阅读说明：本技术 一种复合消泡剂及其在生产瓶罐器皿玻璃中的应用 (Composite defoaming agent and application thereof in production of bottle ware glass ) 是由 谢俊 陈发伟 韩建军 阮健 于 2017-05-23 设计创作，主要内容包括：本发明公开了一种复合消泡剂及其在生产瓶罐器皿玻璃中的应用。具体地说,所述复合消泡剂包括主体成分和溶剂成分,所述主体成分包括破泡剂和泡壁减薄剂。本发明还公开了一种使用所述复合消泡剂生产瓶罐器皿玻璃的方法以及所述复合消泡剂在生产瓶罐器皿玻璃中的应用。本发明的所述复合消泡剂通过施用在漂浮的玻璃液气泡壁上的泡壁减薄剂产生新的小气泡以达到减薄气泡壁的作用,同时通过减小气泡壁局部粘度和表面张力,促进气泡破裂,以达到不需要提高瓶罐器皿窑炉的最高温度,而能够加速窑炉不同温度区域内玻璃液表面气泡层的破裂,以此提高玻璃液的排泡效率,减少瓶罐器皿玻璃气泡缺陷的影响。(The invention discloses a composite defoaming agent and application thereof in producing glass of bottle and jar vessels. Specifically, the composite defoaming agent comprises a main component and a solvent component, wherein the main component comprises a defoaming agent and a foam wall thinning agent. The invention also discloses a method for producing the bottle and can ware glass by using the composite defoaming agent and application of the composite defoaming agent in producing the bottle and can ware glass. The composite defoaming agent provided by the invention generates new small bubbles by using the bubble wall thinning agent applied to the floating glass liquid bubble wall to thin the bubble wall, and simultaneously promotes bubble breakage by reducing the local viscosity and surface tension of the bubble wall so as to achieve the purpose of accelerating the breakage of a glass liquid surface bubble layer in different temperature areas of a kiln without increasing the highest temperature of a bottle ware kiln, thereby improving the bubble discharging efficiency of glass liquid and reducing the influence of the glass bubble defects of the bottle ware.)

1. A composite defoaming agent comprises a main component and a solvent component, and is characterized in that:

the main component comprises a foam breaker and a foam wall thinning agent.

2. The composite defoamer as set forth in claim 1, wherein:

the flash point of the solvent component is more than or equal to 38 ℃; preferably, the solvent component is one or a mixture of several of diesel oil, aviation kerosene and heavy oil according to any proportion;

the foam breaker is a titanium-containing compound; preferably, the foam breaker is tetrabutyl titanate and/or titanium dioxide; and/or

The bubble wall thinning agent is sodium nitrate and/or potassium nitrate; more preferably, the ratio of the sodium nitrate in the cell wall thinning agent is not less than 90% by mass.

3. The composite defoamer as claimed in claim 1 or 2, wherein:

the main component also comprises a solvent combustion efficiency optimizing agent; preferably, the solvent combustion efficiency optimizing agent is iron glutarate; more preferably, the mass percentage of the solvent combustion efficiency improver in the main component is not higher than 3%.

4. The composite defoamer as claimed in any one of claims 1 to 3, wherein:

the mass ratio of the main component to the solvent component is 1:2-23, and more preferably 1: 9-18;

the mass percentage of the foam breaker in the main component is not lower than 90%; and/or

The mass percentage of the foam wall thinning agent in the main body component is not higher than 7%.

5. The composite defoamer as claimed in any one of claims 1 to 4, wherein:

the particle size of a powder raw material in the main component of the composite antifoaming agent is not more than 100 meshes; preferably, a 140-mesh sieve is passed through; and/or

The main component is dissolved in the solvent component or suspended in the solvent component in a solid particle state.

6. A method for producing glass for bottle and jar ware, characterized in that the method is defoamed using the composite defoamer as claimed in any one of claims 1 to 5.

7. The method of claim 6, wherein:

the representative components of the bottle, can and vessel glass and the mass percentage content thereof are as follows: SiO 2₂65-76wt％，Al₂O₃1.5-6wt％，CaO+MgO+BaO₃-14wt％，Na₂O+K₂O+Li₂O 7-16wt％，Cr₂O₃0-0.5wt％，NiO 0-0.2wt％，CuO 0-0.5wt％，Co₃O₄0-0.1wt％，MnO 0-6wt％，TiO₂0-5wt％，Fe₂O₃0-2wt％；

Preferably, the daily usage amount of the composite antifoaming agent when the composite antifoaming agent is used for producing the glass of the bottle and can ware is not more than 0.10 wt% of the daily melting amount of the glass;

it is also preferable that the use temperature is not less than 1250 deg.C, for example, 1500 deg.C or more, and more preferably 1250 to 1500 deg.C.

