Patent
US 12,539,497 B2METHOD FOR PREPARING TUBULAR GRAPHENE COMPOSITE MEMBRANE
Wanqin Jin, Kang Huang, Gongping Liu
Nanjing University of Technology, Nanjing (CN)·Feb. 3, 2026·US
Copyright © 2026 Matter42. All rights reserved.
Patent
Atlas literature
Patent
US 12,539,497 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a schematic diagram of the membrane preparing device;
FIG. 2 is a picture of the real single tubular support in Embodiment 1;
FIG. 3 is a picture of the real 19-channel tubular support in Embodiment 2;
FIG. 4 is a picture of the real single tubular hollow fiber in Embodiment 3;
FIG. 5 is an electronic microscope photograph of the surface of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 6 is an electronic microscope photograph of the cross section of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 7 is a result figure of methanol/water separation of the oxidized graphene membrane prepared in Embodiment 3.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method for preparing tubular graphene composite membrane through vacuum suction; the specific steps are as follows: (1) Preprocessing of a support: selecting a tubular ceramic membrane as a support; drying it after flushing with water; sealing one end of the support with a sealant and connecting the other end of the support to a vacuum pump with a pipeline through a surge flask and a pressure regulating valve; (2) Preparation of a membrane preparing solution: dis-solving a graphene material into a solvent; obtaining a uniformly dispersed membrane preparing solution through ultrasonic processing; (3) Preparation of membrane: immersing the tubular support processed in Step (1) in the membrane prepar-ing solution; starting the vacuum pump and holding for 1-12 hours after the pressure is stabilized; (4) Placing the prepared membrane in a vacuum drying oven and dry the membrane under 25° C.-50° C. 5 6
The method according to claim 1, wherein the tubular ceramic membrane support is a single tubular support, a multi-channel tubular support, a single tubular hollow fiber support, a multi-channel hollow fiber or a honeycomb ceramic support.
The method according to claim 1, wherein a material of the tubular ceramic membrane support is one or two of ZnO, Al₂O3, TiO₂ or ZrO2.
The method according to claim 1, wherein, the sealant is one of polyurethane sealant, phenolic resin sealant, sili-cone sealant, vulcanized silicone sealant, epoxy resin sealant or polyacrylic resin sealant.
The method according to claim 1, wherein, the solvent is one of water, ethyl alcohol, DMF, methyl alcohol or DMSO.
The method according to claim 1, wherein, the gra-phene material is one of graphene, sulfhydrylated graphene, oxidized graphene, hydroxylated graphene, aminated gra-phene, or carboxylated graphene.
The method according to claim 1, wherein, the con-centration of the membrane preparing solution is 0.001-1 mg/mL.
The method according to claim 1, wherein, the pressure of the vacuum pump is 100-2000 Pa. ∗ ∗ ∗ ∗ ∗
Embodiments described in the patent, grouped by the materials and process steps they use.
4 materials1 process step
Graphene membrane prepared on the surface of a single tubular ZrO₂/Al₂O₃ ceramic support using vacuum suction. Graphene dissolved in DMF at 0.001 mg/mL, ultrasonicated, support immersed and vacuum held at 1000 Pa for 12 hours, dried at 40°C. Single-component gas characterization showed H₂/N₂ ideal selectivity of 67, H₂/CO₂ of 85, H₂/CH₄ of 139.
4 materials1 process step
Aminated graphene membrane prepared on the surface of a 19-channel TiO₂/Al₂O₃ tubular ceramic support. Aminated graphene dissolved in ethyl alcohol at 0.03 mg/mL, ultrasonicated, vacuum held at 2000 Pa for 5 hours, dried at 25°C. CO₂/N₂ ideal selectivity of 35 and CO₂/CH₄ of 72.
3 materials1 process step
Oxidized graphene membrane prepared on a single tubular hollow fiber Al₂O₃ support. Oxidized graphene dissolved in water at 0.1 mg/mL, ultrasonicated, vacuum held at 100 Pa for 3 hours, dried at 50°C. Methanol/water pervaporation showed max. separation factor of 42.
