CN107162403A - A kind of composite anti-foaming agent produced suitable for ordinary plate glass - Google Patents

Abstract

The invention discloses a composite defoamer suitable for the production of ordinary flat glass, which mainly includes a main component and a solvent component, and the main component contains a foam breaker composed of a titanium compound, a foam wall thinner composed of sodium sulfate and calcium sulfate , and solvent combustion efficiency optimizer pentadiferron; the solvent component contains diesel oil, aviation kerosene, heavy oil or a mixture thereof in any proportion, the flash point of the solvent is ≥38°C, and the main component is dissolved in the solvent or suspended in the solvent in the state of solid particles. The composite defoamer of the present invention can achieve the effect of thinning the bubble wall by generating new small bubbles on the floating glass liquid bubble wall, and at the same time, promote the bubble rupture by reducing the local viscosity and surface tension of the bubble wall, so as to achieve no It is necessary to increase the maximum temperature of the ordinary flat glass furnace, so as to accelerate the rupture of the bubble layer on the surface of the glass liquid in different temperature ranges of the furnace, so as to improve the bubble removal efficiency of the glass liquid and reduce the influence of ordinary flat glass bubble defects.

Description

A Composite Defoamer Applicable to the Production of Ordinary Flat Glass

technical field

The invention belongs to the technical field of melting in the production process of ordinary flat glass, and more specifically relates to a composite defoamer suitable for the production of ordinary flat glass.

Background technique

In the production process of ordinary flat glass, due to the high temperature decomposition and melting of silica sand, sulfate, carbonate and other raw materials, a large amount of gas such as CO ₂ , SO ₂ , H ₂ O will be released, and a large number of bubbles will be formed in the molten glass. The bubble layer almost covers the non-ingredient coverage area in the ordinary flat glass furnace, and the thickness of the bubble layer is 10mm to 100mm. The existence of bubble defects in the molten glass seriously affects the pass rate of ordinary flat glass products and becomes an important factor affecting production efficiency.

Usually, in order to reduce the bubbles in the molten glass, the radius of the bubbles can be increased by adding a certain proportion of clarifying agent to the glass raw material. The principle is: the clarifying agent decomposes at high temperature to produce gases such as SO2, O2, etc. The gas generated by the decomposition is combined to increase the radius of the bubbles so that they can float to the liquid surface of the glass liquid; it is also possible to increase the temperature of the glass liquid and reduce the viscosity of the glass liquid (such as by heating) to promote the discharge of the bubbles in the glass liquid , At the same time, the rise of the temperature of the molten glass also reduces the surface tension of the molten glass and promotes the rupture of the foam layer floating on the surface of the molten glass.

However, although the use of clarifiers can increase the diameter of a large number of bubbles and float to the surface of the glass liquid, since the surface tension of the glass liquid itself does not change, except for a few bubbles with particularly large diameters, they will rupture after floating to the surface of the glass liquid. After the bubbles float to the surface of the glass liquid, they will gather together and stack up to form a foam layer. The existence of the foam layer prevents the floating efficiency of the bubbles in the glass liquid on the one hand, and on the other hand, it will form between the glass liquid and the burning flame on the upper part of the kiln. A layer of reflection and heat insulation affects the absorption of heat by the glass liquid. By continuously heating the glass liquid to promote the discharge and rupture of the bubbles, on the one hand, the existence of the foam layer will affect the heating efficiency; In order to ensure the bursting of all bubbles on the surface of the molten glass, the temperature of the molten glass must be heated to a very high level, which will consume a lot of energy. At the same time, the long-term ultra-high temperature will also affect the overall life of ordinary flat glass furnaces.

Contents of the invention

The technical problem to be solved by the present invention is to provide a composite defoamer suitable for the production of ordinary flat glass in view of the above-mentioned deficiencies in the prior art, which can thin the bubble wall and promote the bursting of the bubbles without increasing the temperature of the ordinary flat glass kiln. The highest temperature can improve the bubble removal efficiency of the glass liquid and reduce the influence of bubble defects in ordinary flat glass.

