阅读说明：本技术 一种新型环保高白料瓶罐玻璃 (novel environment-friendly high-whiteness material bottle and can glass ) 是由 沈序宾 杨克勇 于 2019-11-28 设计创作，主要内容包括：本发明公开了一种新型环保高白料瓶罐玻璃,以重量百分比表示,其含有以下组分：SiO<Sub>2</Sub>：72－75％,Al<Sub>2</Sub>O<Sub>3</Sub>：1.5－2.5％,CaO：8－12％,MgO：1－3％,(Na<Sub>2</Sub>O+K<Sub>2</Sub>O)：12－14％,B<Sub>2</Sub>O<Sub>3</Sub>：1－3％,Li<Sub>2</Sub>O：0.2－1.0％,BaO：0.2－1.0％,CeO<Sub>2</Sub>：0.1－0.5％以及适量的物理脱色剂。本发明的新型环保高白料瓶罐玻璃,在未增加制造成本的情况下,通过改变主要原料的配比和引入新物质,使高白料瓶罐玻璃的机械强度和化学稳定性都得到了提高,克服了传统高白料瓶罐玻璃易碎、易析钠的问题,从而满足了酒厂高速罐装的需求,同时,本发明使用不含氟、砷、锑的澄清剂,达到了环保和食品安全的要求。(The invention discloses novel environment-friendly high-whiteness glass for bottles and cans, which comprises the following components in percentage by weight 2 ：72－75％，Al 2 O 3 ：1.5－2.5％，CaO：8－12％，MgO：1－3％，(Na 2 O+K 2 O)：12－14％，B 2 O 3 ：1－3％，Li 2 O：0.2－1.0％，BaO：0.2－1.0％，CeO 2 : 0.1-0.5% and proper amount of physical decolorant. The novel environment-friendly high-whiteness glass bottle and can improves the mechanical strength and the chemical stability of the high-whiteness glass bottle and can and overcomes the problems of fragility and easy sodium precipitation of the traditional high-whiteness glass bottle and can without increasing the manufacturing cost, and simultaneously, the novel environment-friendly high-whiteness glass bottle and can meet the requirements of environmental protection and food safety by using a clarifying agent which does not contain fluorine, arsenic and antimony.)

1, novel environment-friendly high-whiteness bottle and can glass, which is characterized by comprising the following components in percentage by weight₂：72－75％，Al₂O₃：1.5－2.5％，CaO：8－12％，MgO：1－3％，(Na₂O+K₂O)：12－14％，B₂O₃：1－3％，Li₂O：0.2－1.0％，BaO：0.2－1.0％，CeO₂: 0.1-0.5% and proper amount of physical decolorant.

2. The new environmentally friendly high white glass bottle and can glass according to claim 1, wherein the glass component of the environmentally friendly high white glass bottle and can glass does not contain arsenic oxide, antimony oxide and fluoride.

3. The novel environmentally friendly high-whiteness glass bottle and can as defined in claim 2 wherein the physical decolorant is or a combination of erbium oxide, selenium and cobalt oxide.

4. The novel environment-friendly high-whiteness glass bottle and can as defined in claim 3, wherein the physical decolorant is a combination of erbium oxide, selenium and cobalt oxide, wherein the erbium oxide is added in an amount of 80-120g/t, the selenium is added in an amount of 6-14g/t, and the cobalt oxide is added in an amount of 0.3-2.0 g/t.

5. The environmentally friendly glass bottle and can product of claim 4, wherein the physical decolorant comprises erbium oxide in an amount of 100g/t, selenium in an amount of 10g/t, and cobalt oxide in an amount of 1 g/t.

6. The novel environmentally friendly high-whiteness glass bottle and can as defined in claim 5, wherein in the preparation of the environmentally friendly glass bottle and can product, the glass is clarified by using a cerium oxide composite clarifier, wherein the cerium oxide composite clarifier is a combination of cerium oxide, sodium nitrate and barium sulfate.

7. The novel environment-friendly high-whiteness bottle and can glass as defined in claim 6, wherein the cerium oxide composite clarifier is added in an amount of 0.1-0.5%, wherein "%" represents the weight percentage of the total raw materials of the glass.

8. The of claims 1-7, wherein the melting temperature is 1525 ± 10 ℃, the forming temperature is 1223 ± 10 ℃, the upper annealing temperature is 618 ± 10 ℃, and the lower annealing temperature is 510 ± 10 ℃ in the process for making the glass.

Technical Field

The invention relates to the technical field of white material bottle and can glass, in particular to novel environment-friendly high-white material bottle and can glass.

