低碳玻璃配方对玻璃熔制过程及CO2排放的影响

doi:10.16552/j.cnki.issn1001-1625.2025.1124

摘要/Abstract

摘要：

玻璃熔制过程能耗高、碳排放量大，原料中碳酸盐的分解与燃料燃烧是主要碳排放来源。为探究从原料端减碳的可行途径，本文基于固定的目标氧化物组成，采用热重-差示扫描量热分析法结合高温熔融实验，研究传统配方、两种减碳配方及掺50%（质量分数）碎玻璃配方，共4组配方的反应热、熔化行为和CO₂排放。结果表明，以硅酸钙替代传统原料中的碳酸钙并配合NaOH作为高效助熔剂的配方节能降碳协同效益最显著，理论总热耗较传统配方降低约21.1%，总CO₂排放量减少65.4%。掺入50%碎玻璃可使熔化温度较传统配方降低50 ℃并减排37.1%，但减碳潜力受限于残余碳酸盐。若以硅酸盐代替碳酸盐而未配高效助熔剂，则因熔化温度升高导致能耗上升34.7%。研究表明，引入硅酸盐代替碳酸盐并加入高效助熔剂是玻璃工业源头减碳的有效途径，通过明确低碳原料体系对应的熔化温度与热耗水平，为原料配方设计及玻璃生产工艺制度优化提供了理论依据。

关键词: 玻璃熔制, 碳排放, 减碳原料, 热耗, 碎玻璃

Abstract:

The glass melting process is characterized by high energy consumption and significant carbon emissions， mainly resulting from the decomposition of carbonates in raw materials and the combustion of fuels. To explore the feasibility of carbon reduction from the raw material perspective， four glass batch formulations with a fixed target oxide composition were designed in this paper， including a conventional batch， two low-carbon batches without carbonates， and a batch containing 50% （mass fraction） cullet. Thermogravimetric-differential scanning calorimetry analysis combined with high-temperature melting experiments were conducted to investigate reaction heat， melting behavior， and CO₂ emissions. The results show that the greatest synergistic benefit of energy saving and carbon reduction achieves when calcium silicate is used to replace calcium carbonate in traditional raw materials， in conjunction with NaOH as an efficient fluxing agent， reducing the theoretical total heat consumption by about 21.1% and the total CO₂ emissions by 65.4% compared with the conventional batch. The incorporation of 50% cullet reduced the melting temperature by 50 ℃ compared with the conventional batch and achieved a 37.1% reduction in CO₂ emissions， though its potential is limited by residual carbonates. In contrast， replacing carbonates with silicates without the assistance of efficient fluxing agents result in a 34.7% increase in energy consumption due to the elevated melting temperature. This study demonstrates that replacing carbonates with silicates and employing NaOH as an efficient fluxing agent constitutes an effective source-side decarbonization pathway for the glass industry. By clarifying the melting temperature and energy consumption levels of low-carbon raw material systems， this work provides theoretical guidance for optimizing raw material formulations design and supports the development of low-carbon glass production processes.

Key words: glass melting, carbon emission, low-carbon material, heat consumption, cullet

中图分类号:

TQ171

刘晨宇, 张文露, 李从云, 曾健华, 李路瑶, 韩建军, 王静. 低碳玻璃配方对玻璃熔制过程及CO₂排放的影响[J]. 硅酸盐通报, 2026, 45(3): 1083-1093.

LIU Chenyu, ZHANG Wenlu, LI Congyun, ZENG Jianhua, LI Luyao, HAN Jianjun, WANG Jing. Effect of Low-Carbon Glass Batch Formulations on Glass Melting Process and CO₂ Emissions[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 1083-1093.

图/表 12

表1 玻璃的目标氧化物组成

Table 1 Target oxide composition of glass

Oxide component	SiO₂	CaO	Al₂O₃	Na₂O	Li₂O
Mass fraction/%	73.9	7.6	2.6	15.8	0.2

表2 四组配方中各原料组分质量占比

Table 2 Mass fraction of raw material components in four batch formulations

Formulation No.	Mass/g	Mass fraction/%
Formulation No.	Mass/g	Na（AlSi₃O₈）	LiAl（Si₂O₆）	SiO₂	CaCO₃	CaSiO₃	Na₂CO₃	Li₂CO₃	Na₂SiO₃	NaOH	Cullet
Ⅰ	116.6	11.5	—	55.7	11.6	—	20.8	0.4	—	—	—
Ⅱ	104.2	10.0	2.0	55.0	—	15.0	—	—	—	18.0	—
Ⅲ	100.0	10.4	2.1	43.3	—	15.6	—	—	28.6	—	—
Ⅳ	107.5	5.7	—	27.8	5.8	—	10.5	0.2	—	—	50.0