A composite defoamer suitable for the production of ordinary flat glass comprises a main component and a solvent component, and the main component includes a foam breaker titanium compound.

According to the above scheme, the main component also includes sodium sulfate and/or calcium sulfate as foam wall thinners.

According to the above solution, the main component also includes a solvent combustion efficiency optimizer pentadiferron.

Further preferably, the main component is composed of a foam breaker titanium-containing compound, a foam wall thinner sodium sulfate and/or calcium sulfate, and a solvent combustion efficiency optimizer pentaferric iron.

Furthermore, the mass percentage of the foam breaking agent in the main component of the composite defoamer is not less than 80%, preferably not less than 90%.

Furthermore, the mass percentage of the foam wall thinner in the main component of the composite defoamer is not higher than 10%, preferably not higher than 5%.

Furthermore, the mass percentage of the solvent combustion efficiency optimizer in the main component of the composite defoamer is not higher than 10%, preferably not higher than 5%.

According to the above scheme, the solvent component has a flash point ≥ 38° C., and its main component is dissolved in the solvent component or suspended in the solvent component in the state of solid particles. Preferably, the solvent component is a mixture of one or more of oils such as diesel oil, aviation kerosene, and heavy oil in any proportion.

According to the above scheme, the titanium-containing compound of the foam breaker is mainly one or more mixtures in any proportion of tetrabutyl titanate (C ₁₆ H ₃₆ O ₄ Ti), titanium dioxide, etc., and its main function can reduce The local surface tension of the small bubble wall accelerates the bubble breaking.

According to the above scheme, the described bubble wall thinning agent is mainly sodium sulfate and calcium sulfate, etc., which can mainly generate new small bubbles on the bubble walls to thin the bubble walls and make the bubbles easy to burst.

According to the above scheme, the solvent combustion efficiency optimizer is mainly ferrocene (Fe(C ₅ H ₅ ) ₂ ), its main function is to improve the combustion efficiency of the solvent component, and it can also optimize the main component of the defoamer and the solvent component The safety of use, and to ensure the requirements of Fe ₂ O ₃ ≤ 2000ppm for ordinary flat glass products.

According to the above scheme, the particle size of the powder raw material in the main component of the composite defoamer must satisfy a 100-mesh sieve, preferably a 130-mesh sieve.

The composite defoamer for the production of a common flat glass is characterized in that the ratio of the main component of the composite defoamer to the solvent component is only related to the chemical composition of the produced common flat glass product, but not to the heating method of the kiln. irrelevant;

According to the above scheme, the mass ratio of the main component of the composite defoamer to the solvent is 1:2-25, preferably 1:9-23.

The composite defoamer of the present invention is mainly suitable for ordinary flat glass products, its representative components and their mass percentages: SiO ₂ 70-73wt%, Al ₂ O ₃ 0.5-3wt%, CaO+MgO+BaO+ SrO _9-13wt %, Na2O ₊ K2O _{+ Li2O13-16wt} %, _{Fe2O3≤2000ppm} .

The composite defoamer of the present invention is suitable for the production of ordinary flat glass, its daily use amount is not higher than 0.15wt% of the glass daily melting amount, and its use temperature is not lower than 1200°C.

The main technical idea of the present invention: the present invention mainly aims at the characteristics of large production capacity, easy melting, and wide control of iron element of ordinary flat glass products compared with special glass, and develops a composite defoamer suitable for the production of ordinary flat glass. It can effectively eliminate the bubble layer floating on the surface of the furnace glass liquid during the melting process, and at the same time, it cannot have any adverse effects on the performance of ordinary flat glass products.

