Method for preparing chemical formulation comprising neutralized component

Abstract

The present invention relates to a continuous process for preparing a homogeneous chemical formulation comprising at least water, an ionic surfactant and a co-surfactant. The method comprises the steps of: mixing at least one precursor of an ionic surfactant, a co-surfactant and a neutralizing agent by at least one mixing device selected from the group consisting of a continuous stirred tank reactor, a high shear mixer, a mixing pump, a static mixer and a mixing nozzle; and removing the obtained chemical formulation through an outlet. The method is suitable for blending surfactant formulations comprising neutralized components, and is particularly suitable for neutralized components that form gels with water in the absence of co-surfactants.

Description

[0001] This invention relates to a continuous method for preparing chemical formulations comprising at least water, an ionic surfactant, and a co-surfactant. Background Technology

[0002] Chemical formulations prepared by neutralizing acids or bases have a wide range of applications. For example, surfactant compositions prepared by neutralizing the acid precursor of a surfactant can be used in oil fields such as enhanced oil extraction methods, or in gas fields, or these surfactant compositions can be used in liquid or gel detergent compositions.

[0003] The manufacture of these chemical formulations can sometimes present challenges, such as:

[0004] The neutralized form of acid or base may react with water present in the composition to form highly viscous products such as gels, and generate a significant amount of heat during the process. This hinders the handling and further processing of the product, such as mixing the product with other components and the establishment of efficient continuous processes.

[0005] The blending method is crucial. Depending on how the blending is performed, problems such as phase separation, agglomeration, and the presence of solid particles may occur. Some of these problems are caused by the low miscibility of precursors (e.g., acid precursors) in neutralizing agent solutions (e.g., alkaline solutions); and the high viscosity products formed when the neutralized ionic surfactant reacts with water to form a gel.

[0006] The reaction between the precursor and the neutralizing agent requires particularly good mixing. Since the neutralization reaction is very rapid and is therefore primarily controlled by the mixing rate, very short mixing times and high homogeneity are highly beneficial.

[0007] Undesirable side reactions may occur in the presence of other components. For example, when a co-surfactant is present, it may react with the neutralizer or with the precursor. These side reactions are undesirable and lead to the formation of undesirable byproducts, loss of product performance, and degradation of the feedstock. Another consequence is that an excess of neutralizer may be needed to compensate for undesirable side reactions between the neutralizer and the third component.

[0008] Several methods for obtaining aqueous solutions of anionic surfactants prepared in situ are known in the art. However, these known methods still have some drawbacks.

[0009] Some known methods result in compositions containing low levels of surfactant and high levels of water. However, the larger amount of water reduces the activity of the final product, thereby decreasing performance and increasing transportation costs and equipment size.

[0010] Other known methods result in final aqueous solutions with high viscosity, which are difficult to handle and pump. This is the case when, for example, a co-surfactant (such as anionic or nonionic surfactant) is not present in the composition. Co-surfactants can help improve the solubility of neutralized acids in the aqueous phase.

[0011] In some known methods that use co-surfactants, the precursor is contacted with a neutralizing agent before a completely homogeneous mixture of the precursor and the co-surfactant is obtained. In this case, the gel phase that forms between the neutralized ionic surfactant and water is not prevented and will form as an intermediate phase during the method. Therefore, this method typically requires the use of a larger amount of water and a neutralization loop with high shear homogenization units.

[0012] Another drawback of known methods is that they may be based on discontinuous batch processes, where the reaction takes place in a mixer into which the starting material is introduced, and intermediates or final products are removed after a certain mixing and / or reaction time. Batch processes are disadvantageous because they require long preparation times, which are associated with increased production costs. There is also a risk of contamination due to the fact that the corresponding systems used for batch processes must be purged and refilled, and then repeated multiple times as needed. It is also undesirable that large amounts of air are frequently introduced into the system, which can lead to product degradation.

[0013] Furthermore, when the known methods are based on continuous processes, these methods include the disadvantage of using circulating reactors, where most of the reaction mixture is circulated through the reactor, while only a small portion of the mixture is continuously discharged. The disadvantages of such circulating reactors are that they require very large volumes and powerful pumps, and satisfactory backmixing can only be achieved through large circulation ratios or additional mixing devices. Generally, methods using mixing loops are less efficient than single-pass systems.

[0014] The following patents or patent applications have disclosed some known methods:

[0015] US 6,794,347 B2 aims to reduce the viscosity of aqueous surfactant solutions by preparing chemical formulations with low surfactant content and high water content, particularly chemical formulations containing surfactants and about 50% to 90% water.

[0016] US 4,261,917 discloses a method for preparing an aqueous solution or slurry containing 60 to 75 wt.% of a sulfate of a higher alcohol or an epoxide adduct of said alcohol. However, examples show that chemical formulations obtained by this method have high viscosity, i.e., a viscosity between 130 and 180 poise at 40°C.

[0017] EP 0507402 A1 discloses a continuous method for producing detergents using a circulating reactor, wherein an acidic precursor of an anionic surfactant is neutralized with a neutralizing agent in the presence of a nonionic surfactant, preferably an ethoxylated fatty alcohol.

[0018] EP 2922945 B1 and WO 2014 / 079702 A1 disclose a continuous method for producing liquid detergents or cleaning agents by continuously mixing separate volumetric flows of at least one acid precursor of an anionic surfactant and a neutralizing agent via a dynamic circulating mixer (i.e., a closed online mixer with recirculation). An example of EP 2922945 B1 illustrates a continuous method in which the acid precursor, neutralizing agent, and water are first combined, the resulting mixture is optionally passed through a static mixer, and a co-surfactant (e.g., a fatty alcohol sulfate) is subsequently added to the dynamic circulating mixer. Specifically, in example E2, they disclose a method for preparing a chemical formulation comprising the steps of mixing NaOH and water in a static mixer, subsequently adding a LAS acid in a dynamic liquid mixer, and subsequently adding a fatty alcohol ether sulfate (an anionic co-surfactant), NaCl, and phosphoric acid in another static mixer.

[0019] WO 2006 / 069118 A2 discloses a continuous method for preparing a surfactant composition by mixing a surfactant acid precursor with at least a molar equivalent of a neutralizing agent using one or more static mixers. Additional components may also be present and may be fed into the method at any stage. However, none of the examples in WO 2006 / 069118 A2 show a method containing additional components. Furthermore, these examples do not mention the viscosity of the obtained chemical formulation, the active content of the surfactant in the obtained chemical formulation, or the molar ratio of the acid precursor to the neutralizing agent used.