Background

The formula of the currently common high-whiteness bottle and can glass (also called soda-lime glass) comprises silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, sodium oxide, potassium oxide and additives, and the components in weight ratio are as follows: silicon dioxide (SiO)₂) 70-73% of aluminum oxide (Al)₂O₃) 0.8-1.5%, calcium oxide (CaO) 8-12%, magnesium oxide (MgO) 1-3%, disodium oxide and dipotassium oxide (Na)₂O+K₂O) 14-16%, and additivesThe addition agent is 1-3%, although the glass meets the production and quality requirements of most bottles and cans, the mechanical strength of the glass is not suitable for the requirements of high-speed filling production in the existing winery and is easy to break, meanwhile, the glass has low chemical stability, is easy to generate a sodium precipitation phenomenon in a humid environment, has a short storage period and influences on production and food safety, and in addition, most of the traditional bottle and can glasses adopt arsenic-antimony clarifying agents in the production process, and fluoride is added to accelerate clarification, so the mode is not suitable for the current safety and environmental protection requirements, and therefore improvement needs to be carried out on the existing glass formula so as to solve the problems.

Disclosure of Invention

The invention aims to provide novel environment-friendly high-whiteness bottle and can glass with high mechanical strength and high chemical stability to solve the defects in the prior art.

The technical scheme adopted by the invention is that novel environment-friendly high-whiteness bottle and can glass is characterized by comprising the following components in percentage by weight₂：72-75％，Al₂O₃：1.5-2.5％，CaO： 8-12％，MgO：1-3％，(Na₂O+K₂O)：12-14％，B₂O₃：1-3％，Li₂O：0.2-1.0％， BaO：0.2-1.0％，CeO₂: 0.1-0.5% and proper amount of physical decolorant.

, according to the novel environment-friendly high-whiteness glass bottle and can, the glass component of the environment-friendly high-whiteness glass bottle and can does not contain arsenic oxide, antimony oxide and fluoride.

, the physical decolorant is the combination of erbium oxide, selenium and cobalt oxide .

And , adding erbium oxide, selenium and cobalt oxide as physical decolorants, wherein the amount of erbium oxide is 80-120g/t, the amount of selenium is 6-14g/t, the amount of cobalt oxide is 0.3-2.0g/t, and t represents the amount of glass liquid or total raw materials.

Preferably, in the physical decolorant, the addition amount of erbium oxide is 100g/t, the addition amount of selenium is 10g/t, and the addition amount of cobalt oxide is 1 g/t.

, when preparing the environment-friendly glass bottle and can product, using cerium oxide composite clarifier to clarify the glass, wherein the cerium oxide composite clarifier is the combination of cerium oxide, sodium nitrate and barium sulfate.

, the cerium oxide composite clarifier is added in an amount of 0.1-0.5%, wherein "%" represents the weight percentage of the total raw materials of the glass.

, in the process of manufacturing the glass bottle, the melting temperature is 1525 + -10 ℃, the forming temperature is 1223 + -10 ℃, the upper limit of the annealing temperature is 618 + -10 ℃, and the lower limit of the annealing temperature is 510 + -10 ℃.

In the invention, in order to obtain high-whiteness glass bottle with high mechanical strength and chemical stability, the inventor adopts a mode of increasing the content of silicon dioxide, compared with other lifting modes, the mode of increasing the content of silicon dioxide is most direct, the mechanical strength is improved most obviously, and the chemical stability is good, however, the glass melting temperature is overhigh due to the increase of the content of silicon dioxide, the crystallization problem is easy to generate, and in order to overcome the adverse effects, the inventor reduces the content of aluminum oxide and (Na)₂O+K₂O) content, thereby lowering the melting temperature and maintaining the increase in strength (Na)₂O can reduce the mechanical strength, chemical stability and thermal stability of the glass, because the content is reduced as much as possible), and at the same time, boron oxide, lithium oxide and barium oxide are introduced, and the oxides have the functions of improving the mechanical strength, thermal stability, chemical stability, fluxing and the like of the glass, so that the mechanical strength of the glass as a whole is obviously improved, the chemical stability is stable, the raw materials are low in cost, and for a single raw material, the oxide is also which is a frequently added component in the glass raw material, but the oxide is not combined and matched for use, and after the combination and matching of the oxide and the raw material, the surface tension of the glass is finally improved from 324.78dyn/cm to 332.96dyn/cm, and the coefficient of thermal expansion is increased from 81.07 x 10 to 332.96dyn/cm^-7℃^-1Down to 77.38X 10^-7℃^-1The effect is obvious, and the obtained high-whiteness material can glass does not haveEasy to break, high in chemical stability, effectively solves the problem of sodium precipitation, and overcomes the defects of the existing high-white material bottle and can glass.