In the high temperature state of 1600°C or higher in the ordinary flat glass furnace, tetrabutyl titanate (C ₁₆ H ₃₆ O ₄ Ti) undergoes oxidative combustion reaction to form high-temperature TiO ₂ ultrafine particles (for example, the foam breaker directly uses titanium dioxide TiO ₂ is directly sprayed with the solvent, and TiO ₂ superfine particles are directly obtained) and fall on the bubble wall of the bubble layer in the kiln. Due to the high polarity of the Ti-O bond in TiO ₂ , the gaseous state in the high-temperature space in the kiln adsorbed on the surface Water dissociates and polarizes it, that is, H-OH dissociates into hydroxyl-OH, and the dissociated hydroxyl-OH enters the glass liquid forming the bubble wall, reducing the viscosity and surface tension of this area, and this corresponding To a certain extent, the bubbles will burst;

At the same time, in the process of forming ordinary flat glass, the bubble wall thinner sodium sulfate and calcium sulfate are sprayed into the bubble layer of the glass liquid, and under high temperature conditions, a decomposition reaction occurs on the bubble wall, and CaSO ₄ is decomposed into CaO, SO ₃ , O ₂ , Na ₂ SO ₄ is decomposed into Na ₂ O, SO ₃ , O ₂ , tiny traces of CaO and Na ₂ O enter into the molten glass, and have no effect on the performance of the glass product, while O ₂ and SO ₃ Many new small bubbles are generated on the glass liquid bubble wall to achieve the effect of thinning the bubble wall, so that the bubble wall becomes easy to break under the same conditions;

In addition, because the solvent in the composite defoamer of the present invention is a conventional fuel component, because pentaferrous iron can improve fuel combustion efficiency and reduce the amount of flue gas after combustion, a certain amount of pentaferrous iron is introduced in the defoamer, but At the same time, it is considered that pentaferrous iron eventually enters the molten glass in the form of iron oxide or ferrous oxide, which will have a certain impact on the transmittance index of ordinary flat glass products, but ordinary flat glass products with broad transmittance requirements, such as For anti-ultraviolet glass, architectural glass, automotive glass, etc., the amount of pentamethylene diferron can be appropriately increased; for ordinary flat glass used in photovoltaic cells, because of its high requirement for visible light transmittance, the Fe ₂ O in the product ₃ ≤150ppm, it is necessary to strictly control the introduction of pentaferric iron.

Through the above principles, the present invention has developed a composite defoamer suitable for the production of ordinary flat glass, which can accelerate the formation of the bubble layer on the surface of the glass liquid in different temperature regions of the kiln without raising the maximum temperature of the ordinary flat glass production kiln. Cracking, the foam layer is basically eliminated, and the qualified rate of ordinary flat glass production is significantly improved.

Compared with prior art, the beneficial effect of the present invention is:

First, the present invention develops a compound defoamer that can promote the rupture of the bubble layer on the surface of the glass liquid during the production process of ordinary flat glass, and thins the bubbles by generating new small bubbles on the bubble wall of the floating glass liquid At the same time, by reducing the local viscosity and surface tension of the bubble wall, it can promote the collapse of the bubbles, so as to achieve the need not to increase the maximum temperature of the ordinary flat glass furnace, but to accelerate the rupture of the bubble layer on the surface of the glass liquid in different temperature regions of the furnace. , so as to improve the bubble removal efficiency of the glass liquid and reduce the impact of bubble defects in ordinary flat glass.

Second, the chemical composition introduced by the composite defoamer of the present invention will not have any adverse effects on the physical and chemical properties of ordinary flat glass products, and the furnace heating methods (such as pure electric boost heating, electric boost and pure oxygen Composite heating, pure oxygen heating, air fluxing heating, oxygen-enriched combustion-supporting heating) have little impact on the production of ordinary flat glass products.

Description of drawings

Fig. 1 is a schematic diagram of a melting device for ordinary flat glass, in which, 1-melting furnace, 2-platinum bowl, 3-glass melting sample, 4-supporting table for melting sample bowl, 5-composite defoamer injection pipe, 6- Electric heating rod.