[0020] WO 2015 / 138275 A1 discloses a surfactant composition for use in enhanced oil extraction, the surfactant composition comprising a neutralizing agent (e.g., NaOH solution), an acid precursor of an anionic surfactant (i.e., C... 15 / 17 Alkylbenzene sulfonic acid (ABS) and co-surfactant (i.e., tristyrylphenol (TSP)-PO) 35 -EO 25 (Ammonium salts of sulfates). WO2015 / 138275 A1 discloses a method in the example on page 8 (paragraphs 1 and 2 on page 8) in which NaOH is mixed with an alkoxy sulfate surfactant until a homogeneous solution is obtained, and then ABS is added to the NaOH-sulfate mixture while mixing.

[0021] WO 01 / 79412 A1 discloses a method for preparing a chemical formulation in an example on page 28, the method comprising the following steps: mixing a blend of linear alkylbenzene sulfonic acid (LAS) and a nonionic surfactant in a Sulzer-type static mixer, subsequently adding 50% NaOH to neutralize 30%-50% of the LAS, pumping the mixture into a static online mixer, then adding sufficient NaOH to complete the neutralization and pumping the resulting mixture through a dynamic online mixer.

[0022] WO 2013 / 092049 A1 discloses a method for preparing a chemical formulation in Comparative Example A, the method comprising the steps of: mixing C12-14 straight-chain alkylbenzene sulfonic acid (LAS acid) with sodium lauryl ether sulfate (SLES 3EO) having 3 moles of EO (etc.), followed by adding NaOH until the pH is 6.5, thereby neutralizing the LAS acid.

[0023] JP-A 64-47755 discloses a method for preparing a chemical formulation in Example 1, the method comprising the steps of: mixing a nonionic surfactant with a LAS acid in an iron reactor tank, followed by adding 45 wt.% NaOH for neutralization.

[0024] Therefore, the object of the present invention is to provide an improved continuous method for preparing chemical formulations containing neutralized components, which reduces undesirable side reactions and produces a final product with good processing properties.

[0025] Surprisingly, the applicant has discovered a continuous method of the present invention for producing chemical formulations comprising water, an ionic surfactant, and a co-surfactant via in-situ neutralization of precursors of ionic surfactants, which provides the following advantages:

[0026] • Efficient continuous methods

[0027] • Less investment required for specialized equipment such as high-shear homogenizers and containers

[0028] • The viscosity of any mixture prepared during this method shall not exceed the highest viscosity of any individual component.

[0029] • Avoid or minimize undesirable side effects.

[0030] • Compared to other manufacturing methods, it reduces the amount of excess neutralizer required. Summary of the Invention

[0031] Therefore, the present invention relates to a method for preparing a chemical formulation comprising at least water, an ionic surfactant, and a co-surfactant via in-situ neutralization of a precursor of an ionic surfactant, wherein the method is continuous and includes the following steps:

[0032] i) Mixing at least one precursor of an ionic surfactant, a co-surfactant, and a neutralizing agent using at least one mixing device selected from the group consisting of a continuous stirred tank reactor, a high-shear mixer, a mixing pump, a static mixer, and a mixing nozzle.

[0033] ii) Remove the obtained chemical formulations through the export process. Attached Figure Description

[0034]

[0035] exist Figure 1 and Figure 2 Explanation of the reference numerals used in the accompanying drawings:

[0036] (1) The source of precursors or neutralizers of ionic surfactants,

[0037] (2) Sources of co-surfactants

[0038] (3) The source of the neutralizing agent or the precursor of the ionic surfactant shall be determined based on the one not selected in (1).

[0039] (4) The first mixing device, preferably a static mixer.

[0040] (5) A second mixing device, preferably a static mixer.

[0041] (6) Export of the obtained chemical composition

[0042] (7) Connection between T-shaped parts and three-way valve

[0043] (8) Recirculation pipeline Detailed Implementation

[0044] The specific embodiments, examples, and drawings disclosed herein are for illustrative purposes and do not limit the scope of the invention.

[0045] The continuous method of the present invention includes the following steps:

[0046] i) Mixing at least one precursor of an ionic surfactant, a co-surfactant, and a neutralizing agent using at least one mixing device selected from the group consisting of a continuous stirred tank reactor, a high-shear mixer, a mixing pump, a static mixer, and a mixing nozzle.

[0047] ii) Remove the obtained chemical formulations through the export process.

[0048] This method is applicable to surfactant formulations containing neutralized components, and is particularly applicable to neutralized components that form gels with water in the absence of co-surfactants.

[0049] More specifically, the disclosed method can be used to prepare surfactant blends for applications such as enhanced oil extraction or liquid or gel detergent compositions.

[0050] The at least one precursor, co-surfactant, and neutralizer of the ionic surfactant can be added independently from their source to the pipes connected to the mixing device or directly to the mixing device.

[0051] As used throughout this invention, the term "precursor" refers to an acidic or basic precursor of an ionic surfactant.

[0052] As used throughout this invention, the term "source" for any component is intended to cover any kind of source. In one embodiment, the source may be a storage tank or an ISO container. Multiple sources, such as multiple storage tanks, may be used. Preferably, such storage tanks are mobile, allowing them to be easily relocated, for example, between manufacturing sites. In some embodiments of the invention, the storage tank may be a tank container, a tank trailer, or a tank truck. Essentially, these tanks can have any shape and size. In one embodiment, the tank may be cylindrical. The volume of the tank is not limited. As mentioned, a mobile tank may have a volume of 1 m³. 3 Up to 100 m 3 For example, 10 m 3 up to 50 m 3 The volume. The storage tank can also be used as a buffer tank to ensure an uninterrupted supply of components. When the storage tank needs to be heated, for example to maintain the pumpability of the components (i.e., with a viscosity below 2500 mPas), electrically heated, liquid-heated, or steam-heated ISO containers or tanks can be used.

[0053] The sources of precursors, co-surfactants, and neutralizers can be chosen independently.

