多孔炭材料用于低碳烃分离的研究进展

doi:10.11949/0438-1157.20241222

摘要/Abstract

摘要：

低碳烃(C₁~C₃)混合物的分离与纯化是石油化工行业可持续发展的关键技术环节之一。物理吸附分离技术由于能耗低、易再生和操作简便的特点，在这一领域具有应用潜力。而研发温和条件下低能耗、高选择性吸附分离C₁~C₃的固体吸附材料是关键。多孔炭因其优异的化学稳定性、可调控的孔隙结构和表面化学性质，在低碳烃分离和纯化领域受到广泛关注。结合本课题组研究工作，综述了多孔炭材料在C₁~C₃的天然气(包含煤层气)及烯烃烷烃分离体系的研究进展及分离机理，总结了孔隙结构与表面极性调控方面的研究成果。最后，分析了多孔炭材料在分离低碳烃时所面临的挑战，展望了未来发展方向。

关键词: 多孔炭材料, 低碳烃, 吸附剂, 吸附, 分离

Abstract:

Separation and purification of low carbon hydrocarbon (C₁—C₃) mixtures is one of the key processes for sustainable development of the petrochemical industry. Physical adsorption separation technology has a potential for application in this field due to its advantages of low energy consumption, easy regeneration and simple operation. The key is to develop solid adsorption materials with low energy consumption and high selectivity for adsorption and separation of C₁—C₃ under mild conditions. Porous carbon has attracted extensive attention in the field of separation and purification of low-carbon hydrocarbons due to its excellent chemical stability, adjustable pore structure and surface chemical properties. Based on our recent progress, this paper reviews the research progress and separation mechanisms of porous carbon materials in the separation system of coal bed methane and olefin-alkanes from C₁, C₂, and C₃, with emphasis on the research results relating to the modulation of the pore structure and the surface polarity. Finally, we discuss the challenges faced by porous carbon materials in separating low carbon hydrocarbons, and envisage the future development direction, especially the potential of porous carbon materials in efficient and economic separation technology.

Key words: porous carbons, light hydrocarbon, adsorbents, adsorption, separation

中图分类号:

TQ 028.1

巴雅琪, 吴涛, 邸安頔, 陆安慧. 多孔炭材料用于低碳烃分离的研究进展[J]. 化工学报, 2025, 76(5): 2136-2157.

Yaqi BA, Tao WU, Andi DI, Anhui LU. Progress in porous carbons for efficient separation of gaseous light hydrocarbon[J]. CIESC Journal, 2025, 76(5): 2136-2157.

图/表 18

图1 炭质吸附剂对气体分子的分离机制示意图

Fig.1 Schematic diagram of the separation mechanism of gas molecules by carbon adsorbents

表1 不同气源中CH4及其他气体组分比例［9-15］

Table 1 Ratio of CH4 and other gas components in different gas sources ［9-15］

组分	体积分数/%
组分	天然气	沼气	炼厂气	裂解气	油田气	煤层气	页岩气
CO₂	0~10	25~65	1~2	—	1~36	<5	0~10
CH₄	60~70	40~75	3~25	20~25	30~65	20~50	69~95
C₂H₄	—	—	—	20~25	—	—	—
C₂H₆	5~20	—	2~15	0~5	5~20	—	0-2
C₃H₆	—	—	—	—	—	—	—
C₃H₈	2~15	—	2~15	0-5	2~20	—	0~2
H₂	—	—	50~90	10~20	—	—	0~1
N₂	0~25	—	—	—	0~5	39~70	0~30
其他	0~15	0~10	0~10	25~30	5~25	10~16	0~1

表2 C1~C3气体分子物化性质［23］

Table 2 Table of physical and chemical properties of C1—C3 gas molecules［23］

吸附质	沸点/K	动力学直径/nm	偶极矩/（10^-18 esu·cm）	四极矩/（10^-26 esu·cm²）	极化率/（10^-25 cm³）
CO₂	194.7	0.33	0	4.3	29.1
CH₄	111.6	0.38	0	0	26.0
C₂H₄	169.4	0.42	0	1.5	42.5
C₂H₆	184.6	0.44	0	0.65	44.3~44.7
C₃H₆	225.5	0.46	0.366	—	62.6
C₃H₈	231.0	0.43~0.52	0.084	—	62.9~63.7

图2 CH4/N2分子与样品表面羧基/羟基/醛基之间的相互作用能(a); CH4和N2在官能团上的相互作用能的绝对差值(ΔIE) (b) [27]; (N+O)含量与CO2(c)和CH4(d)捕获能力的关系（298 K，15 kPa条件下，小于0.7 nm的孔容）[28]

