自适应精准控温型液相色谱柱温箱的设计与评价

doi:10.3724/SP.J.1123.2023.11021

摘要/Abstract

摘要：

高效液相色谱系统作为诸多领域的关键分析手段,提升其分离效率、稳定性和普适性是研究重点。在该技术手段中,流动相的组成和比例、固定相的种类以及色谱柱的尺寸等显著影响分离效果,色谱柱和流动相的温度对分离效果也起到了至关重要的作用。高效液相色谱系统通常采用柱温箱进行温度控制,高精度的温度控制可提升色谱分离性能、缩短分析时间、确保分析结果的重复性。本文创新性地改进了柱温箱的结构,通过融合多种先进温度控制算法,实现了高精度、宽范围(4~90 ℃)的连续升降温控制,为色谱分析方法发展开辟了新路径。此改进摒弃了复杂的硬件系统,仅通过软件优化即达成了高度稳定的控温效果,控温精度提升至±0.1 ℃。此外,通过优化保温结构与采用环保隔热材料,也增强了控温精细化能力;对于热源热传导机制的研究,进一步提升了柱温箱的综合性能。结果表明,该改进显著提高了色谱分离的重复性和稳定性,为高效色谱分析方法的发展奠定了坚实基础。

关键词: 精准控温, 算法, 传热原理, 液相色谱, 柱温箱

Abstract:

High performance liquid chromatography (HPLC) is a key analytical technique that is used in a number of fields. Improving the separation efficiency, stability, and universality of HPLC has been a continuing analytical-chemistry focus. In chromatographic separation, factors such as the composition and ratio of the mobile phase, the type of stationary phase, and the dimensions of the chromatographic column significantly affect the separation efficiency. In addition, the temperatures of the chromatographic column and mobile phase are also important for achieving separation. The column oven is usually used to stably control the column temperature in the HPLC separation system. Indeed, highly accurate temperature control ensures superior separation performance, short analysis times, and repeatability. In this study, we innovatively improved the traditional column oven by combining a variety of temperature-control algorithms to deliver continuous and highly accurate temperature control in the wide 4-90 ℃ range, and by exploring a new chromatographic-method development route. Instead of focusing on the complex hardware system, we optimized the software to achieve highly stable and accurate (±0.1 ℃) temperature control. Temperature-control performance was further improved by optimizing the structure of the thermal insulation and employing reliable and environmentally friendly thermal-insulation materials. Additionally, the thermal conduction of the heat-source device is discussed based on the heat-transfer principle with the aim of improving the performance of the column oven. The improved column oven delivered significantly enhanced chromatographic-separation repeatability and stability thereby reliably guaranteeing the development of highly efficient chromatographic analysis methods.

Key words: precise temperature control, algorithm, heat transfer principle, liquid chromatography, column oven

中图分类号:

O658

任兴发, 邵锋伟, 吴勇, 廖信明, 王卓, 周林娟, 何旭鸿, 张维冰. 自适应精准控温型液相色谱柱温箱的设计与评价[J]. 色谱, 2025, 43(2): 177-184.

REN Xingfa, SHAO Fengwei, WU Yong, LIAO Xinming, WANG Zhuo, ZHOU Linjuan, HE Xuhong, ZHANG Weibing. Design and evaluation of a liquid chromatographic column oven with adaptive and precise temperature control[J]. Chinese Journal of Chromatography, 2025, 43(2): 177-184.

图/表 9

图 1 (a)柱温箱结构设计图及(b)柱温箱内循环流体模拟图

Fig. 1 (a) Diagram depicting the structural design of the column oven and (b) a simulation showing circulating fluid in the column oven

图 2 柱温箱控制系统示意图

Fig. 2 System control diagram for the column oven CDS: controller data system; DLL: dynamic link library; RS232: recommended standard 232; Wlan: wireless local area network; Hub: Hub (network); MCU: microcontroller unit; TTL: transistor-transistor logic; LED: light-emitting diode.

表1 柱温箱控温策略

Table 1 Temperature control strategy for the column oven

Application scenario	Room temperature condition	Temperature difference	Instruction
Target temperature>cavity temperature	relatively stable	large	fast heating➝slow heating
	relatively stable	small	slow heating
	slowly rising	large	slow heating
	slowly declining	small	slow heating
Target temperature<cavity temperature	relatively stable	large	fast cooling➝slow cooling
	relatively stable	small	slow cooling
	slowly rising	large	fast cooling→slow cooling
	slowly declining	little	slow cooling
Target temperature≈cavity temperature	relatively stable	minimal	quick switching between
≈room temperature			heating and cooling

表2 精确控温实现方式

Table 2 Implementation methods for precise temperature control

Condition	Operation	Algorithms
A<B	normal heating	heating PID algorithm and dual Peltier following algorithm
A≥B≥D	finely tuned heating	extreme PWM algorithm
B<C	normal cooling	cooling PID algorithm and dual Peltier following algorithm
C≤B≤D	finely tuned cooling	extreme PWM algorithm

图 3 升温测试温度监测走势图

Fig. 3 Temperature monitoring trend chart for heating test

图 4 降温测试温度监测走势图

Fig. 4 Temperature monitoring trend chart for cooling test

图 5 柱温箱从室温升、降至设定温度的测试图

Fig. 5 Test diagram for the column oven during heating and cooling from room temperature to set temperatures

图 6 柱温箱极端升降温测试图

Fig. 6 Test diagram for the column oven during extreme heating and cooling

表3 主要控温点的控温准确度和稳定性

Table 3 Temperature-control accuracy and stability at the main temperature-control points

Temp./℃ ¹⁾	Time/s ²⁾	Accuracy/℃	Stability/℃
4	480	±0.1	±0.1
10	300	±0.1	±0.1
20	240	±0.1	±0.1
25	500	±0.1	±0.1
35	480	±0.1	±0.05
50	240	±0.1	±0.1
60	300	±0.1	±0.1
70	240	±0.1	±0.1
80	280	±0.1	±0.1
90	300	±0.1	±0.1

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