[0054] In another embodiment, the precursor can be manufactured in situ. In this case, the source of the precursor can be understood as the reactor used to prepare the precursor. The reactor used in the method of the present invention to prepare the precursor and the mixing device can be connected by pipeline. In this embodiment, one or more buffer tanks connected by pipeline can be placed between the reactor used in the method of the present invention to prepare the precursor and the mixing device used in the method of the present invention to ensure an uninterrupted supply of the precursor.

[0055] As used throughout this invention, the term "pipeline" encompasses both rigid pipelines (such as conduits) and flexible pipelines (such as hoses or flexible metal pipes). A pipeline can, of course, include both rigid and flexible sections. The diameter of the pipeline can be, for example, from 50 mm to 80 cm. The flow in the system is typically laminar, but can also be turbulent.

[0056] In one embodiment of the invention, in step i), at least one precursor of the ionic surfactant, the co-surfactant, and the neutralizing agent are simultaneously added from their sources to the mixing apparatus. In this further preferred embodiment, the mixing apparatus is preferably a continuous stirred tank reactor or a high-shear mixer.

[0057] In different embodiments of the invention, step i) is divided into four sub-steps, namely i-1), i-2), i-3), and i-4), which will be explained in further detail below. In this additional preferred embodiment, the mixing device is preferably a static mixer.

[0058] In the method of this invention, the neutralization of the precursor can be partial or complete. In this embodiment, the molar ratio of the acid value or base value of the precursor to the neutralizing agent is in the range of 1:0.1 to 1:2.

[0059] In a preferred embodiment, the degree of neutralization of the precursor during the method may be at least 80 wt.%, more preferably at least 90 wt.%, and even more preferably, substantially all of the precursor is neutralized during the method.

[0060] In another embodiment, the molar ratio of the acid or base value of the precursor to the neutralizing agent is in the range of 1:1 to 1:1.5, preferably 1:1 to 1:1.1.

[0061] In another embodiment, the residence time of the components in the at least one mixing device may be less than 30 seconds, preferably less than 15 seconds, and more preferably less than 10 seconds.

[0062] In a preferred embodiment of the invention, the pressure inside the mixing device is higher than 200,000 Pa.

[0063] The time span between the point where the precursor comes into contact with the co-surfactant and the point where a homogeneous chemical formulation with a neutralized precursor is obtained is less than 15 minutes, preferably less than 2 minutes, and most preferably less than 1 minute.

[0064] In a preferred embodiment, the obtained chemical formulation may have a pH value of at least 7, preferably between 8 and 12.

[0065] In one embodiment of the invention, the viscosity of any mixture prepared during the method is not higher than the highest viscosity of the individual components.

[0066] The obtained chemical formulation may have a high concentration of surfactant, that is, the chemical formulation may have an active content of at least 80 wt.%, preferably at least 85 wt.%.

[0067] After chemical formulations containing ionic surfactants and co-surfactants are present in the mixing apparatus, they should be cooled to a stable temperature. This can be done using a heat exchanger or by mixing with a cold liquid.

[0068] In step ii) of the method, the obtained chemical formulation can be removed through an outlet.

[0069] In a preferred embodiment, the heat exchanger is located at or near the outlet of step ii).

[0070] In a preferred embodiment, the method does not use a dynamic circulating mixer, and preferably does not use any circulating mixer.

[0071] In another preferred embodiment, the method does not use any circulating reactor.

[0072] Further description of sub-steps i-1), i-2), i-3), and i-4):

[0073] In sub-step i-1), the precursor and co-surfactant can be fed from their sources into a common pipeline via a pump. Alternatively, in sub-step i-1), the neutralizer and co-surfactant can be fed from their sources into a common pump via a pump.

[0074] Any type of pump can be used in the method of the present invention. Preferably, a positive displacement pump or a centrifugal pump is used.

[0075] In one embodiment of the invention, the recirculation line can be used to regulate the flow rates of the precursor and co-surfactant to the desired values ​​before feeding these components into a common pipeline. For this purpose, a three-way valve and a T-joint can be used. At the start of the method, the three-way valve is positioned to allow the feed components to be fed into the recirculation line; once the desired flow rate is reached, the position of the three-way valve is switched, and the feed components are fed into the common pipeline. This embodiment provides the advantages of avoiding quality problems during the start-up of the method and enabling faster start-up, shutdown, and idle procedures. Figure 2 This embodiment is shown in the figure, wherein the reference numerals indicate:

[0076] (1) The source of precursors or neutralizers of ionic surfactants,

[0077] (2) Sources of co-surfactants

[0078] (3) The source of the neutralizing agent or the precursor of the ionic surfactant shall be determined based on the one not selected in (1).

[0079] (4) The first mixing device, preferably a static mixer.

[0080] (5) A second mixing device, preferably a static mixer.

[0081] (6) Export of the obtained chemical composition

[0082] (7) Connection between T-shaped parts and three-way valve

[0083] (8) Recirculation pipeline

[0084] In sub-step i-2), a mixture of the precursor and the co-surfactant (or alternatively, a mixture of the neutralizer and the co-surfactant) is introduced into at least one first mixing device selected from the group consisting of: a continuous stirred tank reactor (CSTR), a high-shear mixer, a mixing pump, a static mixer, and a mixing nozzle.

[0085] In a preferred embodiment, the first mixing device is a static mixer.

[0086] High-shear mixers are familiar to technicians. They are a type of mixing device used in various industries, including pharmaceuticals, food, and chemicals. High-shear mixers are designed to generate intense mechanical forces, thereby mixing, dispersing, or emulsifying liquids and solids. A mixer typically consists of a rotor and stator that generate a high-speed flow and impart a velocity of 1000 s to the material being processed. -1 Or even higher shear forces. This high shear helps break down particles and enhances the homogeneity and stability of the mixture. High-shear mixers are typically used in applications requiring thorough mixing, particle size reduction, or the production of stable emulsions.

[0087] Static mixers are well-known to those skilled in the art. A static mixer must be able to operate in a continuous process and be capable of mixing fluids. Suitable static mixers include, for example, split-and-recombine type mixers, microchannel mixers, and T-joints in piping. Static mixers preferably have a length-to-diameter ratio of at least 8. It is desirable that the inner diameter of the static mixer is similar to or equal to the inner diameter of the piping.

[0088] For the method of the present invention, a static mixer is particularly preferred over a dynamic mixer because a static mixer requires lower energy input and thus results in energy savings and lower operating costs. Static mixers also require lower capital investment, and this is especially true for multi-stage high-shear dynamic mixers, which have significantly higher lifetime costs than the static mixers used in the method of the present invention.

