TWI616560B - Pickling solution, use and preparation method thereof - Google Patents

Abstract

An acid washing liquid, a use thereof and a preparation method thereof, the acid washing liquid may comprise, by weight percentage, 0.5 to 12% of sulfamic acid; 0.5 to 12% of an ethylene glycol component; 0.5 to 12% of a halide component; and an organic acid component 0.5 to 12%; and 100% by weight of water to the total weight. The pickling solution can be used to clean scales containing ammonia nitrogen deposits, zinc oxides and calcium oxides, and does not cause environmental pollutants containing organic phosphoric acid after washing.

Description

Pickling solution, use thereof and preparation method

The present invention relates to a cleaning solution, and more particularly to an acid washing liquid having foaming properties, its use and a preparation method.

In various industrial applications, since inorganic acids (such as sulfuric acid, hydrochloric acid, nitric acid, etc.) are relatively inexpensive and relatively easy to obtain, inorganic acids are often used in industrial cleaning applications, for example, acidizing metal materials with acid washing liquids. Dipping rust and surface descaling.

For example, Chinese Patent Application No. CN 102284247A "A method for cleaning a reverse osmosis system" discloses a conventional pickling solution which may contain an aqueous solution of a cleaning agent having a pH value of about 3.0±0.5, the cleaning agent may be composed of a mixed acid and an anti-scaling dispersing agent, and the anti-scaling dispersing agent may be selected from at least one of an organic phosphoric acid, a carboxylic acid homopolymer and a carboxylic acid copolymer, but after the organic phosphoric acid is discharged, It is easy to cause environmental pollution problems in rivers.

In addition, the Chinese Patent Application No. CN 1030618C "Stainless Steel Pickling Liquid and Method of Use" discloses another conventional pickling liquid which may contain a nitric acid content of 8 to 15% and a hydrofluoric acid content of 2 to 4%. An aqueous solution having a hydrogen peroxide content of 2 to 4%, but the aqueous solution is not suitable for cleaning scale containing ammonia nitrogen deposits, zinc oxides and calcium oxides.

In view of this, it is necessary to provide an acid washing solution to solve the problems of the conventional technology.

The main object of the present invention is to provide an acid washing liquid which can be used for cleaning scale containing ammonia nitrogen deposits, zinc oxides and calcium oxides, and which does not cause environmental pollutants containing organic phosphoric acid after washing.

A secondary object of the present invention is to provide a use of an acid wash which can be used for cleaning The scale containing ammonia nitrogen deposits, zinc oxides and calcium oxides will not cause environmental pollutants containing organic phosphoric acid after washing.

Another object of the present invention is to provide a method for preparing an acid washing liquid which can be used for cleaning scale containing ammonia nitrogen deposits, zinc oxides and calcium oxides, and which does not cause environmental pollutants containing organic phosphoric acid after washing.

To achieve the above object, the present invention provides an acid washing liquid which may comprise, by weight percentage, 0.5 to 12% of sulfamic acid, 0.5 to 12% of an ethylene glycol component, 0.5 to 12% of a halide component, and 0.5 to 12% of an organic acid component. Up to 12%; and water to 100% by weight.

In one embodiment of the present invention, the glycol component may be selected from the group consisting of ethylene glycol 600, ethylene glycol 800, and ethylene glycol 1000.

In one embodiment of the invention, the glycolic component can be ethylene glycol 1000.

In one embodiment of the invention, the halide component may be selected from the group consisting of cuprous chloride, sodium chloride, potassium chloride, zinc chloride, and potassium iodide.

In one embodiment of the invention, the halide component can be potassium iodide.

In one embodiment of the present invention, the organic acid component may be selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid.

In an embodiment of the invention, the organic acid component may be propionic acid.

In one embodiment of the present invention, the total weight percentage of the sulfanilic acid, the ethylene glycol component, the halide component, and the organic acid component may be 20 to 30%.

In order to achieve the above object, the present invention further provides the use of the above acid washing liquid, which can be applied to cleaning a scale of a heat exchanger.

In an embodiment of the invention, the heat exchanger can be an ammonia distillation tray plate heat exchanger.

In an embodiment of the invention, the foulant may comprise ammonia nitrogen deposits, zinc oxides, and calcium oxides.

In an embodiment of the invention, the pickling solution may have a pH between 1 and 3 during the cleaning of the scale of the ammonia distillation tray plate heat exchanger.

