A kind of purifying firmware and the method for long-term maintenance of boiler water impurity concentration using the purifying firmware

Abstract

The application discloses a kind of purification firmware and the method for long-acting maintenance of water impurity concentration of furnace using the purification firmware, the purification firmware includes impurity replacement, high-temperature binder, room temperature binder;The impurity replacement is one of Na glass, K glass, Na3PO4, K3PO4, Na2HPO4, K2HPO4, Na5P3O 10 , K5P3O 10 , Na2H2P2O7, Na4P2O7, K2H2P2O7, K4P2O7, Na3P3O9, K3P3O9 Or mixture of two or more above. The application also discloses the preparation method and use method of the above-mentioned purification firmware. Using the application can continuously replace the Na, K impurity content in furnace water during the glass product hardening process, stabilize the surface stress of glass, enhance the strength of glass, so as to maintain the impurity content concentration in furnace water, avoid the adverse effects such as glass surface stress fluctuation, frequent replacement of furnace water.

Description

Technical Field

[0001] The present invention relates to the technical field of glass production and manufacturing, and in particular to a purification fixture and a method for maintaining the impurity concentration of boiler water in a long term by using the purification fixture. Background Art

[0002] When existing glass is strengthened, the Na and Li in the glass are replaced by K and Na in the boiler water, which increases the Na and Li content in the boiler water. As the concentration of Na and Li ions in the boiler water continues to increase, the surface stress of the strengthened glass continues to decrease, and the strength of the glass will also continue to decrease. When the surface stress of the strengthened glass is lower than the specification requirements, it is necessary to change the boiler water or add additives to reduce the impurity content. Changing the boiler water not only has low operational efficiency, but also has low boiler water utilization efficiency. The radius of Li ions is small, and their impurity concentration has a very significant impact on the surface stress and strength of the glass. Generally, replacement powder is added to the boiler water to replace the Li ions in the boiler water. Na impurities have little effect on the surface stress of the glass, so the boiler water has a long life, and the boiler water is directly replaced when the life is up.

[0003] The technical defects of adding replacement powder to replace Li ions in boiler water are as follows:

[0004] 1. NaLi2PO4 precipitation is generated during the powder replacement process. If the precipitation is incomplete, it will cause defects such as blue, foggy, and white spots on the glass;

[0005] 2. After adding powder for a maximum of 2 times, the sediment will completely cover the heating tube, causing abnormal furnace temperature and inability to produce.

[0006] 3. If the amount of powder added is too small, the Li content is too high, and the life of the boiler after water renewal is shortened. If powder is added a second time, the same waiting time will be required again.

[0007] 4. Too much powder is added, the Li content is low, and Li salt needs to be added. In addition, the newly generated Li during the hardening process will precipitate with the excess powder, causing defects such as blue, hazy, and white spots in the glass. Summary of the Invention

[0008] An object of the present invention is to provide a purification firmware.

[0009] To achieve the above-mentioned purpose, the present invention adopts the following scheme:

[0010] A purification firmware comprising the following components by mass percentage:

[0011] Impurity replacement 10-100%;

[0012] High temperature adhesive 0-80%;

[0013] Room temperature binder 0-30%;

[0014] The sum of the above components is 100%, and each component is not 0;

[0015] The impurity displacer is one or a mixture of two or more of Na glass, K glass, Na3PO4, K3PO4, Na2HPO4, K2HPO4, Na5P3O 10 , K5P3O 10 , Na2H2P2O7, Na4P2O7, K2H2P2O7, K4P2O7, Na3P3O9, and K3P3O9.

[0016] Preferably, the high-temperature binder includes one or a mixture of glass, metal, clay, and inorganic oxide.

[0017] Preferably, the purification solid further includes a pore-forming agent, and the pore-forming agent includes one of ammonium carbonate, ammonium bicarbonate, ammonium chloride, coal powder, carbon powder, natural fiber, high-molecular polymer, and organic acid.