[0089] In one embodiment, the mixture obtained in sub-step i-1) is introduced directly into the first static mixer after the precursor stream and the co-surfactant stream are combined.

[0090] In one embodiment of the invention, the mixture prepared in step i-2) is substantially homogeneous upon exiting the at least one first static mixer. The homogeneity of the mixture can be evaluated by the coefficient of variation of its concentration. In one embodiment, the coefficient of variation of the concentration of the mixture prepared in sub-step i-2) is less than 10%, preferably less than 5%, and more preferably less than 1%.

[0091] The coefficient of variation (CV) of concentration can be calculated as follows:

[0092]

[0093] Where s is the concentration of a random sample of the mixture, and It is the average concentration of the mixture.

[0094] A coefficient of variation of concentration below 10% indicates that the mixture has achieved a level of homogeneity such that when a random sample is taken from the mixture, the concentration of that sample will deviate from the average concentration of the mixture by only 10%. Therefore, the lower the coefficient of variation of concentration, the higher the homogeneity of the mixture.

[0095] Achieving good homogeneity in sub-step i-2) has the advantage that the viscosity of any mixture prepared during the method is not higher than the highest viscosity of the individual components.

[0096] As stated above, many chemical formulations prepared by neutralizing acids or bases present additional difficulties, namely, the neutralized form of the acid or base reacts with water present in the composition to form highly viscous products such as gels. This increases the difficulty of handling the product, mixing the product with other components, and setting up efficient continuous processes.

[0097] This often occurs, for example, in the preparation of surfactant compositions for oilfield or detergent applications via neutralizing an acidic precursor of the surfactant.

[0098] In sub-step i-3) of the method, the mixture obtained in sub-step i-2) is combined with at least one neutralizing agent. The neutralizing agent reacts with the precursor to form an ionic surfactant. Alternatively, in sub-step i-3), the mixture obtained in sub-step i-2) is combined with at least one precursor of an ionic surfactant.

[0099] In one embodiment, the time span between the start of sub-steps i-1) and i-3) is less than 10 minutes, preferably less than 2 minutes, and particularly preferably less than 1 minute. Reducing the contact time between the unneutralized precursor and the co-surfactant is beneficial because the two components may react undesirably, thus forming undesirable byproducts and reducing the efficiency of the method, decreasing the yield, or degrading the quality of the product.

[0100] For example, when using sulfonic acid derivatives as precursors and ammonium salts of sulfate derivatives as co-surfactants, the acidic nature of the free sulfonic acid leads to desulfurization of the co-surfactant, resulting in a loss of product performance. Premixing the ammonium salt of the sulfate derivative with a base as a neutralizing agent will cause ion exchange between the ammonium salt and the alkali metal, releasing harmful ammonia.

[0101] Therefore, by achieving a substantially homogeneous mixture of the precursor and co-surfactant within 10 minutes, preferably within 2 minutes, and especially preferably within 1 minute, the method of the present invention provides all the advantages of lower viscosity in mixing the precursor and co-surfactant, while avoiding or minimizing the disadvantages of unwanted reaction byproducts of the precursor and co-surfactant.

[0102] In one embodiment of the invention, a neutralizing agent (or alternatively, a precursor of an ionic surfactant) is added to the mixture prepared in sub-step i-2) at a location located after the at least one first mixing device and before the at least one second mixing device.

[0103] In sub-step i-4) of the method, the mixture obtained in sub-step i-3) is passed through at least one second mixing device, which is selected from the group consisting of a continuous stirred tank reactor, a high-shear mixer, a mixing pump, a static mixer and a mixing nozzle.

[0104] The characteristics of the second mixing device may be the same as or different from those of the first mixing device.

[0105] In one embodiment, the residence time of the component in any mixing device (first mixing device or second mixing device) may be less than 30 seconds, preferably less than 15 seconds, and more preferably less than 10 seconds.

[0106] In a preferred embodiment, either the first or second mixing device is a static mixer. In another preferred embodiment, both the first and second mixing devices are static mixers. Static mixers offer the advantage of obtaining a homogeneous mixture within a short time period, which facilitates better conversion of the main desired reaction in the method while avoiding or minimizing undesirable side reactions.

[0107] Due to the energy input required for the mixing action in the static mixer, there is an increased pressure in front of the mixer compared to behind it, when viewed in the flow direction. Typically, the pressure inside the static mixer is higher than atmospheric pressure. This is particularly preferred because it plays a role in preventing unwanted side reactions. That is, it relates to side reactions that occur as equilibrium reactions and form byproducts with vapor pressures higher than atmospheric pressure at the process temperature. The pressure increase can be generated by the flow of components through the static mixer or by applying pressure using a pump or gas.

[0108] exist Figure 1 This particularly preferred embodiment is shown in the figure, wherein the reference numerals indicate:

[0109] (1) Sources of precursors for ionic surfactants

[0110] (2) Sources of co-surfactants

[0111] (3) Source of neutralizing agent

[0112] (4) The first mixing device, preferably a static mixer.

[0113] (5) A second mixing device, preferably a static mixer.

[0114] (6) Export of the obtained chemical composition

[0115] In another preferred embodiment, the reference numerals in the figures indicate the following:

[0116] (1) Source of neutralizing agent

[0117] (2) Sources of co-surfactants

[0118] (3) Sources of precursors for ionic surfactants

[0119] (4) The first mixing device, preferably a static mixer.

[0120] (5) A second mixing device, preferably a static mixer.

[0121] (6) Export of the obtained chemical composition.

[0122] If the precursor is acid, a temperature rise is expected during neutralization, depending on the acid content in the precursor. Therefore, after the homogeneous chemical formulation containing ionic surfactants and co-surfactants is present in the second mixing unit, it should be cooled to a stable temperature. This can be done using a heat exchanger or by mixing with a cold liquid.

[0123] Chemical components

[0124] Abbreviations used:

[0125] PO = Propylene oxide

[0126] EO = Ethylene oxide

[0127] TSP = Triphenylphenylphenol

[0128] ABS = Alkylbenzenesulfonic acid

[0129] LABS = linear alkylbenzene sulfonic acid

[0130] As used throughout this invention, the term "precursor" refers to a precursor of an ionic surfactant.

[0131] Ionic surfactants are formed in situ through the reaction of appropriate precursors and neutralizing agents.