In an embodiment of the present invention, the acid washing liquid may have a foaming property when the pH value is 1.

In an embodiment of the present invention, in the process of cleaning the scale of the ammonia distillation tray plate heat exchanger, if the pH value of the acid washing liquid is greater than 3, the sulfamic acid may be additionally added or not used yet. The acid wash is washed to restore the weight percentage of the sulfamic acid to 0.5 to 12% and to restore the pH of the acid wash to between 1 and 3.

In order to achieve the above object, the present invention further provides a method for preparing the above acid washing liquid, which may comprise the steps of: dissolving 0.5 to 12% by weight of sulfamic acid and 0.5 to 12% of a halide component in water to produce a first mixed liquid; adding 0.5 to 12% by weight of an ethylene glycol component and 0.5 to 12% of an organic acid component to the first mixed liquid to produce a second mixed liquid; After the second mixture was uniformly mixed, it was allowed to stand for at least 60 minutes to prepare the pickling liquid.

In one embodiment of the present invention, the glycol component may be selected from the group consisting of ethylene glycol 600, ethylene glycol 800, and ethylene glycol 1000.

In one embodiment of the invention, the glycolic component can be ethylene glycol 1000.

In one embodiment of the invention, the halide component may be selected from the group consisting of cuprous chloride, sodium chloride, potassium chloride, zinc chloride, and potassium iodide.

In one embodiment of the invention, the halide component can be potassium iodide.

In one embodiment of the present invention, the organic acid component may be selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid.

In an embodiment of the invention, the organic acid component is propionic acid.

In one embodiment of the present invention, the total weight percentage of the sulfamic acid component, the ethylene glycol component, the halide component, and the organic acid component may be 20 to 30%.

The above and other objects, features, and advantages of the present invention will become more apparent from Furthermore, the directional terms mentioned in the present invention, such as upper, lower, top, bottom, front, rear, left, right, inner, outer, side, surrounding, central, horizontal, horizontal, vertical, longitudinal, axial, Radial, uppermost or lowermost layer, etc., are only used in the reference embodiment to help explain the direction and relative relationship between objects. Therefore, the directional terminology used is for the purpose of illustration and understanding of the invention.

First, an acid washing liquid according to an embodiment of the present invention is exemplified by weight percentage May contain: 0.5 to 12% of sulfanilic acid (sulfanilic acid); 0.5 to 12% of ethylene glycol class; 0.5 to 12% of halide component; organic acid Acid class) 0.5 to 12%; and 100% by weight of water.

In one embodiment, the glycol component is selected from the group consisting of ethylene glycol (polyethylene glycol, PEG) 600, ethylene glycol 800, and ethylene glycol 1000, for example, preferably Ethylene glycol 1000 is used to simplify the composition of the material and achieve better reaction results, but not limited to this.

In one embodiment, the halide component is selected from the group consisting of cuprous chloride (CuCl), sodium chloride (NaCl), potassium chloride (KCl), zinc chloride (ZnCl ₂ ), and potassium iodide (KI). A group, for example, preferably potassium iodide, is used to simplify the composition of the material and achieve a better reaction effect, but not limited thereto.

In one embodiment, the organic acid component is selected from the group consisting of formic acid (HCOOH), acetic acid (CH ₃ COOH), propionic acid (CH ₃ CH ₂ COOH), butyric acid (CH ₃ CH ₂ CH ₂ -COOH), and oxalic acid ( A group consisting of H ₂ C ₂ O ₄ ), for example, preferably propionic acid, is used to simplify the composition of the material and achieve a better reaction effect, but not limited thereto.

In addition, the method for preparing the pickling liquid of the embodiment of the present invention may comprise the steps of: dissolving 0.5 to 12% by weight of sulfamic acid and 0.5 to 12% of a halide component in water to produce a first mixture. a liquid mixture; adding 0.5 to 12% by weight of an ethylene glycol component and 0.5 to 12% of an organic acid component to the first mixed liquid to produce a second mixed liquid; and the second mixed liquid After uniformly mixing, it was allowed to stand for at least 60 minutes to prepare the pickling liquid.

For example, a preparation environment of the pickling solution is exemplified by atmospheric pressure and room temperature of 25 degrees (° C.). First, the solid material in the above components can be dissolved in a pure water, for example, sulfamic acid, chloride Copper, sodium chloride, potassium chloride, zinc chloride, potassium iodide or the like to produce the first mixed liquid; then, the liquid material in the above components may be added to the first mixed liquid, for example, ethylene glycol 600, Ethylene glycol 800, ethylene glycol 1000, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, etc. to produce the second mixed liquid; then, the second mixed liquid may be uniformly mixed and allowed to stand for at least 60 minutes. To prepare the pickling solution, the following examples are given, but not limited thereto.

