prior art wherein a humate solution is reacted with an acid salt of the substituted ammonium compound except that the amount of acid used is the amount used in the presently disclosed process, i.e. an amount of acid sufficient to react with all of the base used in preparing the humate solution. The amount of concentrated hydrochloric acid needed to form a salt with the excess amine groups in the Partial Amide 0.7 is only 7.5 parts.
该工艺与现有技术中所述的腐殖酸盐溶液与取代铵化合物的酸盐反应的工艺相同，只是所用的酸量是本公开工艺中所用的酸量，即足以与制备腐殖酸盐溶液时所用的全部碱反应的酸量。与部分酰胺 0.7 中的过量胺基团形成盐所需的浓盐酸量仅为 7.5 份。

EXAMPLE 8 示例 8
An aqueous humate solution was prepared containing 1110 parts hot water, 48.2 parts of sodium tetraborate decahydrate, 31.87 parts of Texas lignite (containing 5 moisture), and 95.63 parts North Dakota lignite (containing moisture) by mixing with a low shear mixer for five minutes. The temperature of the humate solution was maintained in the range from . to parts of dimethyl dihydrogenatedtallow 60 ammonium chloride ( active) and 91.8 parts of Partial Amide 0.5 prepared from tetraethylenepentamine were added and mixed for 5 minutes. The pH was 7.6. Thereafter 60.8 parts of sulfuric acid was slowly added and mixed 5 minutes. The pH was 4.0 . 246 parts of lime were then added and mixed five minutes. The substituted ammonium humate was then filtered in a Buchner funnel and the time for the filter cake to show was measured as an indication of the relative filtration rate. The slurry thus took 3.75 minutes for filtration.
通过使用低剪切力搅拌器搅拌五分钟，制备出腐植酸水溶液，其中包含 1110 份热水、48.2 份十水四硼酸钠、31.87 份德克萨斯州褐煤（含 5 水分）和 95.63 份北达科他州褐煤（含 水分）。将腐殖酸盐溶液的温度保持在 至 的范围内，加入部分二甲基二氢化乌桕 60 氯化铵（ 活性）和 91.8 部分由四乙烯五胺制备的部分酰胺 0.5，混合 5 分钟。pH 值为 7.6。然后缓慢加入 60.8 份 硫酸并混合 5 分钟。pH 值为 4.0。然后加入 246 份石灰并混合 5 分钟。然后在布氏漏斗中过滤取代的腐植酸铵，并测量滤饼出现的时间，以显示相对过滤率。因此，浆液的过滤时间为 3.75 分钟。

The procedure of Example 8 was repeated except that 80 parts of sulfuric acid was used. The pH was 3.0 and the filtration time was 1.87 minutes.
除了使用 80 份 硫酸外，重复例 8 的步骤。pH 值为 3.0，过滤时间为 1.87 分钟。

EXAMPLE 10 示例 10
An aqueous humate solution was prepared containing 425 parts hot tap water, 7.5 parts sodium hydroxide, and 68.6 parts of a lignite ( moisture, humic acid (dry basis)) by mixing at low shear for 15 minutes at
将 425 份热自来水、7.5 份氢氧化钠和 68.6 份褐煤（ 水分， 腐殖酸（干基））混合，制备腐殖酸水溶液。
F. 50 parts of the Partial Amide 0.5 used in Example 8 were added and mixed for 5 minutes. 47 parts of sulfuric acid were added and mixed 5 minutes. 2.5 parts of hydrated lime were added and mixed 5 minutes. The substituted ammonium humate The product was then dried at . and ground. The filtration time of the slurry was 3 minutes.
F. 加入 50 份实施例 8 中使用的部分酰胺 0.5，混合 5 分钟。加入 47 份 硫酸并混合 5 分钟。加入 2.5 份熟石灰并混合 5 分钟。然后在 下干燥并研磨。浆液的过滤时间为 3 分钟。

25 The procedure of Example 10 was repeated using 66.5 parts of a lignite ( moisture, humic acid, dry basis). The filtration time was 2 minutes.
25 使用 66.5 份褐煤（ 水分， 腐殖酸，干基）重复例 10 的步骤。过滤时间为 2 分钟。

30 The procedure of Example 10 was repeated using 72.9 parts of a lignite containing moisture and humic acid, dry basis. The filtration time was 15 minutes.
30 重复例 10 的步骤，使用 72.9 份含 水分和 腐殖酸的褐煤（干基）。过滤时间为 15 分钟。

The procedure of Example 10 was repeated using 68.0 parts of a lignite containing moisture and humic acid, dry basis. Various partial amides were used as indicated in Table 1.
使用 68.0 份含 水分和 腐殖酸（干基）的褐煤，重复例 10 的步骤。如表 1 所示，使用了各种部分酰胺。