[0132] Unless otherwise specified, precursors, ionic surfactants, and co-surfactants can be straight-chain or branched molecules.

[0133] In one embodiment, the ionic surfactant may be an anionic surfactant selected from the group consisting of alkylbenzene sulfonates, preferably having C 10-32 Alkyl chain long linear alkylbenzene sulfonates; primary alkyl sulfonates and secondary alkyl sulfonates, preferably C 10-15 Primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates, preferably C 19-28 Inner olefin sulfonates or C 12-23 α-olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates; and combinations thereof.

[0134] Therefore, in this embodiment, the precursor is the acidic form of the at least one selected anionic surfactant. That is, the precursor can be selected from: alkylbenzene sulfonic acid, preferably having C... 10-32 Long-chain linear alkylbenzene sulfonic acids (LABS); primary alkyl sulfonic acids and secondary alkyl sulfonic acids, preferably C 10-15 Primary alkyl sulfonic acids; alkyl ether sulfonic acids; olefin sulfonic acids; alkyl xylene sulfonic acids; dialkyl sulfosuccinic acids; and fatty acid ester sulfonic acids.

[0135] In another preferred embodiment, the ionic surfactant is an alkylbenzene sulfonate, preferably having a C0... 10-32 A linear alkylbenzene sulfonate with a long alkyl chain, and the precursor is an alkylbenzene sulfonic acid, preferably having a C10+. 10-32 Long-chain linear alkylbenzene sulfonic acid (LABS).

[0136] In another preferred embodiment, the anionic surfactant may have sodium as a counterion.

[0137] When the ionic surfactant is anionic and the precursor is an acidic form of at least one selected anionic surfactant, the neutralizing agent may be a base.

[0138] In one embodiment, the neutralizing agent may be an aqueous solution of an alkali selected from the following: NaOH, KOH, NH4OH, Na2CO3, NaHCO3, K2CO3, KHCO3, Ca(OH)2, Mg(OH)2, sodium acetate, potassium acetate or NH4 acetate, preferably an aqueous solution of NaOH.

[0139] In a preferred embodiment, the aqueous solution of the neutralizing agent may have an active content of 2 to 98 wt.%, preferably 20 to 80 wt.%, and more preferably 45 to 60 wt.%.

[0140] In a preferred embodiment of the invention, the precursor is an acid, the neutralizing agent is a base, and the first ionic component is an anion.

[0141] The co-surfactant may be different from the ionic surfactant and may be selected as ionic or nonionic, preferably anionic or nonionic, and more preferably anionic.

[0142] Examples of anionic cosurfactants are carboxylates, sulfonates, or sulfates.

[0143] Carboxylates may be selected from at least one of the following: C 12-32 -alkylPO 2-50 EO 2-100 Carboxylates, C 12-32 -alkylPO 2-50 Carboxylates, C 12-32 -alkylEO 2-100 Carboxylate, Tristyrylphenol (TSP)PO 2-50 EO 2-100 Carboxylates, other monoalkyl, dialkyl and trialkylphenol alkoxycarboxylates, cocamidopropyl betaine, other C 12-20 Betaine or sulfobetaine. Preferably, the carboxylate can be selected from C 28 -alkyl-PO 25 -EO 45 -Carboxylate.

[0144] Sulfates may be selected from at least one of the following: TSP, PO 2-50 EO 2-100 Sulfates or other monoalkyl, dialkyl, and trialkylphenol alkoxy sulfates, C 12-32 -alkylPO 2-50 EO 2-100 Sulfate, C 12-32 -alkylPO 2-50Sulfates, or C 12-32 -alkylEO 2-100 Sulfate. Preferably, the sulfate may be selected from TSP-PO. 35 -EO 20 Sulfates.

[0145] Sulfonates can be selected from at least one C 10-20 Alkylbenzene sulfonates (ABS), olefin sulfonates such as C 12-30 Inner olefin sulfonates, C 12-20 α-olefin sulfonates, C 12-28 Glyceryl sulfonate, C 12-28 Diphenyl oxide disulfonate. Preferably, the sulfonate may be selected from dodecylbenzene sulfonate.

[0146] In one embodiment, the anionic co-surfactant has ammonium as a counterion.

[0147] In another preferred embodiment, the co-surfactant is a sulfate having ammonium as a counterion, most preferably TSP-PO. 35 -EO 25 -SO4 - NH4 + .

[0148] Examples of cationic cosurfactants are ammonium salts comprising four hydrocarbon radicals, such as alkoxylated amines, like (2-hydroxyethyl)(2-hydroxyhexadecyl)dimethylammonium salts as chloride or bromide salts.

[0149] Examples of nonionic cosurfactants are alkoxylated surfactants, such as polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers, alkylphenol polyethylene glycol ethers, end-sealed polyethylene glycol ethers, mixed ethers and hydroxyl mixed ethers, and fatty acid polyethylene glycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyethylene glycol ethers may also be used. Another important class of nonionic surfactants used according to the invention can be polyol surfactants, and in particular glycoside surfactants, such as alkyl polysaccharides and fatty acid glucosamides.

[0150] Preferred alkyl polysaccharides, especially those containing long-chain fatty alcohols or branched or unbranched C-chains, are preferred. 8-18 Alkyl polyglucosides of mixtures of long-chain fatty alcohols with alkyl chains, and sugars with a degree of oligomerization (DP) between 1 and 10, preferably 1 to 6, particularly 1.1 to 3, and most preferably 1.1 to 1.7, are, for example, C10 sugars. 8-10 Alkyl-1,5-glucoside (DP is 1.5).

[0151] Preferred fatty alcohol alkoxylated compounds (fatty alcohol polyethylene glycol ethers), particularly alkoxylated, unbranched or branched, saturated or unsaturated C-terminals of ethylene oxide (EO) and / or propylene oxide (PO) with an alkoxylation degree up to 30. 8-22 Alcohols, preferably with a degree of ethoxylation of less than 30, more preferably 12 to 28, particularly 20 to 28, and more preferably 25, are ethoxylated C. 12-22 Fatty alcohols, such as C with 25 EOs 16-18 Fatty alcohol ethoxylates. Example

[0152] The applicant has made the following examples and comparative examples to quantitatively demonstrate at least some of the advantages of the method of the invention, particularly minimizing undesirable side reactions and reducing the excess of necessary neutralizing agents.