3 materials1 process step
Carboxylated graphene membrane prepared on a honeycomb ZnO₂ ceramic support. Hydroxylated graphene dissolved in DMSO at 1 mg/mL, ultrasonicated, vacuum held at 500 Pa for 1 hour, dried at 30°C. Ethyl alcohol/water pervaporation showed max. separation factor of 63.
Layer stacks claimed or described, ordered top of device to substrate.
tubular graphene composite membrane
Materials described outside the worked examples.
tubular ceramic membrane
graphene material
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
H2/N2 ideal selectivity | 67 dimensionless | graphene |
H2/CO2 ideal selectivity | 85 dimensionless |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 6
Patent
Atlas literature
Patent
US 12,539,497 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a schematic diagram of the membrane preparing device;
FIG. 2 is a picture of the real single tubular support in Embodiment 1;
FIG. 3 is a picture of the real 19-channel tubular support in Embodiment 2;
FIG. 4 is a picture of the real single tubular hollow fiber in Embodiment 3;
FIG. 5 is an electronic microscope photograph of the surface of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 6 is an electronic microscope photograph of the cross section of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 7 is a result figure of methanol/water separation of the oxidized graphene membrane prepared in Embodiment 3.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method for preparing tubular graphene composite membrane through vacuum suction; the specific steps are as follows: (1) Preprocessing of a support: selecting a tubular ceramic membrane as a support; drying it after flushing with water; sealing one end of the support with a sealant and connecting the other end of the support to a vacuum pump with a pipeline through a surge flask and a pressure regulating valve; (2) Preparation of a membrane preparing solution: dis-solving a graphene material into a solvent; obtaining a uniformly dispersed membrane preparing solution through ultrasonic processing; (3) Preparation of membrane: immersing the tubular support processed in Step (1) in the membrane prepar-ing solution; starting the vacuum pump and holding for 1-12 hours after the pressure is stabilized; (4) Placing the prepared membrane in a vacuum drying oven and dry the membrane under 25° C.-50° C. 5 6
The method according to claim 1, wherein the tubular ceramic membrane support is a single tubular support, a multi-channel tubular support, a single tubular hollow fiber support, a multi-channel hollow fiber or a honeycomb ceramic support.
The method according to claim 1, wherein a material of the tubular ceramic membrane support is one or two of ZnO, Al₂O3, TiO₂ or ZrO2.
The method according to claim 1, wherein, the sealant is one of polyurethane sealant, phenolic resin sealant, sili-cone sealant, vulcanized silicone sealant, epoxy resin sealant or polyacrylic resin sealant.
The method according to claim 1, wherein, the solvent is one of water, ethyl alcohol, DMF, methyl alcohol or DMSO.
The method according to claim 1, wherein, the gra-phene material is one of graphene, sulfhydrylated graphene, oxidized graphene, hydroxylated graphene, aminated gra-phene, or carboxylated graphene.
The method according to claim 1, wherein, the con-centration of the membrane preparing solution is 0.001-1 mg/mL.
The method according to claim 1, wherein, the pressure of the vacuum pump is 100-2000 Pa. ∗ ∗ ∗ ∗ ∗
Embodiments described in the patent, grouped by the materials and process steps they use.
4 materials1 process step
Graphene membrane prepared on the surface of a single tubular ZrO₂/Al₂O₃ ceramic support using vacuum suction. Graphene dissolved in DMF at 0.001 mg/mL, ultrasonicated, support immersed and vacuum held at 1000 Pa for 12 hours, dried at 40°C. Single-component gas characterization showed H₂/N₂ ideal selectivity of 67, H₂/CO₂ of 85, H₂/CH₄ of 139.
4 materials1 process step
Aminated graphene membrane prepared on the surface of a 19-channel TiO₂/Al₂O₃ tubular ceramic support. Aminated graphene dissolved in ethyl alcohol at 0.03 mg/mL, ultrasonicated, vacuum held at 2000 Pa for 5 hours, dried at 25°C. CO₂/N₂ ideal selectivity of 35 and CO₂/CH₄ of 72.