Fig.2 Interaction energy between CH4/N2 molecules and the surface carboxylic/hydroxyl/aldehyde groups of the samples (a); Absolute difference of the interaction energies (ΔIE) between CH4 and N2 on functional groups[27] (b); The relationship of (N+O)-contents with CO2 (c) and CH4 (d) capture capacity at 298 K under 15 kPa and <0.7 nm pore volume[28]

图3 (a) 基于 GCMC 模拟的分离系数[37]; (b) CH4对N2的亨利选择性与在0.7~1.3 nm范围内的孔隙体积比单位表面积的相关性[38]

Fig.3 (a) The separation coefficient based on GCMC simulation[37]; (b) Correlation of Henry’s selectivity of CH4 over N2 with pore volume in the range of 0.7—1.3 nm reduced to unit surface area[38]

图4 (a) PCNPs 的原子力显微镜（AFM）图像; (b) 根据273 K时对CO2的吸附测定的微孔尺寸分布和微孔体积（1 Å=0.1 nm）; (c) PCNPs和SCNPs在2 kPa（298 K）条件下吸附CH4的动力学比较; (d) PCNPs、13X分子筛以及CMS对CH4的突破曲线[50]

Fig.4 (a) AFM images of PCNPs and corresponding cross-section analysis for the dashed orange line in the images; (b) Micropore size distribution and micropore volume determined from CO2 adsorption at 273 K; (c) The comparison of kinetic adsorption of CH4 for PCNPs and SCNPs at 2 kPa (298 K); (d) Breakthrough curves of PCNPs, 13X zeolite and CMS for CH4[50]

表3 典型多孔炭吸附剂的理化性质和 CH4/N2 吸附分离性能汇总

Table 3 Summary of the physicochemical properties and CH4/N2 adsorption separation performances of typical porous carbon adsorbents

吸附剂	比表面积/(m²/g)	总孔容/(cm³/g)	微孔孔容/(cm³/g)	吸附量/(mmol/g)		选择性	文献
吸附剂	比表面积/(m²/g)	总孔容/(cm³/g)	微孔孔容/(cm³/g)	CH₄	N₂	选择性	文献
ACK₂N₁	1981	0.83	0.78	3.00^①	0.75^①	7.1^②	[25]
ClCTF-1-650	974	0.37	0.37	1.34	0.32	8.6	[26]
PRC-850	776	0.57	0.19	1.12	—	5.5~9.3^③	[27]
PS-2-450	1089	0.55	0.42	1.13	0.22	7.6	[28]
PZS-900	896	—	—	1.88	0.66	4.5	[29]
10%Ni/C	1367	—	0.37	1.16	0.31	5.3^⑤	[30]
C-PVDC-700	1130	0.45	0.25	1.57	~0.35	5.5^⑤	[38]
GOC-2	1306	0.67	—	1.82	—	5.8	[39]
CGUCs-1-8	1071	0.44	0.37	~1.3	~0.40	5.0	[40]
AC-KP	1549	0.62	0.28	1.87	0.67	6.5^②	[41]
PCNPs	690	—	0.26	1.17	0.28	10.1^④	[50]

图5 (a) 25℃下活性炭对CH4的吸附等温线; （b）通过拟合 0℃下的CO2吸附数据得到的活性炭微孔尺寸分布[64]

Fig.5 (a) Micropore size distributions of the activated carbon, obtained by fitting CO2 adsorption data at 0℃; (b) Methane adsorption isotherms at 25℃ on the activated carbons. The lines represent the fitting of the virial equation[64]

表4 典型多孔炭吸附剂的理化性质和 CO2/CH4 吸附分离性能汇总

Table 4 Summary of the physicochemical properties and CO2/CH4 adsorption separation performances of typical porous carbon adsorbents

吸附剂	比表面积/(m²/g)	总孔容/(cm³/g)	微孔孔容/(cm³/g)	吸附量/(mmol/g)		选择性	文献
吸附剂	比表面积/(m²/g)	总孔容/(cm³/g)	微孔孔容/(cm³/g)	CO₂	CH₄	选择性	文献
SA-1-700	1406	0.72	0.60	4.20	1.53	8.0^①	[53]
NAC-4	1593	0.76	0.21	3.33	0.57	5.8	[56]
GL	310	0.13	0.11	1.62^②	0.45^②	54.0^②	[60]
PS	790	0.33	0.26	3.63^②	1.38^②	15.0^②	[60]
NPC-725	314	0.21	0.14	3.22	1.02	24.3^①	[61]
Glc-Cs	3153	2.06	0.30	22.40^③	10.00^③	27.0^③	[66]

图6 300 K时S掺杂石墨狭缝孔的CH4/C2H4(a), CH4/C2H6(b), CH4/C3H6(c)和CH4/C3H8(d)选择性与压力的关系[75]

Fig. 6 CH4/C2H4(a), CH4/C2H6(b), CH4/C3H6(c) and CH4/C3H8 (d) selectivity of S-graphite slit pore versus the adsorption pressure at 300 K[75]