[0153] In the example, TSP-PO is used. 35 -EO 20 Ammonium salts of sulfates are used as co-surfactants, using C 15-16 Alkylbenzene sulfonic acid is used as a precursor for ionic surfactants, and NaOH is used as a neutralizing agent.

[0154] One of the undesirable reactions that may occur between these components is TSP-PO. 35 -EO 20 The reaction between the ammonium salt of sulfate and NaOH releases ammonia.

[0155] To evaluate the occurrence of this undesirable side reaction, ammonium ions are measured in the co-surfactant used as a starting material and in the obtained chemical formulation. Ideally, the amount of ammonium cations should remain constant. However, if the co-surfactant reacts with the neutralizing agent, the amount of ammonium cations will decrease due to the release of ammonia.

[0156] Method for quantifying the amount of ammonium cations

[0157] The content of ammonium cations was measured by ion chromatography using a 940 Professional IC Vario.

[0158] Sample preparation was as follows: Approximately 0.1 g and 0.2 g of sample were weighed into 25 mL volumetric flasks, diluted to the mark with eluent, and homogenized by sonication. For analysis by ion chromatography, the sample solution was diluted with eluent with appropriate calibration range. The eluent used was 2.5 mmol / L HNO3.

[0159] For quantification, external calibration was performed using ammonium standard solutions at the following concentrations: 0.1, 0.2, 0.5, 0.7, 1, 2, 5, and 10 mg / L. Peak areas were used for evaluation.

[0160] Example 1 of the present invention:

[0161] According to such Figure 2 The setup shown is used for the blending process, where (1) is the source of the precursor of the ionic surfactant, (2) is the source of the co-surfactant, and (3) is the source of the neutralizer.

[0162] TSP-PO 35 -EO 20 The ammonium salt of sulfate was metered into the static mixer at a rate of 12 g / min. C was metered into the mixture at a rate of 8.59 g / min. 10-32 Alkylbenzene sulfonic acid. Sodium hydroxide solution was added at a rate of 1.915 g / min.

[0163] Prepare chemical formulations having the following components, on a minute-by-minute basis:

[0164]

[0165] The temperature of the blend, after neutralization but before cooling, rises to 60°C and then drops to 38°C after cooling.

[0166] This method produces stable and homogeneous blends with a pH > 8 (measured as a 2 wt.% solution in deionized water) and no obvious gaseous byproducts.

[0167] Given that the ABS starting material used has an acid value of 147 mg KOH / g, which is equal to 105 mg NaOH / g, this indicates that theoretically, 1.801 g of a 50 wt.% aqueous solution of NaOH should be sufficient to completely neutralize the ABS, i.e., the acid values ​​of NaOH and ABS are equimolar. In practice, 1.915 g is required for this experiment, meaning the molar ratio of the precursor (i.e., ABS) acid value to the neutralizing agent (i.e., NaOH) is 1:1.06.

[0168] The required excess neutralizing agent is very small. This provides the first indication that undesirable side reactions can be avoided by using the method of the present invention.

[0169] To demonstrate that the undesirable side reactions between the co-surfactant and the neutralizing agent, and the resulting loss of ammonium, are significantly reduced in the method of this invention, the amount of ammonium cations was measured in the co-surfactant used as a starting material and in the obtained chemical formulation. The results are summarized in the table below:

[0170]

[0171] The results clearly show that only 6.23% of the co-surfactant reacted with the neutralizing agent, thus producing TSP-PO. 35 -EO 20 The sodium salt of sulfate is released and ammonia is produced. This is approximately 90% smaller than in Comparative Example 1 and approximately 76% smaller than in Comparative Example 2, as will be seen later.

[0172] Example 2 of the present invention:

[0173] According to such Figure 2 The setup shown is used for the blending process, where (1) is the source of the neutralizing agent, (2) is the source of the co-surfactant, and (3) is the source of the precursor of the ionic surfactant.

[0174] First, mix NaOH solution with TSP-PO 35 -EO 20 Sulfates are mixed, then C 10-32 Alkylbenzene sulfonic acid is mixed in. TSP-PO 35 -EO 20 The ammonium salt of sulfate was metered into the static mixer at a rate of 12 g / min. C was metered into the mixture at a rate of 8.59 g / min. 10-32 Alkylbenzene sulfonic acid. Sodium hydroxide solution was added at a rate of 1.915 g / min.

[0175] Prepare chemical formulations having the following components, on a minute-by-minute basis:

[0176]

[0177] The temperature of the blend, after neutralization but before cooling, rises to 58°C and then drops to 32°C after cooling.

[0178] This method produces stable and homogeneous blends with a pH > 8 (measured as a 2 wt.% solution in deionized water) and no obvious gaseous byproducts.

[0179] Given that the ABS starting material used has an acid value of 147 mg KOH / g, which is equal to 105 mg NaOH / g, this indicates that theoretically, 1.801 g of a 50 wt.% aqueous solution of NaOH should be sufficient to completely neutralize the ABS, i.e., the acid values ​​of NaOH and ABS are equimolar. In practice, 1.915 g is required for this experiment, meaning the molar ratio of the precursor (i.e., ABS) acid value to the neutralizing agent (i.e., NaOH) is 1:1.06.

[0180] The required excess neutralizing agent is very small. This provides the first indication that undesirable side reactions are reduced by using the method of the present invention.

[0181] To demonstrate that the undesirable side reactions between the co-surfactant and the neutralizing agent, and the resulting loss of ammonium, are significantly reduced in the method of this invention, the amount of ammonium cations was measured in the co-surfactant used as a starting material and in the obtained chemical formulation. The results are summarized in the table below:

[0182]

[0183] The results clearly show that only 13.44% of the co-surfactant reacted with the neutralizing agent, thus producing TSP-PO. 35 -EO 20 The sodium salt of sulfate is released and ammonia is produced. This is approximately 86% smaller than in Comparative Example 1 and approximately 84% smaller than in Comparative Example 2, as will be seen later.

[0184] Comparison Example 1:

[0185] This comparative example is based on WO 2015 / 138175, and in particular on Example 2 described on page 8.

[0186] For the comparative example, a 250 mL four-necked flask was used. The flask was cooled in a water bath and equipped with two dropping funnels. It was stirred with a stirrer to mix the components.