3 materials1 process step
Oxidized graphene membrane prepared on a single tubular hollow fiber Al₂O₃ support. Oxidized graphene dissolved in water at 0.1 mg/mL, ultrasonicated, vacuum held at 100 Pa for 3 hours, dried at 50°C. Methanol/water pervaporation showed max. separation factor of 42.
3 materials1 process step
Carboxylated graphene membrane prepared on a honeycomb ZnO₂ ceramic support. Hydroxylated graphene dissolved in DMSO at 1 mg/mL, ultrasonicated, vacuum held at 500 Pa for 1 hour, dried at 30°C. Ethyl alcohol/water pervaporation showed max. separation factor of 63.
Layer stacks claimed or described, ordered top of device to substrate.
tubular graphene composite membrane
Materials described outside the worked examples.
tubular ceramic membrane
graphene material
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
H2/N2 ideal selectivity | 67 dimensionless | graphene |
H2/CO2 ideal selectivity | 85 dimensionless |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 6
Patent
Atlas literature
Patent
US 12,539,497 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a schematic diagram of the membrane preparing device;
FIG. 2 is a picture of the real single tubular support in Embodiment 1;
FIG. 3 is a picture of the real 19-channel tubular support in Embodiment 2;
FIG. 4 is a picture of the real single tubular hollow fiber in Embodiment 3;
FIG. 5 is an electronic microscope photograph of the surface of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 6 is an electronic microscope photograph of the cross section of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 7 is a result figure of methanol/water separation of the oxidized graphene membrane prepared in Embodiment 3.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method for preparing tubular graphene composite membrane through vacuum suction; the specific steps are as follows: (1) Preprocessing of a support: selecting a tubular ceramic membrane as a support; drying it after flushing with water; sealing one end of the support with a sealant and connecting the other end of the support to a vacuum pump with a pipeline through a surge flask and a pressure regulating valve; (2) Preparation of a membrane preparing solution: dis-solving a graphene material into a solvent; obtaining a uniformly dispersed membrane preparing solution through ultrasonic processing; (3) Preparation of membrane: immersing the tubular support processed in Step (1) in the membrane prepar-ing solution; starting the vacuum pump and holding for 1-12 hours after the pressure is stabilized; (4) Placing the prepared membrane in a vacuum drying oven and dry the membrane under 25° C.-50° C. 5 6
The method according to claim 1, wherein the tubular ceramic membrane support is a single tubular support, a multi-channel tubular support, a single tubular hollow fiber support, a multi-channel hollow fiber or a honeycomb ceramic support.
The method according to claim 1, wherein a material of the tubular ceramic membrane support is one or two of ZnO, Al₂O3, TiO₂ or ZrO2.
The method according to claim 1, wherein, the sealant is one of polyurethane sealant, phenolic resin sealant, sili-cone sealant, vulcanized silicone sealant, epoxy resin sealant or polyacrylic resin sealant.
The method according to claim 1, wherein, the solvent is one of water, ethyl alcohol, DMF, methyl alcohol or DMSO.
The method according to claim 1, wherein, the gra-phene material is one of graphene, sulfhydrylated graphene, oxidized graphene, hydroxylated graphene, aminated gra-phene, or carboxylated graphene.
The method according to claim 1, wherein, the con-centration of the membrane preparing solution is 0.001-1 mg/mL.
The method according to claim 1, wherein, the pressure of the vacuum pump is 100-2000 Pa. ∗ ∗ ∗ ∗ ∗
Embodiments described in the patent, grouped by the materials and process steps they use.
4 materials1 process step
Graphene membrane prepared on the surface of a single tubular ZrO₂/Al₂O₃ ceramic support using vacuum suction. Graphene dissolved in DMF at 0.001 mg/mL, ultrasonicated, support immersed and vacuum held at 1000 Pa for 12 hours, dried at 40°C. Single-component gas characterization showed H₂/N₂ ideal selectivity of 67, H₂/CO₂ of 85, H₂/CH₄ of 139.