Figure 2 is a reference standard sample with poor bubbles in the molten sample of ordinary flat glass.

Figure 3 is a reference standard sample with medium bubbles in the molten sample of ordinary flat glass.

Figure 4 is a reference standard sample with good bubbles in the molten sample of ordinary flat glass.

detailed description

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the present invention is not limited to the following examples.

In the following examples, the common flat glass chemical composition used is the main component: SiO ₂ 72.0wt%, Al ₂ O ₃ 1.0wt%, CaO 8.5wt%, MgO 3.8wt%, Na ₂ O 13.5wt%, K ₂ O 0.5wt%, Fe ₂ O ₃ 1000ppm. Because the mixed heavy oil needs to be heated to reduce its viscosity and increase its fluidity, and the pipeline needs to be treated at the same time, so the solvent component used in the embodiment uses aviation kerosene as a representative example.

Examples 1-28

A composite defoamer suitable for the production of ordinary flat glass, including main components and solvent components, each specific composition and defoaming effect, the initial temperature and target temperature point in the temperature process system of the melting sample are shown in Table 1 Show.

In order to confirm the influence of the composite defoaming agent of the present invention on the defoaming effect of ordinary flat glass, for different common flat glass melting samples under the same formula, the composite foaming agent of each embodiment is injected slowly and continuously in a small amount under the same conditions In the special melting furnace, after the same cooling process, the temperature is lowered to room temperature, and the residual bubbles at the end of the melting sample are observed. The specific process is as follows:

(1) The raw material types and dosage of ordinary flat glass are: 300 grams of ordinary silica sand, 3.6 grams of feldspar powder, 93.0 grams of soda ash, 18.2 grams of limestone powder, 79.4 grams of dolomite powder, 4.8 grams of Glauber's salt; 0.14 grams of carbon powder; composite defoamer Usage amount is 750 milligrams (0.15wt% adopting raw material weight);

(2) The temperature process system of the melting sample is as follows: the first step, the melting furnace is raised to 1200°C, and the spare raw materials described in step (1) are put in at this temperature; The heating rate is heated to the initial temperature point of 1300 °C; the third step is to spray 350 mg of composite defoamer with air after reaching 1300 °C; the fourth step is to continue to increase the temperature at a rate of 100 °C/hour Warm up to the target temperature point, atomize the remaining 250 mg of compound defoamer with air, and then pass it in, and keep it warm for half an hour; step 5, cool down to 1300°C at a cooling rate of 100°C/hour; step 6, reach 1300°C After that, continue to cool down to room temperature rapidly, and the cooling speed is the fastest speed without damaging the equipment; the seventh step, after cooling to room temperature, take out the sample, observe the bubbles in the sample, and compare it with the reference standard sample described in Figure 2-4 Compare to determine the defoaming effect.

Table 1

By above-mentioned embodiment and table 1 data as can be known:

First of all, using the composite defoamer of the present invention can achieve better defoaming effect for ordinary flat glass production. Among them, when the mass ratio of the foam breaker in the composite defoamer is 98% of the main component, and the mass ratio of the foam wall thinner to the foam breaker is 2%, the target temperature for defoaming can be reduced by 5°C.

Moreover, in the composite defoamer suitable for the production of ordinary flat glass according to the present invention, for the main component, the larger the proportion of the defoamer, the better the defoaming effect. As shown by the above data, the defoamer When the proportion of the main component of the agent n-butyl titanate and titanium oxide is reduced from 100% to 91%, the overall trend of the defoaming effect is relatively worse; Under the condition that the component ratio is greater than 94%, the mass ratio of the main component and the solvent component in the composite defoamer has no obvious influence on the defoaming effect; , the larger the mass ratio of the main component to the solvent component, the better the defoaming effect. In particular, when the mass ratio of the main component to the solvent component is 1:5 or 1:10, even if the defoamer is reduced to 91%, a moderate degree of defoaming effect can be obtained, and a moderate degree of defoaming effect is not suitable for the actual large Scale production is also acceptable.