表5 典型多孔炭吸附剂的理化性质和 C2~3H x /CH4 吸附分离性能汇总

Table 5 Summary of the physicochemical properties and C2-3H x /CH4 adsorption separation performances of typical porous carbon adsorbents

吸附剂	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	吸附量/(mmol/g)			选择性		文献
吸附剂	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	CH₄	C₂H₆	C₃H₈	C₂H₆/CH₄	C₃H₈/CH₄	文献
A-AC-4	3131	1.92	—	1.18	6.59	11.76	15.1^①	88.8^①	[72]
SMC3	1999	0.81	0.69	1.00	5.28	8.39	27.1^①	146.0^①	[73]
C-PVDC-800	1211	0.45	0.45		5.22	5.19	74.9	3387.2	[74]
UC800	3839	2.3	1.13	1.26	7.19	12.02	9.1	41.8	[76]
FCP-1-KC	800	0.4	0.36	1.70	5.10	5.30	71.0^②	386.0^②	[78]
NPC-Li	3579	1.49	—	0.48	7.67	3.55	8.0	336.0	[79]

图7 (a) 最小分子尺寸从0.33 nm（CO2）到0.5 nm（i-C4H10）在273 K和N2在77 K的条件下在PDA-C900上的吸附平衡等温线; (b) 根据Dubinin-Astakhov方程计算的不同探针气体在PDA-C x 上的孔隙体积（从左到右的数据点分别由PDA-C x 上的CO2、Ar、C2H4、C3H6、C2H6、C3H8、CF4和i-C4H10等探针气体计算得出。而富含杂原子的PDA-C300和PDA-C500由于主客体相互作用较强，因此不包括极化率较高的C3H6、C3H8和i-C4H10）; (c) PDA-C x 的孔径分布（y轴的孔隙体积差(∆V)是由连续尺寸的探针得到的。从VCO2中减去VAr，从VAr中减去VC2H4，以此类推）[80]

Fig.7 (a) Sorption equilibrium isotherms of various gas probes with minimum molecular dimensions ranging from 0.33 nm (CO2) to 0.5 nm (i-C4H10) at 273 K and N2 at 77 K on PDA-C900 materials; (b) The pore volumes of PDA-C x calculated from different probe gases based on the Dubinin-Astakhov equation (the data points from left to right were calculated from probing gases of CO2, Ar, C2H4, C3H6, C2H6, C3H8, CF4, and i-C4H10 for PDA-C x . While C3H6, C3H8, and i-C4H10 with high polarizability were excluded for heteroatom-rich PDA-C300 and PDA-C500 due to stronger host-guest interaction); (c) The pore size distributions of PDA-C x (the differential pore volume (∆V) of y-axis was obtained from probes with successive sizes. VAr was subtracted from VCO2, VC2H4 from VAr, and so on)[80]

图8 (a) 基于分子印迹概念的三种类型聚合物单体的结构示意图; (b) MP-B、MP-P和MP-E在Ar气氛中的DSC曲线; (c) MC-E（左）、MC-P（中）和MC-B（右）在298 K下对C2H4/C2H6的吸附-脱附等温线[83]

Fig.8 (a) Structure schematic of the three types of polymer monomers with the incorporated amines with different carbon chains; (b) The DSC curves of MP-B, MP-P, and MP-E in argon atmosphere; (c) C2H4/C2H6 adsorption-desorption isotherms for MC-E (left), MC-P (medium), and MC-B (right) at 298 K[83]

图9 FAU-ZTC (a)、EMT-ZTC (b)和beta-ZTC (c)的结构示意图和石英模型; 303 K时吸附剂对乙烷和乙烯的吸附等温线：FAU-ZTC (d), EMT-ZTC (e), beta-ZTC (f)[89]

Fig.9 Schematic structures and schwarzite models of FAU-ZTC (a), EMT-ZTC (b), and beta-ZTC (c); Adsorption isotherms of ethane and ethylene by adsorbents at 303 K: FAU-ZTC (d), EMT-ZTC (e), beta-ZTC (f)[89]

表6 典型多孔炭吸附剂的理化性质和C2H4/C2H6吸附分离性能汇总

Table 6 Summary of the physicochemical properties and C2H4/C2H6 adsorption separation performances of typical porous carbon adsorbents