[0018] Preferably, the room-temperature binder includes one or a mixture of polyvinyl alcohol, methyl cellulose, ethyl cellulose, cellulose acetate, 2-hydroxyethyl cellulose, triacetate cellulose, cellulose acetate butyrate, and starch.

[0019] Another object of the present application is to provide a preparation method of the above-mentioned purification solid, which specifically includes:

[0020] (1) pressing the impurity displacer, the high-temperature binder, and the room-temperature binder into a green body with a certain shape and structure according to a certain proportion;

[0021] (2) sintering the pressed green body.

[0022] Preferably, the pressure in the step (1) is 0.5-1 MPa.

[0023] The sintering temperature in the step (2) is 700-800 degrees.

[0024] The present application also provides a method for long-term maintenance of the impurity concentration in the boiler water by using the above-mentioned purification solid, which includes:

[0025] (1) pressing the impurity displacer, the high-temperature binder, and the room-temperature binder into a green body with a certain shape and structure according to a certain proportion;

[0026] (2) sintering the pressed green body to obtain a sintered body.

[0027] (3) The present application also provides a method for long-term maintenance of the impurity concentration in the boiler water by using the above-mentioned purification solid, which includes:

[0028] The sintered body prepared above is fixed on a hardened frame and immersed in furnace water together with the glass product.

[0029] Furthermore, it also includes real-time monitoring and detection of the concentration of lithium ions in boiler water.

[0030] Furthermore, the monitoring and detection methods include using atomic absorption spectroscopy and inductively coupled plasma spectrometry.

[0031] The present invention uses impurity replacement materials, high-temperature adhesives, room-temperature adhesives, etc. to make purification fixtures, and places the purification fixtures together with the glass hardening frame and the glass in high-temperature molten salt, so that ions in the purification solidification structure exchange with impurity ions in the high-temperature molten salt, thereby reducing the impurity concentration in the high-temperature molten salt. In this way, the Na and K impurity contents can be continuously replaced directly during the hardening process of the glass product, thereby maintaining the impurity content concentration in the furnace water, avoiding adverse effects such as surface stress fluctuation, sedimentation, and furnace water replacement, and stabilizing the surface stress and strength of the glass. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with specific embodiments.

[0033] First, the present invention provides a purification firmware, which includes the following components by mass percentage:

[0034] Impurity replacement 10-100%;

[0035] High temperature adhesive 0-80%;

[0036] Pore ​​forming agent (optional) 0-30%;

[0037] Room temperature binder 0-30%;

[0038] The sum of the above components is 100%, and each component is not 0;

[0039] Impurity replacement materials are raw materials that can replace impurity ions in high-temperature molten salts. Specifically, impurity replacement materials are Na glass, K glass, Na3PO4, K3PO4, Na2HPO4, K2HPO4, Na5P3O 10 、K5P3O 10 , Na2H2P2O7, Na4P2O7, K2H2P2O7, K4P2O7, Na3P3O9, K3P3O9, or a mixture of two or more. The replacement of ions with larger radii by monovalent ions with smaller radii offsets the squeezing effect on the glass surface, thereby reducing the surface stress and, consequently, the strength of the glass. Therefore, the impurity replacement agent is generally a monovalent metal salt with a larger radius than the impurity ions in the high-temperature molten salt, and the molar concentration of the impurities in the impurity replacement agent is lower than the molar concentration of the impurities in the high-temperature molten salt.

[0040] The purification solid in the present application can be dense or porous, and the porous structure is more conducive to the exchange speed of the impurity displacer and the impurity ions in the high-temperature molten salt, and is conducive to reducing the impurity ion exchange time of the impurity displacer.

[0041] The high-temperature binder is a raw material that can bind the impurity displacer together to maintain a certain shape and strength during the high-temperature molten salt hardening process, including but not limited to glass, metal, clay, metal oxide, inorganic oxide and mixture, etc. High-temperature resistant materials, including but not limited to powder, paste, aqueous solution of compounds, organic solution of compounds or mixture, etc. These raw materials can soften or react under conditions not lower than the temperature of the high-temperature molten salt, thereby binding the impurity displacer together.