8. The method according to claim 6 or 7, characterized in that:

the starting temperature point for step (1), step (4) and step (5) is independently 1250 ℃;

in the steps (1) and (3), the heating rate of the heating is independently 100 ℃/h; in the step (4), the cooling speed is 100 ℃/h; and/or in the step (5), the cooling speed is the fastest speed under the condition of not damaging equipment; and/or

In step (3), the target temperature point is maintained for a period of 30 minutes.

9. The method according to any one of claims 6 to 8, wherein:

the composite antifoaming agents of the first part, the second part and the third part are independently introduced after air atomization; preferably, the introduction is continuous introduction; preferably, the mass ratio of the composite antifoaming agent of the first part, the composite antifoaming agent of the second part and the composite antifoaming agent of the third part is 5:4: 1;

it is further preferred that the method further comprises, after step (6), step (7): the condition of bubbles in the sample was observed and compared with the defoaming effect of the reference standard sample to determine the defoaming effect.

10. Use of the composite defoamer of any one of claims 1 to 5 for the production of bottle and can ware glass;

preferably, the glass for making bottle-can ware is produced by the method of any one of claims 6 to 9.

Technical Field

The invention belongs to the technical field of melting in the production process of bottle-can ware glass, and particularly relates to a composite defoaming agent and application thereof in producing bottle-can ware glass.

Background

In the production process of glass for bottle and jar utensils, the raw materials of silica sand, feldspar, soda ash and nitrate can release CO in the high-temperature decomposition and melting process₂、NO/NO₂、H₂A large amount of gas such as O and the like forms a large amount of bubbles in the glass liquid, the bubble layer almost covers the non-ingredient covering area in the glass kiln of the bottle and jar ware, the thickness of the bubble layer is 10 mm-100 mm, meanwhile, because the bottle and jar ware glass usually has colors, such as beer is green or brown, blue glass bottles for oral liquid and the like, the use of a colorant causes the temperature gradient of the glass liquid in the depth direction to be increased, the rising efficiency of the bubbles in the depth direction of the glass liquid is lower, more bubbles remain in the glass liquid, and the qualification rate of the glass products of the bottle and jar ware is seriously influenced.

Generally, to reduce bubbles in molten glass, the bubble radius can be increased by adding a certain proportion of fining agent to the glass raw material, and the principle is as follows: the fining agent decomposing at high temperature to produce, for example, NO/NO₂、O₂A gas which combines with a gas generated by the decomposition of the glass raw material to increase the radius of bubbles so as to float up to the liquid surface of the molten glass; the expulsion of bubbles from the molten glass can also be promoted by increasing the temperature of the molten glass and reducing the viscosity of the molten glass (e.g., by heating), and thus, the increase in the temperature of the molten glass also reduces the surface tension of the molten glass and promotes the collapse of the foam layer floating on the surface of the molten glass.

However, although the use of the fining agent can promote the bubble diameter of a large amount of bubbles to increase and float to the surface of molten glass, the surface tension of the molten glass does not change, so that a small number of bubbles with particularly large diameters float to the surface of the molten glass and then are broken, most of the bubbles float to the surface of the molten glass and then are gathered together to form a foam layer in a laminated manner, and the foam layer is present to prevent the floating efficiency of the bubbles in the molten glass, and to form a reflection and heat insulation layer between the molten glass and the combustion heating flame at the upper part of the furnace, so that the absorption of heat by the molten glass is influenced. And promote the bubble through constantly heating the glass liquid and discharge and break, on the one hand because the foam blanket exists can influence heating efficiency, and on the other hand, except glass liquid surface tension, receive the bubble footpath size of bubble, the difference of bubble wall thickness, want to guarantee the breaking of all bubbles on glass liquid surface, glass liquid temperature will heat to very high, will certainly consume a large amount of energy, and long-time ultra-high temperature also can influence the whole life-span of bottle jar household utensils glass kiln simultaneously.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a composite defoaming agent, in particular to a composite defoaming agent suitable for producing glass of bottle and tank utensils and application thereof aiming at the defects in the prior art, wherein the bubble wall is thinned and bubble breakage is promoted, the highest temperature of a bottle and tank utensil kiln is not required to be increased, the bubble discharging efficiency of glass liquid is increased, and the influence of the bubble defects of the glass of the bottle and tank utensils is reduced.