, in order to meet the current requirement for environmental protection, the invention obviously prevents the traditional arsenic-antimony clarifier and fluoride from being reused, and in order to find the substitute of arsenic-antimony clarifier, the inventor obtains through many years of experiments, the cerium oxide composite clarifier which takes cerium oxide as the main effective component can completely substitute arsenic-antimony clarifier and can achieve the equivalent clarification effect, CeO₂Being a strong oxidant, pyrolysis gives off oxygen, which can oxidize FeO to Fe₂O₃The coloring capacity of the glass is reduced, and the color and the light transmittance of the glass are improved, so that the glass can be clarified, and the clarification effect is obvious. Meanwhile, in order to achieve the effect of auxiliary clarification, the inventor also adds barium sulfate and sodium nitrate to form a cerium oxide composite clarifier, wherein the barium sulfate and the sodium nitrate can achieve the technical effects of clarification, decoloration and fluxing, and the part of cerium oxide which is not easy to clarify is clarified by the barium sulfate and the sodium nitrate, so that the clarification effect of the cerium oxide is strengthened on the whole, and the high-whiteness material bottle and tank glass is obtained.

In addition, in order to further enhance the clarification effect in step and ensure the color stability of the glass, a physical decolorant is added by the inventor, certainly, the physical decolorant can be a traditional physical decolorant, such as manganese dioxide, selenium, cobalt oxide, nickel oxide and the like, in the invention, under the condition that the main raw materials of the glass are different from the traditional glass, in order to ensure the high-whiteness bottle and can glass, the inventor adopts the combination of erbium oxide, selenium and cobalt oxide to prepare the physical decolorant, wherein the adding amount of erbium oxide is 80-120g/t, the adding amount of selenium is 6-14g/t, the adding amount of cobalt oxide is 0.3-2.0g/t, the collocation of the erbium oxide, the selenium and the cobalt oxide can form complementation, for example, the problem of unstable selenium coloration can be effectively improved, the problem of discoloration of products caused by annealing, post-processing, sunshine and solarization and the like in the glass production process can be completely solved, so that the final glass presents stable transparent color, and the clarification effect is further enhanced.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: the novel environment-friendly high-whiteness glass can improves the mechanical strength and the chemical stability of the high-whiteness glass can by changing the proportion of main raw materials and introducing new substances without increasing the manufacturing cost, overcomes the problems of fragility and easy sodium precipitation of the traditional high-whiteness glass can, meets the requirement of high-speed canning in a winery, and simultaneously uses a clarifying agent which does not contain fluorine, arsenic and antimony, meets the requirements of environmental protection and food safety, and eliminates the environmental protection pressure of the production of winery products.

Detailed Description

For purposes of making the objects, aspects and advantages of the present invention more apparent, the present invention will now be described in detail at with reference to the following examples.

novel environment-friendly high-whiteness bottle and can glass comprises the following components in percentage by weight₂： 72-75％，Al₂O₃：1.5-2.5％，CaO：8-12％，MgO：1-3％，(Na₂O+K₂O)：12-14％，B₂O₃： 1-3％，Li₂O：0.2-1.0％，BaO：0.2-1.0％，CeO₂: 0.1-0.5 percent and a proper amount of physical decolorant, in the novel environment-friendly high-whiteness bottle and can glass, the oxides are mainly introduced by the following raw materials (including the functions of the oxides in the glass):

1. quartz sand: mainly introducing SiO₂Forming the main oxide of the glass and becoming the skeleton, SiO, in the glass₂Can improve the mechanical strength, chemical stability, thermal stability, transparency and viscosity of the glass, but when SiO₂At higher contents, higher melting temperatures are required for the manufacture, which makes the melting of the glass difficult and may cause devitrification, whereas the overall properties of the glass are insufficient, in the present invention, SiO₂The weight ratio of (B) is 72-75%, which is higher than that of the existing white glass bottle, and the specific dosage is selected according to actual production, and can be 72%, 73%, 74%, 75% and the like.

2. Soda ash: mainly introducing Na₂O，Na₂O is a good flux to lower the melting temperature of the glass, and is capable of lowering the viscosity of the glass, increasing the fluidity of the glass, and improving the devitrification property of the glass, but Na is₂O can reduce the mechanical strength, chemical stability and thermal stability of the glass, and the glass is easy to mildew in a humid environment, in order to effectively solve the problem of SiO₂The side effect caused by the increase of the dosage and the reduction of Na₂As a side effect of O, its content should not be too high.