[0042] The pore-forming agent is capable of having abundant pores after the impurity displacer and the high-temperature binder are bonded together at high temperature, which is conducive to effective contact of the high-temperature molten salt with the impurity displacer and improves the displacement speed and reduces the displacement time. It is divided into inorganic and organic categories. The inorganic category includes but is not limited to high-temperature decomposable salts such as ammonium carbonate, ammonium bicarbonate, and ammonium chloride, as well as coal powder and carbon powder. The organic category includes but is not limited to natural fibers, high-molecular polymers, and organic acids. In addition to the composition of the pore-forming agent, the morphology of the pore-forming agent, especially the particle size distribution, also affects the pore-forming characteristics.

[0043] The room-temperature binder is a raw material that can maintain the shape and strength of the impurity displacer, high-temperature binder, and pore-forming agent during molding at room temperature. It includes but is not limited to PVA (polyvinyl alcohol), methyl cellulose, ethyl cellulose, cellulose acetate, 2-hydroxyethyl cellulose, triacetate, cellulose acetate butyrate, starch, etc.

[0044] Some substances can be used as both high-temperature binders and impurity displacers, such as high-Na-content glass, which can be used as both a high-temperature binder and a Li impurity displacer.

[0045] The precipitate NaLi2PO4 generated during the powder displacement process is slow and has very small particles, resulting in a settling time of 24 hours.

[0046] The present application uses a binder such as glass to sinter with a Li displacer such as powder into a Li displacer sintered body, and exchanges Na with Li in the glass waste, avoiding the defect that NaLi2PO4 settles slowly and may not settle completely. Therefore, the Na and K impurity content can be continuously replaced during the hardening process of the glass product, thereby maintaining the impurity content concentration in the furnace water, avoiding the adverse effects of surface stress fluctuations, settling, and changing the furnace water, and stabilizing the surface stress and strength of the glass.

[0047] The specific implementation steps are as follows:

[0048] The high-temperature binder, impurity replacement material, and room-temperature binder are pressed into a blank of a certain shape and structure. The shape includes but is not limited to rectangular, circular, spindle, ring, and other shapes with or without holes. The bonding material includes but is not limited to glass, metal, metal oxide, inorganic oxide, and mixtures of high-temperature resistant binders. The Li replacement material includes but is not limited to Na-containing glass, K glass, Na3PO4, K3PO4, Na2HPO4, K2HPO4, Na5P3O 10 、K5P3O 10 , Na2H2P2O7, Na4P2O7, K2H2P2O7, K4P2O7, Na3P3O9, K3P3O9 or a mixture thereof. Room temperature binders include but are not limited to PVA, methyl cellulose, ethyl cellulose, cellulose acetate, 2-hydroxyethyl cellulose, cellulose triacetate, cellulose acetate butyrate, etc.

[0049] The green body is sintered into an object of a certain shape and structure, including but not limited to dense or porous structures. When the additives are relatively low and the particle size of the high-temperature binder and impurity replacement material during pressing is relatively small, a dense or low-porosity sintered body can be obtained.

[0050] A certain amount of sintered body is placed in the hardening furnace water along with the hardened glass. Because different glass formulations are different, the weight of the sintered body needs to be controlled to maintain the furnace water at an appropriate Li concentration.

[0051] When the sintered body is replaced to a certain extent, it is necessary to replace it with a new sintered body.

[0052] The life of the sintered body can be detected by a rapid method to test the Li, Na or potassium content in the sintered body.

[0053] Example 1

[0054] 1. Mix 1000 g of Na glass powder and 50 g of PVA together and press them into a 200 g donut-shaped green body at a pressure of 0.5 MPa.

[0055] 2. Sinter the pressed green body at 700-800 degrees to form a Li-substituted sintered body with a certain mechanical strength;

[0056] 3. Place the Li-substituted sintered ring on a glass hardened rack and immerse it in 3kg of furnace water along with the glass product. This can significantly offset the concentration of replaced Li ions in the glass product.