In addition, the mass ratio of the foam wall thinner calcium sulfate and sodium sulfate in the main component of the composite defoamer is not higher than 5%, which can fully optimize the defoaming effect; continue to increase its mass ratio in the main component, it will reduce The mass ratio of the foam breaker in the main component, so the defoaming effect tends to decrease. In the composite defoamer, pentamethylenediferron, which promotes the combustion efficiency of the solvent, has no obvious promotion effect on the defoaming effect, and the increase of its mass ratio will cause the mass of the defoamer and the foam wall thinner in the main component of the defoamer to increase. The reduction of the ratio will affect the defoaming effect; in the actual production of ordinary flat glass, considering the large amount of solvent used in the composite defoamer, the combustion efficiency is also a factor affecting the defoaming effect, so the transmittance of the glass Ordinary flat glass for buildings, ordinary flat glass for automobiles, and ordinary anti-ultraviolet ordinary flat glass with relatively loose color requirements will still introduce a certain proportion of pentamethylene diferron; while ordinary ultra-white ordinary flat glass with strict requirements on glass transmittance and color For flat glass (Fe ₂ O ₃ ≤150ppm), the introduction of pentamethylene diferron is strictly controlled.

Practical application: For the actual production of ordinary flat glass, as long as the defoaming effect of using a compound defoamer is better than that of not using a compound defoamer, it is an effective combination. Based on the above data, trial production was carried out in a company's 800 tons/day non-reversing kiln ordinary flat glass float production line. The composition of the agent and the defoaming effect are shown in Table 2. It can be seen that the average number of bubbles in this production line before using the composite defoamer is 1200/hour. After the compound defoamer is introduced, the number of bubbles is reduced to an average of 500/hour. , the effect is obvious.

Table 2

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the creative concept of the present invention, some improvements and changes can also be made, and these all belong to the present invention scope of protection.

Claims (10)

1. a kind of composite anti-foaming agent produced suitable for ordinary plate glass, including bulk composition and solvent composition, its feature exist The mass percent for including foamicide in foamicide titanium-containing compound, bulk composition in the bulk composition is not less than 80%.

2. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute State the quality hundred for also including steep that wall reducer in steep that wall reducer sodium sulphate and/or calcium sulfate, bulk composition in bulk composition Divide ratio not higher than 10%.

3. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute State and also include the matter that solvent efficiency of combustion in the solvent efficiency of combustion optimization iron of agent penta 2, bulk composition optimizes agent in bulk composition Amount percentage is not higher than 10%.

4. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute State flash-point >=38 DEG C of solvent composition, bulk composition be dissolved in solvent composition or with solid particle state be suspended in solvent composition it In.

5. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute It is one or more of mixtures in any proportion in diesel oil, aviation kerosine, heavy oil to state solvent composition.

6. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute The foamicide titanium-containing compound stated is mainly the fourth fat of metatitanic acid four and/or titanium dioxide.

7. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute The powder material in the bulk composition of composite anti-foaming agent is stated, its particle diameter is no more than 100 mesh.

8. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute The mass ratio for stating bulk composition and solvent composition is 1:2-23.

9. a kind of composite anti-foaming agent produced suitable for ordinary plate glass according to claim 1, it is characterised in that institute The representative component and its weight/mass percentage composition for stating ordinary plate glass be：SiO2 70-73wt%, Al2O3 0.5-3wt%, CaO+MgO+BaO+SrO 9-13wt%, Na2O+K2O+Li2O 13-16wt%, Fe2O3≤2000ppm.

10. a kind of application method of composite anti-foaming agent produced suitable for ordinary plate glass described in claim 1, its feature When being the composite anti-foaming agent and being used for ordinary plate glass and produce, day usage amount be not higher than glass day fusing amount 0.15wt%, temperature in use is not less than 1200 DEG C.