The technical scheme adopted by the invention for solving the problems is as follows:

1. a composite defoamer comprising a host component and a solvent component, wherein:

the main component comprises a foam breaker and a foam wall thinning agent.

2. The composite antifoaming agent according to claim 1, wherein:

the flash point of the solvent component is more than or equal to 38 ℃; preferably, the solvent component is one or a mixture of several of diesel oil, aviation kerosene and heavy oil according to any proportion;

the foam breaker is a titanium-containing compound; preferably, the foam breaker is tetrabutyl titanate and/or titanium dioxide; and/or

The bubble wall thinning agent is sodium nitrate and/or potassium nitrate; more preferably, the ratio of the sodium nitrate in the cell wall thinning agent is not less than 90% by mass.

3. The composite antifoaming agent according to claim 1 or 2, wherein:

the main component also comprises a solvent combustion efficiency optimizing agent; preferably, the solvent combustion efficiency optimizing agent is iron glutarate; more preferably, the mass percentage of the solvent combustion efficiency improver in the main component is not higher than 3%.

4. The composite antifoaming agent according to any of claims 1 to 3, wherein:

the mass ratio of the main component to the solvent component is 1:2-23, and more preferably 1: 9-18;

the mass percentage of the foam breaker in the main component is not lower than 90%; and/or

The mass percentage of the foam wall thinning agent in the main body component is not higher than 7%.

5. The composite antifoaming agent according to any of claims 1 to 4, wherein:

the particle size of a powder raw material in the main component of the composite antifoaming agent is not more than 100 meshes; preferably, a 140-mesh sieve is passed through; and/or

The main component is dissolved in the solvent component or suspended in the solvent component in a solid particle state.

6. A method for producing glass for bottle and jar ware, wherein the method adopts the composite antifoaming agent described in any one of claims 1 to 5 for defoaming.

7. The method of claim 6, wherein:

the representative components of the bottle, can and vessel glass and the mass percentage content thereof are as follows: SiO 2₂65-76wt％，Al₂O₃1.5-6wt％，CaO+MgO+BaO₃-14wt％，Na₂O+K₂O+Li₂O 7-16wt％，Cr₂O₃0-0.5wt％，NiO 0-0.2wt％，CuO 0-0.5wt％，Co₃O₄0-0.1wt％，MnO 0-6wt％，TiO₂0-5wt％，Fe₂O₃0-2wt％；

Preferably, the daily usage amount of the composite antifoaming agent when the composite antifoaming agent is used for producing the glass of the bottle and can ware is not more than 0.10 wt% of the daily melting amount of the glass;

it is also preferable that the use temperature is not less than 1250 deg.C, for example, 1500 deg.C or more, and more preferably 1250 to 1500 deg.C.

8. The method of claim 6 or 7, wherein:

the starting temperature point for step (1), step (4) and step (5) is independently 1250 ℃;

in the steps (1) and (3), the heating rate of the heating is independently 100 ℃/h; in the step (4), the cooling speed is 100 ℃/h; and/or in the step (5), the cooling speed is the fastest speed under the condition of not damaging equipment; and/or

In step (3), the target temperature point is maintained for a period of 30 minutes;

9. the method according to any one of claims 6 to 8, wherein:

the composite antifoaming agents of the first part, the second part and the third part are independently introduced after air atomization; preferably, the introduction is continuous introduction; preferably, the mass ratio of the composite antifoaming agent of the first part, the composite antifoaming agent of the second part and the composite antifoaming agent of the third part is 5:4: 1;

it is further preferred that the method further comprises, after step (6), step (7): the condition of bubbles in the sample was observed and compared with the defoaming effect of the reference standard sample to determine the defoaming effect.

10. The application of the composite antifoaming agent in any one of technical schemes 1 to 5 in the production of bottle-can ware glass;

preferably, the glass for producing bottle-can ware is produced by the method of any one of claims 6 to 9.