TABLE 1 表 1

Tall oil fatty acid
妥尔油脂肪酸

The procedure of Example 8 was repeated using 42 parts of sodium tetraborate pentahydrate, 37.5 parts of Texas lignite, dry basis, 112.5 parts of North Dakota lignite, dry basis, 45 parts of dimethyl dihydrogenatedtallow ammonium chloride ( active in isopropanol), and 96 parts of a Partial Amide 0.7 prepared from HPA No. 2 higher polyethenepolyamines which had been quaternized with benzyl chloride. The sample filtered very fast, less than one-half minute.
使用 42 份五水合四硼酸钠、37.5 份得克萨斯州褐煤（干基）、112.5 份北达科他州褐煤（干基）、45 份二甲基二氢化氯化铵（ 异丙醇中的活性物）和 96 份由 HPA 2 号高级多酚多胺制备的部分酰胺 0.7（已用氯化苄季铵化），重复实施例 8 的步骤。样品的过滤速度非常快，不到半分钟。

An aqueous solution of sulfonated humic acid was prepared by refluxing a mixture containing 425 parts water, 7.5 parts sodium hydroxide, 5.0 parts sodium
将含有 425 份水、7.5 份氢氧化钠、5.0 份钠盐的混合物回流，制备磺化腐植酸水溶液。
sulfite, and 50.0 parts lignite, dry basis at . for 3 hours. This process is disclosed in U.S. Pat. No. , incorporated herein by reference. 55 parts of the Partial Amide 0.5 from tetraethylene-pentamine were added and mixed at low shear for 5 minutes at parts of sulfuric acid were added and reacted 5 minutes. The substituted ammonium sulfonated lignite slurry was filtered, dried at ., and ground.
硫铁矿和 50.0 份褐煤（干基），在 下搅拌 3 小时。该工艺已在美国专利 中公开。 号中披露，在此并入作为参考。在 份 硫酸中加入55份四乙烯-戊胺的部分酰胺0.5，并在低剪切力下混合5分钟，反应5分钟。将取代的铵磺化褐煤浆过滤，在 .干燥，并研磨。

The procedure of Example 10 was repeated except that the amount of sulfuric acid was varied and the pH and filtration time measured. No lime was added to these substituted ammonium humate slurries. The data obtained are given in Table 2.
除了改变硫酸的用量并测量 pH 值和过滤时间外，重复例 10 的步骤。在这些取代的腐植酸铵泥浆中没有添加石灰。获得的数据见表 2。

TABLE 2 表 2

*Amount required to neutralize the NaOH in the slurry.
*中和泥浆中 NaOH 所需的量。

The procedure of Example 16 was repeated except that the amount of acid added was 36.8 parts, the theoretical amount required to react with the Partial Amide 0.5 to form the amine salt. The pH was 6.2 and the filtration rate was 9.5 minutes.
重复例 16 的步骤，但酸的加入量为 36.8 份，即与部分酰胺 0.5 反应生成胺盐所需的理论量。pH 值为 6.2，过滤速度为 9.5 分钟。
Several of the organophilic lignite samples were evaluated by mixing 10 grams of each sample in 350 ml . of diesel oil for 5 minutes on a Waring Blendor. Thereafter the fluids were tested for fluid loss according to the API RP 13B procedure. The results are given in Table 3.
通过在 Waring Blendor 上将 10 克样品在 350 毫升柴油中混合 5 分钟，对几种嗜有机褐煤样品进行了评估。然后根据 API RP 13B 程序对流体损失进行测试。结果见表 3。

TABLE 3 表 3

As indicated by the results of Example 15, sulfonated humic acids or sulfonated humic acid-containing materials can be used in the process of the invention. Thus the term "humic acid" or "humic acid-containing material" is intended herein and in the appended claims to include the sulfonated derivatives of humic acid or humic acid-containing materials.
如实施例 15 的结果所示，磺化腐植酸或含磺化腐植酸的材料可用于本发明的工艺中。因此，本文及所附权利要求中的术语 "腐植酸 "或 "含腐植酸材料 "包括腐植酸或含腐植酸材料的磺化衍生物。