[0187] Prepare chemical formulations having the following components:

[0188]

[0189] The flask was pre-filled with NaOH aqueous solution and stirred at 200 rpm. Over a period of 1 hour, ABS and TSP-PO were simultaneously added via two dropping funnels. 35 -EO 20 Ammonium salt of sulfate. The stirring speed was gradually increased from 200 rpm to 800 rpm to compensate for the increased viscosity.

[0190] During the addition of the two surfactants, an exothermic reaction caused a temperature rise, which was stabilized at 40°C by cooling in a water bath. The formation of foam, solid lumps, and solid deposits was observed. The blend was homogenized by further stirring at 800 rpm at 40°C for 2–3 hours.

[0191] The obtained chemical formulation has a pH value higher than 8 (measured as a 2 wt.% solution in deionized water).

[0192] Given that the ABS starting material used has an acid value of 154.5 mg KOH / g, which is equal to 110 mg NaOH / g, this indicates that theoretically, 7.49 g of a 50 wt.% aqueous solution of NaOH should be sufficient to completely neutralize the ABS, i.e., the acid values ​​of NaOH and ABS are equimolar. However, 9.09 g is required to perform this experiment, meaning the molar ratio of the precursor (i.e., ABS) acid value to the neutralizing agent (i.e., NaOH) is 1:1.21.

[0193] Due to the setup of this method, an excess of NaOH needs to be added to compensate for TSP-PO. 35 -EO 20 An undesirable side reaction occurs between the ammonium salt of sulfate and NaOH, releasing ammonia. This was confirmed by measuring the concentration of the ammonium cation in the co-surfactant before and in the final chemical formulation. The results are summarized in the table below:

[0194]

[0195] The results clearly show that 96.2% of the co-surfactant reacted with the neutralizing agent, thereby producing TSP-PO. 35 -EO 20 The sodium salt of sulfate releases ammonia gas.

[0196] Comparison Example 2:

[0197] The same method steps as in Comparative Example 1. However, C is used as in Examples 1 and 2 of the present invention. 10-32 Alkylbenzene sulfonic acid.

[0198] Prepare chemical formulations having the following components:

[0199]

[0200] Given that the ABS starting material used has an acid value of 147 mg KOH / g, which is equal to 105 mg NaOH / g, this indicates that theoretically, 7.28 g of a 50 wt.% aqueous solution of NaOH should be sufficient to completely neutralize the ABS, i.e., the acid values ​​of NaOH and ABS are equimolar. However, 8.68 g is required to perform this experiment, meaning the molar ratio of the precursor (i.e., ABS) acid value to the neutralizing agent (i.e., NaOH) is 1:1.19.

[0201] In Comparative Example 1, due to the settings of this method, an excess of NaOH needs to be added to compensate for TSP-PO. 35 -EO 20An undesirable side reaction occurs between the ammonium salt of sulfate and NaOH, releasing ammonia. This was confirmed by measuring the concentration of the ammonium cation in the co-surfactant before and in the final chemical formulation. The results are summarized in the table below:

[0202]

[0203] The results clearly show that 82.7% of the co-surfactant reacted with the neutralizing agent, thereby producing TSP-PO. 35 -EO 20 The sodium salt of sulfate releases ammonia gas.

[0204] Embodiments of the present invention:

[0205] 1. A continuous method for preparing a chemical formulation comprising at least water, an ionic surfactant, and a co-surfactant, wherein the ionic surfactant is prepared in situ by reacting a precursor of the ionic surfactant with a neutralizing agent, and the method comprising the following steps:

[0206] i) Mixing at least one precursor of an ionic surfactant, a co-surfactant, and a neutralizing agent using at least one mixing device selected from the group consisting of a continuous stirred tank reactor, a high-shear mixer, a mixing pump, a static mixer, and a mixing nozzle.

[0207] ii) Remove the obtained chemical formulations through the export process.

[0208] 2. In a preferred embodiment of the present invention, at least one precursor of the ionic surfactant, a co-surfactant, and a neutralizing agent are simultaneously added to the mixing device.

[0209] 3. In a preferred embodiment of the present invention, the mixing device is a continuous stirred tank reactor or a high-shear mixer.

[0210] 4. In a preferred embodiment of the present invention, at least two mixing devices are used.

[0211] 5. In a preferred embodiment of the present invention, step i) includes the following sub-steps:

[0212] i-1) Combining at least one precursor of the ionic surfactant with the co-surfactant.

[0213] i-2) The mixture obtained in sub-step i-1) is fed through at least one first mixing device.

[0214] i-3) The mixture obtained in sub-step i-2) is combined with at least one neutralizing agent.

[0215] i-4) The mixture obtained in sub-step i-3) is fed through at least one second mixing device.

[0216] The first mixing device and the second mixing device are independently selected from the group consisting of: a continuous stirred tank reactor, a high-shear mixer, a mixing pump, a static mixer, and a mixing nozzle.

[0217] 6. In a preferred embodiment of the present invention, step i) includes the following sub-steps:

[0218] i-1) Combine the neutralizing agent with the co-surfactant.

[0219] i-2) Mix the mixture obtained in step u-1).

[0220] i-3) Add at least one precursor of the ionic surfactant, and

[0221] i-4) Mix the mixture obtained in step i-3).

[0222] 7. In a preferred embodiment of the present invention, the first mixing device and / or the second mixing device are static mixers.

[0223] 8. In a preferred embodiment of the invention, the time span between the point where the precursor contacts the co-surfactant and the point where a homogeneous chemical formulation having a neutralized precursor is obtained is less than 15 minutes, preferably less than 2 minutes, and most preferably less than 1 minute.

[0224] 9. In a preferred embodiment of the invention, the time span between the point where the neutralizing agent contacts the co-surfactant and the point where a homogeneous chemical formulation having a neutralized precursor is obtained is less than 15 minutes, preferably less than 2 minutes, and most preferably less than 1 minute.

[0225] 10. In a preferred embodiment of the present invention, the precursor is an acid, the neutralizing agent is a base, and the ionic component is an anion.

[0226] 11. In a preferred embodiment of the invention, the precursor is selected from the group consisting of alkylbenzene sulfonic acid, preferably having a C0... 10-32 Long-chain linear alkylbenzene sulfonic acids (LABS); primary alkyl sulfonic acids and secondary alkyl sulfonic acids, preferably C 10-15 Primary alkyl sulfonic acids; alkyl ether sulfonic acids; olefin sulfonic acids; alkyl xylene sulfonic acids; dialkyl sulfosuccinic acids; and fatty acid ester sulfonic acids.