In one embodiment, the components in the pickling solution may be, for example, sulfamic acid 1%, ethylene glycol 1000%, potassium iodide 1%, propionic acid 1%, and water supplemented to 100% by weight. %. Thereby, the amount of raw material used can be reduced to further reduce the cost of cleaning.

In one embodiment, the components in the pickling solution may be, for example, 10% sulfamic acid, 10% ethylene glycol, 10% potassium iodide, 10% propionic acid, and 100% water added. %. Thereby, the concentration of the components participating in a descaling reaction can be increased for use in cleaning applications requiring enhanced descaling effects.

In one embodiment, the components in the pickling solution may be, for example, sulfamic acid in 1%, ethylene glycol 800 in 1%, cuprous chloride in 1%, acetic acid in 1%, and water in the supplement. To 100%. Thereby, the amount of raw material used can be reduced to further reduce the cost of cleaning.

In one embodiment, the components in the pickling solution may be, for example, sulfamic acid 10%, ethylene glycol 800%, copper chloride 10%, acetic acid 10%, and water supplemented. To 100%. Thereby, the concentration of the components participating in the descaling reaction can be increased for use in cleaning applications requiring enhanced descaling effects.

In one embodiment, the total weight percentage of the sulfamic acid, the ethylene glycol component, the halide component, and the organic acid component may be 20 to 30%, for example, the sulfamic acid, the ethylene glycol. The weight percentage of the component, the halide component and the organic acid component may be 6.25%, so as to prepare an acid washing liquid suitable for cleaning a metal material (such as a heat exchanger, etc.) at a suitable material cost. However, it is not limited to this.

In addition, the use of the pickling liquid of the embodiment of the present invention can be applied to cleaning a scale of a heat exchanger, such as: a scale applied to an ammonia distillation tray plate heat exchanger, the scale can include Ammonia nitrogen deposits, zinc oxides and calcium oxides, but not limited to this. It should be noted that if the plate heat exchanger contains a cast iron component, for example, a cast iron containing iron, carbon, barium, manganese, and a small amount of elements such as phosphorus and sulfur, the organic acid component of the acid pickling liquid. Formic acid should be avoided. For example, acetic acid, propionic acid, butyric acid or oxalic acid can be used to prevent formic acid from remaining on the surface of the cast iron. After heating, it will decompose to produce carbon monoxide toxic gas.

In an embodiment, the pH of the pickling solution may be between 1 and 3 during the cleaning of the scale of the ammonia distillation tray plate heat exchanger, for example, the freshly prepared acid washing liquid. The pH value (pH value) may be 1, and the acidity and alkali value of the acid pickling liquid may have a better effect of foaming property, and may be used for cleaning the ammonia distillation tray plate heat exchanger. The following is an example of the cleaning process. , but not limited to this.

For example, during the cleaning process, the pickling solution and the scale are mutually produced Chemical reaction, as the cleaning time increases, the acidity and alkalinity of the acid washing liquid will gradually increase. Since the hydrogen hydroxide ion of polyethylene glycol is gradually replaced by other ions, the foaming property of the acid washing liquid will gradually gradually Decrease, when the residual foaming property in the pickling liquid is insufficient for cleaning, if the pH value is increased to more than 3, the sulfamic acid or the acid washing liquid which has not been used for washing may be additionally added to make the sulfamic acid The weight percentage is restored to 0.5 to 12%, and the pH of the pickling solution is restored to between 1 and 3 to achieve an appropriate cleaning effect in the subsequent cleaning process.

For example, the above-mentioned pickling liquid can be used to clean the scale of the plate heat exchanger for a cleaning time (for example, 60 minutes) at a temperature of 80 degrees, in order to calculate the change of the heat transfer coefficient of the plate heat exchanger before and after the cleaning. The value is used as the basis for determining the cleaning effect and cleaning time, but not limited to this.

The pickling liquid of the above embodiment of the present invention contains polyethylene glycol and sulfamic acid, and can wash the knot containing ammonia nitrogen deposit, zinc oxide and calcium oxide by using hydrogen hydroxide ion and foaming property in the pickling liquid. The scale is removed from the ammonia distillation tray plate heat exchanger.