Compared with the prior art, the invention has the beneficial effects that:

firstly, the invention develops a composite defoaming agent capable of promoting the breakage of a bubble layer on the surface of glass liquid in the production process of bottle ware glass, the effect of thinning the bubble wall is achieved by generating new small bubbles on the floating glass liquid bubble wall, and the breakage of the bubbles is promoted by reducing the local viscosity and the surface tension of the bubble wall, so that the highest temperature of a bottle ware kiln does not need to be improved, the breakage of the bubble layer on the surface of the glass liquid in different temperature areas of the kiln can be accelerated, the bubble discharging efficiency of the glass liquid is improved, and the influence of the glass bubble defects of the bottle ware glass is reduced.

Secondly, the chemical composition introduced by the composite defoaming agent cannot generate any adverse effect on the physical and chemical properties of the glass product of the bottle and tank ware, and the influence of a kiln heating mode (such as pure electric boosting heating, electric boosting and pure oxygen composite heating, pure oxygen heating, air boosting heating and oxygen-enriched combustion-supporting heating) on the production of the glass product of the bottle and tank ware is small.

Drawings

FIG. 1 is a schematic diagram of a sample melting device for glass of a bottle-can vessel, wherein 1 is a sample melting furnace, 2 is a platinum bowl, 3 is a glass sample melting, 4 is a sample melting bowl support table, 5 is a composite defoaming agent injection pipe, and 6 is an electric heating rod;

FIG. 2 is a reference standard sample of poor glass frit bubbles;

FIG. 3 is a reference standard sample of glass frit bubbles in the middle;

FIG. 4 is a reference standard sample for better glass frit bubbling.

Detailed Description

As described above, the invention provides in a first aspect a composite antifoaming agent suitable for use in the production of bottle and can ware glass, comprising a main component and a solvent component, wherein the main component comprises a titanium-containing compound as a defoaming agent.

According to the scheme, the main body component further comprises a bubble wall thinning agent sodium nitrate and/or potassium nitrate.

According to the scheme, the main component also comprises a solvent combustion efficiency optimizing agent of the glutaric iron.

Further preferably, the main component is composed of a titanium-containing compound as a foam breaker, sodium nitrate and/or potassium nitrate as a foam wall thinning agent, and pentylenetetrazol as a solvent combustion efficiency optimizing agent.

Further, the mass percentage of the main component of the composite antifoaming agent which meets the antifoaming agent is not less than 90%, preferably not less than 93%.

Further, the mass percentage of the main component of the composite defoaming agent meeting the foam wall thinning agent is not higher than 7%, and preferably not higher than 5%.

Further, the mass percentage of the agent satisfying the solvent combustion efficiency optimization in the main component of the composite antifoaming agent is not higher than 3%, preferably not higher than 2%.

According to the scheme, the flash point of the solvent component is more than or equal to 38 ℃, and the main component of the solvent component is dissolved in the solvent component or suspended in the solvent component in a solid particle state. Preferably, the solvent component is one or a mixture of several of oils such as diesel oil, aviation kerosene, heavy oil and the like according to any proportion.

According to the scheme, the titanium-containing compound of the foam breaker is mainly tetrabutyl titanate (C)₁₆H₃₆O₄One or a mixture of more of Ti), titanium dioxide and the like in any proportion mainly has the functions of reducing the local surface tension of the bubble wall and accelerating bubble breaking.

According to the scheme, the bubble wall thinning agent is mainly sodium nitrate and/or potassium nitrate and the like, and can mainly enable new small bubbles to be generated on the bubble wall to thin the bubble wall, so that the bubbles are easy to break. Due to the final K in the glass product of the bottle and can ware₂The content of O is low, so the content of sodium nitrate in the foam wall thinning agent is mainly the content, and the mass ratio of the sodium nitrate is not less than 90%.

According to the scheme, the solvent combustion efficiency optimizing agent is mainly ferrocene (Fe (C)₅H₅)₂) The main function of the defoaming agent is to improve the combustion efficiency of solvent components, optimize the use safety of the main components of the defoaming agent and the solvent components, and ensure that the interference on the chromaticity deviation of glass products of bottle containers is less than 2 percent.

According to the scheme, the particle size of the powder raw material in the main component of the composite defoaming agent is required to meet the requirement that a 100-mesh sieve completely passes through the powder raw material, and preferably a 140-mesh sieve completely passes through the powder raw material.

According to the scheme, the mass ratio of the main component to the solvent component of the composite defoaming agent is 1:2-23, and preferably 1: 9-18.