[0227] 12. In a preferred embodiment of the invention, the neutralizing agent is an aqueous solution containing an alkali selected from the group consisting of: NaOH, KOH, NH4OH, Na2CO3, NaHCO3, K2CO3, KHCO3, Ca(OH)2, Mg(OH)2, sodium acetate, potassium acetate, or NH4 acetate, preferably NaOH.

[0228] 13. In a preferred embodiment of the present invention, the co-surfactant is anionic, preferably selected from the group consisting of carboxylates, sulfonates or sulfates, and most preferably sulfates.

[0229] 14. In a preferred embodiment of the present invention, the anionic co-surfactant has ammonium as a counterion; preferably, the co-surfactant is a sulfate having ammonium as a counterion, and most preferably, TSP-PO. 35 -EO 25 -SO4 - NH4 + .

[0230] 15. In a preferred embodiment of the present invention, the molar ratio of the acid value or base value of the precursor to the neutralizing agent is in the range of 1:1 to 1:1.5, preferably 1:1 to 1:1.1.

[0231] 16. In a preferred embodiment of the present invention, the surfactant activity content of the obtained chemical formulation is at least 80 wt.%, preferably 85 wt.%, based on the total weight of all components in the chemical formulation.

[0232] 17. In a preferred embodiment of the present invention, the coefficient of variation of the concentration of the mixture prepared in sub-step i-2) is less than 10%, preferably less than 5%, and more preferably less than 1%.

[0233] 18. In a preferred embodiment of the invention, the residence time of these components in the mixing device is less than 1 minute, preferably less than 30 seconds, and more preferably less than 15 seconds.

Claims

1. A continuous method for preparing a chemical formulation comprising at least water, an ionic surfactant, and a co-surfactant, wherein the ionic surfactant is prepared in situ by reacting a precursor of the ionic surfactant with a neutralizing agent, and the method comprising the following steps: i) The at least one precursor of the ionic surfactant, the co-surfactant, and the neutralizing agent are mixed by at least one mixing device selected from the group consisting of a continuous stirred tank reactor, a high-shear mixer, a mixing pump, an online mixer, a static mixer, and a mixing nozzle. ii) Remove the obtained chemical formulations through export. in The precursor of this ionic surfactant is an acid. This co-surfactant is an anionic type with ammonium as the counterion, and The neutralizing agent is a base that does not contain ammonium cations, and Step i) includes the following sub-steps: i-1) Combining at least one precursor of the ionic surfactant with the co-surfactant. i-2) Mix the mixture obtained in step i-1). i-3) Add at least one neutralizing agent, and i-4) Mix the mixture obtained in step i-3). Or step i) may include the following sub-steps: i-1) Combine the neutralizing agent with the co-surfactant. i-2) Mix the mixture obtained in step u-1). i-3) Add at least one precursor of the ionic surfactant, and i-4) Mix the mixture obtained in step i-3).

2. The method according to claim 1, wherein, Use at least two mixing devices, which are independently selected from continuous stirred tank reactors, high-shear mixers, mixing pumps, static mixers, in-line mixers, and mixing nozzles.

3. The method according to any one of the preceding claims, wherein, Mixing step i-2) is performed in the first mixing apparatus, and mixing step i-4) is performed in the second mixing apparatus. The first mixing device and the second mixing device are independently selected from the group consisting of: continuous stirred tank reactor, high shear mixer, mixing pump, static mixer, online mixer and mixing nozzle.

4. The method according to claim 2 or 3, wherein, The first mixing device and / or the second mixing device is a static mixer.

5. The method according to any one of the preceding claims, wherein, The time span between the point where the precursor contacts the co-surfactant and the point where a homogeneous chemical formulation having a neutralized precursor is obtained is less than 15 minutes, preferably less than 2 minutes, and most preferably less than 1 minute, or wherein the time span between the point where the neutralizer contacts the co-surfactant and the point where a homogeneous chemical formulation having a neutralized precursor is obtained is less than 15 minutes, preferably less than 2 minutes, and most preferably less than 1 minute.

6. The method according to any one of the preceding claims, wherein, The precursor is selected from the group consisting of: alkylbenzene sulfonic acid, preferably having C 10-32 Long-chain linear alkylbenzene sulfonic acids (LABS); primary alkyl sulfonic acids and secondary alkyl sulfonic acids, preferably C 10-15 Primary alkyl sulfonic acids; alkyl ether sulfonic acids; olefin sulfonic acids; alkyl xylene sulfonic acids; dialkyl sulfosuccinic acids; and fatty acid ester sulfonic acids.

7. The method according to any one of the preceding claims, wherein, The neutralizing agent is an aqueous solution of a base selected from the group consisting of: NaOH, KOH, NH4OH, Na2CO3, NaHCO3, K2CO3, KHCO3, Ca(OH)2, Mg(OH)2, sodium acetate, potassium acetate, and NH4 acetate, preferably NaOH.

8. The method according to any one of the preceding claims, wherein, The co-surfactant is selected from the group consisting of carboxylates, sulfonates and sulfates, preferably sulfates.

9. The method according to any one of the preceding claims, wherein, The co-surfactant is a sulfate with ammonium as a counterion, preferably TSP-PO. 35 -EO 25 -SO4 - NH4 + .

10. The method according to any one of the preceding claims, wherein, The molar ratio of the acid or base value of the precursor to the neutralizing agent is in the range of 1:1 to 1:1.5, preferably 1:1 to 1:1.

1.

11. The method according to any one of the preceding claims, wherein, The surfactant activity content of the obtained chemical formulation is at least 80 wt.%, preferably 85 wt.%, based on the total weight of all components in the chemical formulation.

12. The method according to any one of the preceding claims, wherein, The coefficient of variation of the concentration of the mixture prepared in sub-step i-2) is less than 10%, preferably less than 5%, and more preferably less than 1%. The coefficient of variation (CV) for this concentration is calculated using the following formula. Where s is the concentration of a random sample of the mixture, and It is the average concentration of the mixture.

13. The method according to any one of the preceding claims, wherein, The residence time of these components in the mixing device is less than 1 minute, preferably less than 30 seconds, and more preferably less than 15 seconds.

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