Other polyphenolic acids or salts thereof may be useful in the process of the invention. Thus lignosulThit fied tannins; the oxidized, sulfonated, and sulfomethylated derivatives of these polyphenolic compounds; and the water soluble salts of these polyphenolic compounds or these derivatives may be useful in this propolyphenowing U.S. patents all disclose vanous tice this invention: U.S. Pat. No. 2,831,022-sulfonated tannins; U.S. Pat. No. 3,232,870-lignosulfonates; U.S. Pat. No. 3,391,173-sulfomethylated tannins; U.S. Pat. Pat. No. 3,671,428-oxidized lignosulfonates; U.S. Pat. No. -sulfonated humic acids, lignite and oxidized coals; U.S. Pat. No. 3,726,850-ozone oxidized lignins; U.S. Pat. No. 3,956,140-sulfonated lignite, sulfonated phenolic condensates, and sulfomethylated phenolic condensates; U.S. Pat. No. 4,069,034-humic acids; U.S. Pat. No. 4,088,640-ozone oxidized lignosulfonates; and U.S. Pat. No. 4,196,777-oxidized lignosulfonates.
其他多酚酸或其盐类也可用于本发明的工艺中。因此，木质素单宁；这些多酚类化合物的氧化、磺化和磺甲基化衍生物；以及这些多酚类化合物或这些衍生物的水溶性盐均可用于本发明：U.S. Pat.No. 2,831,022-sulfonated tannins；U.S. Pat.No. 3,232,870-lignosulfonates; U.S. Pat.No.3,391,173-磺甲基单宁酸；U.S. Pat.Pat.No.3,671,428-氧化木质素磺酸盐；U.S. Pat.No. -磺化腐殖酸、褐煤和氧化煤；U.S. Pat.No. 3,726,850-ozone oxidized lignins; U.S. Pat.No. 3,956,140-磺化褐煤、磺化酚缩合物和磺化甲基化酚缩合物；U.S. Pat.No. 4,069,034-humic acids; U.S. Pat.No. 4,088,640-ozone oxidized lignosulfonates；以及 U.S. Pat.第 4,196,777 号-氧化木质素磺酸盐。

I claim: 我声称

where is selected from the group consisting of H and , and mixtures thereof; is an aliphatic group containing from 11 to 29 carbon atoms; wherein at least one of the groups are H ;
其中 选自 H 和 组成的组，以及它们的混合物； 是含有 11 至 29 个碳原子的脂肪族基团；其中 基团中至少有一个是 H ；
(c) mixing with said partial amide containing humate solution an acid in an amount sufficient to at least react with all of said alkali metal or ammonium base and produce a pH in the range from about 4.0 to about 6.0 ; and
(c) 与所述含部分酰胺的腐殖酸溶液混合一种酸，其用量至少足以与所述碱金属或铵碱全部反应并产生约 4.0 至约 6.0 的 pH 值；以及
(d) thereafter recovering the organophilic humate; wherein the temperature of the partial amide containing humate solution is above about .
(d) 此后回收嗜有机腐殖酸盐；其中，含部分酰胺的腐殖酸盐溶液的温度高于约 。
2. The process of claim 1 wherein lime is added to the substituted ammonium humate slurry resulting from step (c) to raise the pH of the slurry to the range from about 6.0 to about 8.0 .
2.3.权利要求 1 的工艺，其中在步骤（c）产生的取代腐植酸铵浆液中加入石灰，以将浆液的 pH 值提高到约 6.0 至约 8.0 的范围。
3. The process of claim 1 wherein the amount of acid added in step (c) is greater than the theoretical amount required to react with said alkali metal or ammonium base.
3.4. 权利要求 1 的工艺，其中步骤（c）中加入的酸量大于与所述碱金属或铵碱反应所需的理论量。
4. The process of claim 3 wherein the pH of the acidi6 fied substituted ammonium humate slurry resulting from step ( c ) is in the range from about 2.0 to about 4.0.
4.4.权利要求 3 的工艺，其中步骤（c）产生的酸化取代腐植酸铵浆料的 pH 值在约 2.0 至约 4.0 的范围内。
5. The process of claim 1 wherein said alkali metal or ammonium base used to prepare the humate solution in
5.6. 权利要求 1 的工艺，其中所述碱金属或铵碱用于制备以下腐殖酸溶液
step (a) is selected from the group consisting of sodium hydroxide, sodium tetraborate, and mixtures thereof.
步骤(a)选自氢氧化钠、四硼酸钠及其混合物。
6. The process of claim 1 wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and mixtures thereof.
6.7. 权利要求 1 的工艺，其中所述酸选自盐酸、硫酸及其混合物组成的组。
7. The process of claim 1 wherein the pH of the humate solution is greater than about 7.5 .
7.2.权利要求 1 的工艺，其中腐殖酸溶液的 pH 值大于约 7.5。
8. The process of claim , or 9 wherein said alkali metal or ammonium base is selected from the
8.9.根据权利要求 或9所述的工艺，其中所述碱金属或铵碱选自以下物质
group consisting of sodium hydroxide, sodium tetraborate, and mixtures thereof; and wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and mixtures thereof.
其中所述酸选自盐酸、硫酸及其混合物组成的组。
59 . The process of claim , or 9 wherein lime is added to the substituted ammonium humate slurry resulting from step (c) to raise the pH of the slurry to the range from about 6.0 to about 8.0 .
59 .59.根据权利要求 或9所述的工艺，其中在步骤(c)得到的取代腐植酸铵浆料中加入石灰，以将浆料的pH值提高到约6.0至约8.0的范围。