表3 四组配方样品所设实验温度

Table 3 Experimental temperatures set of samples for four batch formulations

Formulation No.	Predicted melting temperature range/℃	Experimental set temperature/℃
Ⅰ	1 200~1 250	1 200， 1 225， 1 250
Ⅱ	1 200~1 250	1 200， 1 225， 1 250
Ⅲ	1 400~1 500	1 425， 1 450， 1 475
Ⅳ	1 150~1 200	1 175， 1 200， 1 225

图1 四组配方样品的TG-DSC曲线

Fig.1 TG-DSC curves of samples for four batch formulations

表4 四组配方样品所得TG-DSC曲线中主要峰点及峰面积

Table 4 Key peaks and peak areas derived from TG-DSC curves of samples for four batch formulations

Formulation No.	Peak	Peak temperature/℃	Onset temperature/℃	End temperature/℃	Peak area/（J·g^-1）
Ⅰ	a	132.3	112.5	147.0	-13.8
	b	573.8	569.2	578.6	-4.6
	c	685.9	618.1	710.7	-431.0
	d	815.9	806.5	828.6	-58.0
	e	844.6	838.9	850.9	-13.9
Ⅱ	a	92.8	40.7	136.7	-261.9
	b	268.8	254.7	283.5	-7.9
	c	424.7	390.1	440.2	-16.8
	d	573.5	569.2	579.3	-4.2
	e	914.9	898.9	936.3	15.9
Ⅲ	a	78.3	40.2	137.9	-189.4
	b	573.0	569.2	578.1	-4.4
	c	848.7	797.6	917.9	-68.8
	d	982.0	943.0	992.5	-41.9
	e	1 057.6	1 045.2	1 113.2	-66.9
Ⅳ	a	133.4	105.0	145.1	-17.1
	b	663.2	617.2	684.5	-105.9
	c	818.3	804.1	851.9	-233.6
	d	1 257.8	1 249.7	1 267.9	-15.8

表5 四组配方样品的反应热和初始液相形成温度

Table 5 Reaction heat and initial liquid phase formation temperature of samples for four batch formulations

Formulation No.	Endothermic peak area/（J·g^-1）	Exothermic peak area/（J·g^-1）	$Q r x n$ /（J·g^-1）	$T L$ /℃
Ⅰ	521.3	0	521.3	850
Ⅱ	290.8	15.9	274.9	900
Ⅲ	371.4	0	371.4	1 000
Ⅳ	372.4	0	372.4	850

表5 四组配方样品的反应热和初始液相形成温度

Table 5 Reaction heat and initial liquid phase formation temperature of samples for four batch formulations

Formulation No.	Endothermic peak area/（J·g^-1）	Exothermic peak area/（J·g^-1）	$Q r x n$ /（J·g^-1）	$T L$ /℃
Ⅰ	521.3	0	521.3	850
Ⅱ	290.8	15.9	274.9	900
Ⅲ	371.4	0	371.4	1 000
Ⅳ	372.4	0	372.4	850

图2 四组配方样品在三组实验温度下烧制得到的玻璃

Fig.2 Glass samples obtained from four batch formulations at three experimental temperatures

图3 第二组配方在1 500 ℃下熔制得到的玻璃样品

Fig.3 Glass sample obtained from formulation No.II at 1 500 ℃

表6 四组配方进行玻璃生产过程的理论总热耗

Table 6 Theoretical total heat consumption of glass production process for four batch formulations

Formulation No.	$Q r x n$ /（J·g^-1）	$Q s o l i d$ /（J·g^-1）	$Q l i q u i d$ （J·g^-1）	$Q a l l$ /（J·g^-1）
Ⅰ	521.3	1 106.2	633.5	2 261.0
Ⅱ	274.9	1 048.5	460.7	1 784.1
Ⅲ	371.4	1 121.3	620.6	2 113.3
Ⅳ	372.4	1 019.9	509.9	1 902.2

