[0001] This application claims the benefit of the United States Patent Application

Serial No. 61/933,999 filed January 31, 2014, entitled METHOD AND COMPOSITION FOR REDUCING SILICA BASED EVAPORATOR SCALING, which application is hereby incorporated by reference herein in its entirety.

BACKGROUND

[0002] Silica based minerals are present to some degree in all fibrous raw materials used for making paper pulp. A portion of the silica is on the surface of the raw materials as soil particles and a portion is occluded within and among the plant cells. During the cooking process the minerals become fluid borne silicates. For the raw materials containing large amounts of silica, scaling of equipment for use in processing pulping compositions or compositions associated with pulping (e.g. black liquor) can be problematic since the silicates tend to form scale. For equipment having large surface areas such as heat exchangers (especially evaporator tubing and liquor heaters), silicate scaling is economically

troublesome.

[0003] Without intention to be bound to a particular theory, not all types of silica can cause a scaling problem. The type of silica that may contribute the most to the scaling problem is known as reactive silica or colloidal silica. The reactive silica is soluble in solution and may react with hot surfaces and other silica particles. In North America, where the reactive silica is present in very small amounts, evaporators typically may operate for six months to a year between cleaning. While in India where the reactive silica exists in more significant amounts, the evaporators may operate only a few days without cleaning. Thus, there is a need to reduce the amount of scaling in further processes of the pulping

composition or compositions associated with pulping (e.g. black liquor), and to extend the cleaning interval of the corresponding equipment. DETAILED DESCRIPTION

[0004] Features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating the preferred embodiments of the present invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description.

[0005] One aspect of the invention relates to a method for reducing the concentration of reactive silica in a first composition comprising adding a first amount of a calcium salt and a second amount of a magnesium salt to the first composition to form a solid silicate composition comprising one or more silicates, wherein:

the first composition comprises an aqueous solution; and a significant portion of the reactive silica in the first composition is converted to one or more silicate in the solid silicate composition.

[0006] As used herein, "a significant portion" of a component in composition is at least about 25% of the total amount of the component in the composition, at least about 35% of the total amount of the component in the composition, at least about 45% of the total amount of the component in the composition, at least about 50% of the total amount of the component in the composition, at least about 75% of the total amount of the component in the composition, at least about 90% of the total amount of the component in the composition, at least about 95% of the total amount of the component in the composition, at least about 98% of the total amount of the component in the composition, or at least about 99% of the total amount of the component in the composition.

[0007] In certain embodiments, the calcium salt is a soluble calcium salt, e.g. calcium acetate, calcium nitrate, calcium chloride, calcium chlorate, calcium bromide, calcium bromate, and calcium iodide. In certain embodiments, the magnesium salt is a soluble magnesium salt, e.g. magnesium acetate, magnesium bromide, magnesium chlorate, magnesium chloride, magnesium iodide, magnesium sulfate, and magnesium thiosulfate. [0008] In certain embodiments, the molar ratio of the first amount to the second amount is 1 : 1, which is the stoichiometric ratios of calcium ion and magnesium ion in the mineral diopside, MgCaSi ₂ O ₆ . In certain embodiments, the first amount and the second amount are small such that the added calcium salt and the added magnesium salt will not cause significant scaling in later processes.

[0009] MgCaSi ₂ CO ₆ is insoluble in aqueous solutions. In certain embodiments, the diopside crystals act as seed crystals. Once established, silicate will continue to precipitate from the diopside crystals, and deplete the concentration of reactive silicates in the composition to be treated and reduce scaling in equipment used in later processes (e.g., evaporators). In certain embodiments, the amounts of calcium salt and magnesium salt added to the composition to be treated are too small to cause a scaling problem by themselves. In certain embodiments, a significant portion of the calcium ions and magnesium ions added are precipitated as one or more silicates of the solid silicate composition (e.g., MgCaSi ₂ O ₆ ).

[0010] In certain embodiments, the first composition is a pulping composition or a composition associated with pulping (e.g. black liquor), the seed crystals and silicates precipitated therefrom may follow the pulp or remain as unreactive silica in the liquor.

Alternatively, the seed crystals and silicates precipitated therefrom can be cleaned from the pulp by any means (e.g., any conventional means) or can be left on the fiber.

[0011] By precipitating the reactive silica in the solution, the tendency of the solution to form scale in later processes (e.g., evaporation) is reduced because the reactive silicates are precipitated to unreactive silicates. Thus, the method disclosed herein can significantly reduce silica scaling of the first composition in later processes (e.g., evaporation) after treated with said method disclosed herein.

[0012] In certain embodiments, the method further comprises removing a significant portion of the solid silicate composition comprising one or more reactive silicates. The term "a significant portion" is defined the same as set forth supra. The method may also include determining the amount of reactive silicates in the composition to be treated to determine the proper amount of, e.g., calcium salt and magnesium salt to be added.

[0013] Another aspect of the invention relates to a composition or additive for performing the method disclosed herein. One skilled in the art will appreciate that the composition or additive can include a first amount of a calcium salt (e.g. calcium chloride) and a second amount of a magnesium salt (e.g. magnesium chloride) as set forth herein and sufficient to cause the formation of a solid silicate composition when added to a pulp composition or a composition associated to pulping (e.g. a black liquor) and thereby reduce or prevent equipment fouling due to scaling when processing such compositions.

[0014] In certain embodiments, the composition or additive can further comprise one or more chemicals for using in the pulping process such as anthraquinone (AQ). In other embodiments other additives may be included in the composition to aid in dispersion by providing a more uniform and better mixed solution that will react better with the calcium and magnesium ions. Such additives include one or more of surfactants (including anionic, cationic, carboxylates, nonionic, zwitterionic, fluorosurfactant, siloxane), biosurfactants, plasticizers, superplasticizers (e.g., polycarboxylate), defloculatants, polymeric dispersants, polyacrylates, polymethacrylate.

EXAMPLES Example 1

[0015] CaCl ₂ and MgCl ₂ can be added to a black liquor, wherein the molar ratio of

CaCl ₂ :MgCl ₂ is 1 : 1, and a solid silicate composition can be formed from the black liquor. At least 50% of the reactive silica in the black liquor can be removed from the black liquor when it is converted to one or more silicates of the solid silicate composition. The black liquor treated with the method described herein will cause much less scaling compared to the black liquor not treated with the method. The iime-interval between cleaning for equipment used in later processes of the black liquor is increased significantly, e.g., about a few days more.

[00161 Although the invention has been described with respect to specific embodiments and examples, it will be readily appreciated by those skilled in the art that modifications and adaptations of the invention are possible without deviation from the spirit and scope of the invention. Accordingly, the scope of the present invention is limited only by the following claims.