Therefore, the pickling liquid of the above embodiment of the present invention can surely remove scale containing ammonia nitrogen deposits, zinc oxides and calcium oxides, compared to conventional acid pickling liquids (for example, CN1030618C patent application, etc.). Directly used in industrial cleaning applications, for example, it can be directly used to clean the ammonia distillation tray heat exchanger required for a steel smelting process, in order to remove the scale of the ammonia distillation tray plate heat exchanger, Achieve improved cleaning results and high compatibility with existing processes.

In addition, the components of the pickling liquid of the above embodiment of the present invention are easy to obtain and regenerate, and the cleaning effect after regeneration is good. More importantly, the pickling liquid does not contain organic phosphoric acid, compared to conventional acid washing liquids (such as : CN102284247A patent application), it will not cause environmental pollutants containing organic phosphoric acid after cleaning, and can achieve the effects of avoiding increase of environmental load and reducing cost.

The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (22)

An acid washing liquid comprising, by weight percentage, 0.5 to 12% of sulfamic acid; 0.5 to 12% of ethylene glycol; 0.5 to 12% of halide; 0.5 to 12% of organic acid; and water to total The weight percentage is 100%. The pickling solution according to claim 1, wherein the glycol component is selected from the group consisting of ethylene glycol 600, ethylene glycol 800, and ethylene glycol 1000. The pickling solution according to claim 2, wherein the glycol component is ethylene glycol 1000. The pickling solution according to claim 1, wherein the halide component is selected from the group consisting of cuprous chloride, sodium chloride, potassium chloride, zinc chloride and potassium iodide. The pickling solution according to claim 4, wherein the halide component is potassium iodide. The pickling solution according to claim 1, wherein the organic acid component is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid and oxalic acid. The pickling solution according to claim 6, wherein the organic acid component is propionic acid. The pickling solution according to claim 1, wherein the total weight percentage of the sulfamic acid, the ethylene glycol component, the halide component and the organic acid component is 20 to 30%. A use of the pickling liquid according to any one of claims 1 to 8 for cleaning a scale of a heat exchanger. The use of the pickling liquid according to claim 9 wherein the heat exchanger is an ammonia distillation tray heat exchanger. The use of the pickling liquid according to claim 9, wherein the scale comprises ammonia nitrogen deposits, zinc oxides and calcium oxides. The use of the pickling liquid according to claim 9, wherein the pickling solution has a pH of between 1 and 3 during the cleaning of the scale of the ammonia distillation tray plate heat exchanger. The use of the pickling liquid according to claim 12, wherein the pickling liquid has a foaming property when the acid-base value is 1. The use of the pickling liquid according to claim 9, wherein in the process of cleaning the scale of the ammonia distillation tray plate heat exchanger, if the pH value of the pickling liquid is greater than 3, the additional addition is The sulfamic acid or an acid wash that has not been used for washing is such that the weight percentage of the sulfamic acid is restored to 0.5 to 12% and the pH of the acid wash is restored to between 1 and 3. A method for preparing an acid washing liquid, comprising the steps of: dissolving 0.5 to 12% by weight of sulfamic acid and 0.5 to 12% of a halide component in water to produce a first mixed liquid; Adding 0.5 to 12% by weight of the ethylene glycol component and 0.5 to 12% of the organic acid component to the liquid to produce a second mixed liquid; and uniformly mixing the second mixed liquid, and then allowing at least The pickling solution was prepared for 60 minutes. The method for preparing an acid washing liquid according to claim 15, wherein the ethylene glycol component is selected from the group consisting of ethylene glycol 600, ethylene glycol 800, and ethylene glycol 1000. The method for preparing an acid washing liquid according to claim 16, wherein the ethylene glycol component is ethylene glycol 1000. The method for preparing an acid washing solution according to claim 15, wherein the halide component is selected from the group consisting of cuprous chloride, sodium chloride, potassium chloride, zinc chloride and potassium iodide. The method for preparing an acid washing solution according to claim 18, wherein the halide component is potassium iodide. The method for preparing an acid washing solution according to claim 15, wherein the organic acid component is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid. The method for producing an acid washing solution according to claim 20, wherein the organic acid component is propionic acid. The method for preparing an acid washing solution according to claim 15, wherein the total weight of the sulfamic acid component, the ethylene glycol component, the halide component and the organic acid component is 20 to 30 %.