[0057] Without the Li-substituent sintering rings attached to the glass hardening rack, the Li ion concentration in the furnace water increased from 0 to 25 ppm after a batch of glass hardening was completed. With the Li-substituent sintering rings attached, the Li ion concentration increased from 0 to 15 ppm. The glass surface stress remained at 620 MPa, and the 4PB strength of the glass remained at 650 MPa.

[0058] Example 2

[0059] 1. Mix 50g of powder and 50g of glass powder together, then add 0.5g of PVA as an additive and press into a donut-shaped green body at a pressure of 0.5MPa.

[0060] 2. Sinter the pressed green body at 700-800 degrees to form a Li-substituted sintered body with a certain mechanical strength;

[0061] 3. The Li-substituted sintered ring was placed on a glass hardened rack and immersed in 3 kg of furnace water along with the glass product. It was found that the concentration of replaced Li ions in the glass product could be significantly offset.

[0062] Without the Li-substituent sintering rings attached to the glass hardening rack, the Li ion concentration in the furnace water increased from 0 to 25 ppm after a batch of glass hardening was completed. With the Li-substituent sintering rings attached, the Li ion concentration increased from 0 to 9 ppm. The glass surface stress remained at 650 MPa, and the 4PB strength of the glass remained at 700 MPa.

[0063] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A purification firmware, characterized in that: The following components are used in percentage by mass composition: Impurity replacement 10-100%; High temperature adhesive 0-80%; Room temperature adhesive 0-30%; Pore ​​forming agent 0-30%; And the content of each component is not 0; The impurity replacement materials are Na glass, K glass, Na3PO4, K3PO4, Na2HPO4, K2HPO4, Na5P3O 10 、K5P3O 10 , Na2H2P2O7, Na4P2O7, K2H2P2O7, K4P2O7, Na3P3O9, K3P3O9 or a mixture of two or more thereof; the pore-forming agent includes one of ammonium carbonate, ammonium bicarbonate, ammonium chloride, coal powder, carbon powder, natural fiber, high molecular polymer and organic acid; the purification firmware is a sintered body obtained by sintering a blank of a certain shape and structure pressed into a shape by impurity replacement, high-temperature binder, room-temperature binder and pore-forming agent; the high-temperature binder includes one of glass, metal, clay and inorganic oxide or a mixture thereof, the high-temperature binder can soften or react under the condition of not lower than the temperature of high-temperature molten salt to bond the impurity replacement together, and the high-temperature molten salt is a high-temperature molten salt for hardening glass.

2. The purification device according to claim 1, wherein: The room temperature binder includes one or a mixture of polyvinyl alcohol, methyl cellulose, ethyl cellulose, cellulose acetate, 2-hydroxyethyl cellulose, cellulose triacetate, cellulose acetate butyrate, and starch.

3. A method for preparing the purification firmware according to any one of claims 1-2, characterized in that: The following steps are involved: (1) Pressing the impurity replacement material, high temperature binder, room temperature binder, and pore-forming agent into a green body with a certain shape and structure; (2) The pressed green body is sintered to obtain a sintered body.

4. The method according to claim 3, wherein: The pressure of the pressing molding in step (2) is 0.5-1MPa.

5. The method according to claim 3, wherein: The sintering temperature in step (2) is 700-800 degrees.

6. A method for maintaining the impurity concentration of boiler water for a long time using purification hardware, characterized in that: include: The sintered body obtained by the method according to any one of claims 3 to 5 is fixed on a hardened frame and immersed in furnace water together with the glass product.

7. A method for maintaining the impurity concentration of boiler water using purification hardware for a long term according to claim 6, characterized in that: It also includes real-time monitoring and detection of lithium ion concentration in boiler water.

8. The method for maintaining the impurity concentration of boiler water using purification hardware for a long term according to claim 7, characterized in that: The monitoring and detection include using an atomic absorption spectrometer and an inductively coupled plasma spectrometer.