3. Calcite: the CaO is mainly introduced, the mechanical strength, hardness and chemical stability of the glass can be improved by the CaO, the viscosity of the glass can be reduced at high temperature to facilitate melting and clarification of the glass, the viscosity of the glass can be increased at low temperature to improve the hardening speed, but the glass is easy to crystallize due to excessively high CaO content to make the glass brittle and reduce the thermal stability of the glass.

4. Dolomite: MgO is mainly introduced, the function of the MgO is similar to that of CaO, but the addition of the MgO overcomes the characteristic of strong crystallization capability of the CaO, the operation temperature range is widened, the glass forming is facilitated, but the consumption of the MgO is not too much, in the invention, the weight proportion of the MgO is the same as that of the traditional method, namely 1-3%, the specific consumption is selected according to the actual production, for example, the content of the MgO can be 1%, 1.5%, 2%, 2.5%, and the like, and the content of the CaO can be 8%, 9%, 10%, 11%, 12%, and the like.

5. Lithium feldspar: introduction of mainly Al₂O₃、SiO₂、(Na₂O+K₂O)、Li₂The addition of O and lithionite can improve the chemical stability and mechanical strength of glass, reduce the devitrification tendency and thermal expansion coefficient of glass, improve the thermal stability of glass and reduce the corrosion to refractory material. In the present invention, Al₂O₃Can be used for1.5%, 1.7%, 1.9%, 2.0%, 2.2%, 2.5%, etc.

6. Sodium nitrate: mainly introducing Na₂And O is used as a decoloring agent, a clarifying agent and an oxidizing fluxing agent in production.

7. Borax pentahydrate: introduction of mainly B₂O₃，B₂O₃The oxide formed by the glass and silicon-oxygen tetrahedron form a structural network together, so that the expansion coefficient of the glass can be reduced, the thermal stability and the chemical stability of the glass can be improved, the refractive index of the glass can be increased, the gloss of the glass can be improved, the mechanical property of the glass can be improved, the viscosity of the glass can be reduced at high temperature, and the clarification and homogenization of the glass can be facilitated, and the content can be 1%, 2%, 2.5%, 3% and the like.

8. Barium sulfate: BaO is mainly introduced, the BaO is a divalent network exo-oxide, the refractive index, the density, the luster and the chemical stability of the glass can be increased, and the barium sulfate raw material is introduced to play roles in clarification and fluxing.

9. Lithium oxide: li₂O is an extraludos oxide, has a bond breaking effect, is a strong fluxing agent, and is beneficial to improving the melting performance of the batch. Introducing the lithium feldspar as a raw material.

10. Cerium oxide: mainly introducing CeO₂，CeO₂Is a strong oxidant, releases oxygen through pyrolysis, is used as a main clarifying raw material and can oxidize FeO into Fe₂O₃The coloring ability of the glass is reduced, and the color and the light transmittance of the glass are improved.

To better illustrate the effects of the present invention, examples 1-4 and comparative examples (conventional formulations) 1-3 are listed below, as shown in Table 1:

table 1 examples 1-4 and comparative examples 1-3 formulations (based on the final glass formed,% indicates weight percent):

the same procedure was used for the above examples 1-5 and comparative examples 1-3, i.e. a conventional high-whiteness glass can production process was used, except for the difference in temperature parameters in the process steps, as shown in Table 2:

table 2 comparison data of temperature parameters in the production process of high-whiteness jar glass:

item	Melting temperature	Temperature of formation	Upper limit of annealing temperature	Lower limit of annealing temperature
					Examples 1 to 4	1525±10℃	1223±10℃	618±10℃	510±10℃
Comparative examples 1 to 3	1502±10℃	1106±10℃	573±10℃	485±10℃

The product obtained according to the above process parameters, examples 1 to 4 and comparative examples 1 to 3, have the main properties as shown (averaged) in table 3 below:

TABLE 3 comparison of the Main Properties of the examples and comparative examples

The table shows that the novel environment-friendly high-whiteness glass for bottles and cans of the invention has improved mechanical strength and chemical stability, the surface tension is improved from 324.78dyn/cm to 332.96dyn/cm, and the thermal expansion coefficient is improved from 81.07 multiplied by 10^-7℃^-1Down to 77.38X 10^-7℃^-1The invention has obvious effect, overcomes the problems of fragility and easy sodium separation of the traditional high-white material bottle glass, thereby meeting the requirement of high-speed canning in a winery, and simultaneously, the invention uses a clarifying agent without fluorine, arsenic and antimony, thereby meeting the requirements of environmental protection and food safety and eliminating the environmental protection pressure of the production of winery products.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.