The invention relates to a bottle-jar ware glass product mainly suitable for a composite defoaming agent, which comprises the following representative components in percentage by mass: SiO 2₂65-76wt％，Al₂O₃1.5-6wt％，CaO+MgO+BaO 3-14wt％，Na₂O+K₂O+Li₂O 7-16wt％，Cr₂O₃0-0.5wt％，NiO 0-0.2wt％，CuO 0-0.5wt％，Co₃O₄0-0.1wt％，MnO 0-6wt％，TiO₂0-5wt％，Fe₂O₃0-2wt％。

When the composite defoaming agent is used for producing glass of bottle and jar utensils, the daily consumption of the composite defoaming agent is not higher than 0.10 wt% of the daily melting amount of the glass, and the use temperature zone is not lower than 1250 ℃.

The main technical concept of the invention is as follows: the invention mainly aims at various colors and varieties of bottle and jar ware glass products, obvious difference of the added colorants, large temperature gradient in the depth direction of glass liquid and difficult control of bubble defects caused by obvious influence of the added colorants on the heat absorption performance of the glass liquid, and develops a composite defoaming agent suitable for bottle and jar ware glass production, which can efficiently eliminate a bubble layer floating on the surface of the glass liquid in a kiln during melting, can also accelerate the discharge of bubbles in the depth direction of the glass liquid in the kiln, and can not generate any bad influence on the performance of the bottle and jar ware glass products.

Tetrabutyl titanate (C) in high temperature state of more than 1500 ℃ in a glass kiln for bottle and jar ware₁₆H₃₆O₄Ti) to form high-temperature TiO after oxidation combustion reaction₂Ultrafine particles (e.g. titanium dioxide TiO used directly as a foam breaker)₂Then directly sprayed with the solvent to directly obtain TiO₂Ultra-fine particles) on the bubble walls of the bubble layer in the kiln due to the TiO₂The polarity of the Ti-O bond is larger, the gaseous water in the high-temperature space in the kiln adsorbed on the surface is polarized and dissociated, namely H-OH is dissociated into hydroxyl-OH, the dissociated hydroxyl-OH enters glass liquid forming a bubble wall, the viscosity and the surface tension of the area are reduced, and the bubble is broken when the corresponding degree is reached;

meanwhile, in the production process of glass of the bottle-tank vessel, the bubble wall thinning agents of sodium nitrate and potassium nitrate are sprayed into a glass liquid bubble layer, and decomposition reaction, NaNO, occurs on the bubble wall under the high-temperature condition₃Decomposition to Na₂O、NO/NO₂、O₂，KNO₃Decomposition to K₂O、NO/NO₂、O₂Fine and minute amount of K₂O and Na₂O enters into the molten glass and has no influence on the performance of the glass product, and O₂、NO/NO₂A plurality of new small bubbles are generated on the bubble wall of the glass liquid to achieve the effect of thinning the bubble wall, so that the bubble wall is easy to break under the same condition; however, due to the final K in the bottle-can glass product₂The content of O is low, so the content of sodium nitrate in the foam wall thinning agent is mainly the content, and the mass ratio of the sodium nitrate is not less than 90 percent;

in addition, because the solvent in the composite defoamer is a conventional fuel component, and because the pentifron can improve the fuel combustion efficiency and reduce the smoke gas amount after combustion, a certain amount of pentifron is introduced into the defoamer, but considering that the pentifron finally enters the glass liquid in the form of ferric oxide or ferrous oxide, the chromaticity of the glass product of the bottle and can ware can be interfered, although the glass of the bottle and can ware has a certain color, the chromaticity index of the color has a strict requirement, the chromaticity deviation interference is less than 2%, and considering that the introduction of the ferric oxide or the ferrous oxide can obviously influence the use function of the product, the introduction amount of the pentifron is strictly controlled;

through the principle, the invention develops the composite defoaming agent suitable for producing the glass of the bottle and jar ware, the highest temperature of a glass production kiln of the bottle and jar ware is not required to be increased, the breakage of bubble layers on the surface of glass liquid in different temperature areas of the kiln can be accelerated, the foam layer is basically eliminated, and the production qualification rate of the glass of the bottle and jar ware is obviously increased.

As described above, the present invention also provides, in a second aspect, a method for producing glass for bottle and can ware, which comprises defoaming with the composite defoaming agent according to the first aspect of the present invention. In addition, the invention also provides the application of the composite defoaming agent in the first aspect of the invention in the production of bottle-can ware glass; preferably, the glass for making bottle-can ware is produced by the method of the second aspect of the invention.