表6 四组配方进行玻璃生产过程的理论总热耗

Table 6 Theoretical total heat consumption of glass production process for four batch formulations

Formulation No.	$Q r x n$ /（J·g^-1）	$Q s o l i d$ /（J·g^-1）	$Q l i q u i d$ （J·g^-1）	$Q a l l$ /（J·g^-1）
Ⅰ	521.3	1 106.2	633.5	2 261.0
Ⅱ	274.9	1 048.5	460.7	1 784.1
Ⅲ	371.4	1 121.3	620.6	2 113.3
Ⅳ	372.4	1 019.9	509.9	1 902.2

表7 四组配方中由碳酸盐分解产生的碳排放值

Table 7 Carbon emission values produced by carbonate decomposition of four batch formulations

Formulation No.	Component	M/g	MF/%	EF/g	F/%	$E d e c o m p$ /g
Ⅰ	CaCO₃	13.5	99	44/100	100	5.9
	Na₂CO₃	24.3	99	44/106	100	10.0
	Li₂CO₃	0.4	99	44/74	100	0.2
	Total	—	—	—	—	16.1
Ⅱ	—	—	—	—	—	0
Ⅲ	—	—	—	—	—	0
Ⅳ	CaCO₃	6.2	99	44/100	100	2.7
	Na₂CO₃	11.2	99	44/106	100	4.6
	Li₂CO₃	0.2	99	44/74	100	0.1
	Total	—	—	—	—	7.4

表7 四组配方中由碳酸盐分解产生的碳排放值

Table 7 Carbon emission values produced by carbonate decomposition of four batch formulations

Formulation No.	Component	M/g	MF/%	EF/g	F/%	$E d e c o m p$ /g
Ⅰ	CaCO₃	13.5	99	44/100	100	5.9
	Na₂CO₃	24.3	99	44/106	100	10.0
	Li₂CO₃	0.4	99	44/74	100	0.2
	Total	—	—	—	—	16.1
Ⅱ	—	—	—	—	—	0
Ⅲ	—	—	—	—	—	0
Ⅳ	CaCO₃	6.2	99	44/100	100	2.7
	Na₂CO₃	11.2	99	44/106	100	4.6
	Li₂CO₃	0.2	99	44/74	100	0.1
	Total	—	—	—	—	7.4

表8 燃料燃烧所产生的碳排放值

Table 8 Carbon emission values produced by fuel combustion

Formulation No.	CC/（g·J^-1）	OF/%	EF $f$ /（g·J^-1）	AD/J	$E c o m b$ /g
Ⅰ	15.3×10^-6	99	55.5×10^-6	226 103.9	12.5
Ⅱ				178 406.3	9.9
Ⅲ				211 325.9	11.7
Ⅳ				190 216.0	10.6

表8 燃料燃烧所产生的碳排放值

Table 8 Carbon emission values produced by fuel combustion

Formulation No.	CC/（g·J^-1）	OF/%	EF $f$ /（g·J^-1）	AD/J	$E c o m b$ /g
Ⅰ	15.3×10^-6	99	55.5×10^-6	226 103.9	12.5
Ⅱ				178 406.3	9.9
Ⅲ				211 325.9	11.7
Ⅳ				190 216.0	10.6

表9 四组配方在玻璃生产过程中的碳排放总量及差异

Table 9 Total carbon emission amount and differences in glass production process for four batch formulations

Formulation No.	$E d e c o m p$ /g	$E c o m b$ /g	$E t o t a l$ /g	Reduction vs. No. I/%
Ⅰ	16.1	12.5	28.6	0
Ⅱ	0	9.9	9.9	65.4
Ⅲ	0	11.7	11.7	59.1
Ⅳ	7.4	10.6	18.0	37.1

表9 四组配方在玻璃生产过程中的碳排放总量及差异

Table 9 Total carbon emission amount and differences in glass production process for four batch formulations

Formulation No.	$E d e c o m p$ /g	$E c o m b$ /g	$E t o t a l$ /g	Reduction vs. No. I/%
Ⅰ	16.1	12.5	28.6	0
Ⅱ	0	9.9	9.9	65.4
Ⅲ	0	11.7	11.7	59.1
Ⅳ	7.4	10.6	18.0	37.1

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低碳玻璃配方对玻璃熔制过程及CO₂排放的影响

Effect of Low-Carbon Glass Batch Formulations on Glass Melting Process and CO₂ Emissions

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