名称	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	吸附量/(mmol/g)		扩散速率/s^-1		选择性	文献
名称	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	C₂H₄	C₂H₆	C₂H₄	C₂H₆	选择性	文献
PDA-C900	400^①	—	0.21^①	2.25	0.091	4.13 × 10^-3	—	24.7	[80]
CNC-700	317^①	—	0.16^①	1.44	0.093	—	—	15.2	[81]
d-CMS-3	—	—	—	1.52	0.14	2.0 × 10^-3	1 × 10^-5	10.9	[82]
MC-E	317	—	—	2.66	0.17	—	—	15.6	[83]
CMK-3	1182	1.19	—	2.90^②	3.10^②	—	—	0.9	[84]
8CuCl/CMK-3	303	0.37	—	3.60^②	1.30^②	—	—	2.8	[84]
CuCl(8.0)/AC	224	0.38	—	2.60^②	0.70^②	—	—	3.7	[85]
50CPDA@A-ACs	1799	0.72	—	6.30	7.10	—	—	3.0^③	[86]
MGA-750-3	3189	1.48	0.93	5.70	7.00	—	—	4.2^③	[87]
C-PDA-3	3160	1.51	—	6.57	5.10	—	—	1.9^④	[88]
beta-ZTC	3200	—	—	7.30^②	4.90^②	—	—	1.7^⑤	[89]
EMT-ZTC	2980	—	—	5.90^②	4.10^②	—	—	1.6^⑤
FAU-ZTC	2700	—	—	5.00^②	4.00^②	—	—	1.5^⑤

图10 (a) 带筛分层的木框结构炭的制备过程示意图; (b) 木框、聚苯并𫫇嗪聚合物涂层木材 PBZ@W 和带筛分层的木框结构炭 WSCS 的扫描电镜照片; (c) 在298 K和100 kPa条件下，以2 ml/min的流速测量等摩尔二元混合物C3H6/C3H8的WSC、WSCS和PDC的穿透曲线（t1为C3H8的穿透点; t2为C3H6的穿透点）[91]

Fig.10 (a) Schematic preparation procedures for the wood frame structured carbons with sieving layer, WSCS; (b) SEM images of wood frame, polybenzoxazine polymer coated wood, PBZ@W, and wood frame structured carbons with sieving layer, WSCS; (c) Breakthrough curves of WSC, WSCS, and PDC for equimolar binary mixture C3H6/C3H8 with a flow rate of 2 ml/min at 298 K and 100 kPa (t1 is the breakthrough point of C3H8; t2 is the breakthrough point of C3H6)[91]

图11 (a) MC-wiggle 的合成示意图; (b) 87 K时的Ar吸附等温线及(c)相应的孔径分布; (d) 298 K时C3H6/C3H8 的时间分辨吸附曲线; (e) 在环境条件下，以 2 ml/min的流速对等摩尔C3H6/C3H8二元混合物的气体进料的穿透曲线; (f) C3H6/C3H8在摆动介孔中的选择性吸附示意图[98]

Fig.11 (a) Synthesis schematic of MC-wiggle; (b) Ar adsorption isotherms at 87 K and (c) corresponding pore size distributions; (d) Time-resolved adsorption profiles for C3H6/C3H8 at 298 K; (e) Breakthrough curves for gas feed of equimolar binary mixture of C3H6/C3H8 with a flow rate of 2 ml/min under ambient conditions; (f) Illustration of the proposed selective adsorption of C3H6/C3H8 in wiggling mesopores[98]

表7 典型多孔炭吸附剂的理化性质和C3H6/C3H8吸附分离性能汇总

Table 7 Summary of the physicochemical properties and C3H6/C3H8 adsorption separation performances of typical porous carbon adsorbents

吸附剂	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	吸附量/(mmol/g)		扩散速率/s^-1		选择性	文献
吸附剂	比表面积/ (m²/g)	总孔容/ (cm³/g)	微孔孔容/ (cm³/g)	C₃H₆	C₃H₈	C₃H₆	C₃H₈	选择性	文献
PDA-C800	375^①		0.19	1.98	0.054	7.57×10^-3		36.7	[80]
SCMS-0.2-800			0.24	2.54	0.08			31.8	[90]
SCMS-1-800				2.22	0.02			111.0	[90]
WSCS	19^②		0.18	1.72	0.17	2.68×10^-3	6.26×10^-5	10.1	[91]
Carbon-0.2	680		0.18	2.14	0.54	5.2×10^-3	1.1×10^-4	4.0	[92]
SUC-900	458	0.23		2.0	0.055			36.4	[93]
CMS-850	382	0.13		1.53^③	0.66			2.3	[94]
CNP-3				3.03	1.86	9.6×10^-3	8.8×10^-4	1.6	[95]
SCS-800		0.18		2.0	0.25	1.34×10^-4	1.18×10^-6	8.0	[96]
MCC-micro	479^②	0.22^②	0.16^②	2.4	1.1	1.26×10^-2	2.76×10^-5	2.2	[97]
MC-wiggle	413^②			2.6	1.5	4.2×10^-3	2.1×10^-4	1.7	[98]
C-CDMOF-2-700	371^①	0.19^①		1.97	0.13	3.15×10^-3④		15.1	[103]
MFF_8				1.4	2.9	1.2×10^-1	1.4×10^-1	2.1	[106]

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