4 materials1 process step
Aminated graphene membrane prepared on the surface of a 19-channel TiO₂/Al₂O₃ tubular ceramic support. Aminated graphene dissolved in ethyl alcohol at 0.03 mg/mL, ultrasonicated, vacuum held at 2000 Pa for 5 hours, dried at 25°C. CO₂/N₂ ideal selectivity of 35 and CO₂/CH₄ of 72.
3 materials1 process step
Oxidized graphene membrane prepared on a single tubular hollow fiber Al₂O₃ support. Oxidized graphene dissolved in water at 0.1 mg/mL, ultrasonicated, vacuum held at 100 Pa for 3 hours, dried at 50°C. Methanol/water pervaporation showed max. separation factor of 42.
3 materials1 process step
Carboxylated graphene membrane prepared on a honeycomb ZnO₂ ceramic support. Hydroxylated graphene dissolved in DMSO at 1 mg/mL, ultrasonicated, vacuum held at 500 Pa for 1 hour, dried at 30°C. Ethyl alcohol/water pervaporation showed max. separation factor of 63.
Layer stacks claimed or described, ordered top of device to substrate.
tubular graphene composite membrane
Materials described outside the worked examples.
tubular ceramic membrane
graphene material
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
H2/N2 ideal selectivity | 67 dimensionless | graphene |
H2/CO2 ideal selectivity | 85 dimensionless |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 6
Patent
Atlas literature
Patent
US 12,539,497 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a schematic diagram of the membrane preparing device;
FIG. 2 is a picture of the real single tubular support in Embodiment 1;
FIG. 3 is a picture of the real 19-channel tubular support in Embodiment 2;
FIG. 4 is a picture of the real single tubular hollow fiber in Embodiment 3;
FIG. 5 is an electronic microscope photograph of the surface of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 6 is an electronic microscope photograph of the cross section of the oxidized graphene membrane prepared in Embodiment 3;
FIG. 7 is a result figure of methanol/water separation of the oxidized graphene membrane prepared in Embodiment 3.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method for preparing tubular graphene composite membrane through vacuum suction; the specific steps are as follows: (1) Preprocessing of a support: selecting a tubular ceramic membrane as a support; drying it after flushing with water; sealing one end of the support with a sealant and connecting the other end of the support to a vacuum pump with a pipeline through a surge flask and a pressure regulating valve; (2) Preparation of a membrane preparing solution: dis-solving a graphene material into a solvent; obtaining a uniformly dispersed membrane preparing solution through ultrasonic processing; (3) Preparation of membrane: immersing the tubular support processed in Step (1) in the membrane prepar-ing solution; starting the vacuum pump and holding for 1-12 hours after the pressure is stabilized; (4) Placing the prepared membrane in a vacuum drying oven and dry the membrane under 25° C.-50° C. 5 6
The method according to claim 1, wherein the tubular ceramic membrane support is a single tubular support, a multi-channel tubular support, a single tubular hollow fiber support, a multi-channel hollow fiber or a honeycomb ceramic support.
The method according to claim 1, wherein a material of the tubular ceramic membrane support is one or two of ZnO, Al₂O3, TiO₂ or ZrO2.
The method according to claim 1, wherein, the sealant is one of polyurethane sealant, phenolic resin sealant, sili-cone sealant, vulcanized silicone sealant, epoxy resin sealant or polyacrylic resin sealant.
The method according to claim 1, wherein, the solvent is one of water, ethyl alcohol, DMF, methyl alcohol or DMSO.
The method according to claim 1, wherein, the gra-phene material is one of graphene, sulfhydrylated graphene, oxidized graphene, hydroxylated graphene, aminated gra-phene, or carboxylated graphene.
The method according to claim 1, wherein, the con-centration of the membrane preparing solution is 0.001-1 mg/mL.
The method according to claim 1, wherein, the pressure of the vacuum pump is 100-2000 Pa. ∗ ∗ ∗ ∗ ∗
Embodiments described in the patent, grouped by the materials and process steps they use.
4 materials1 process step
Graphene membrane prepared on the surface of a single tubular ZrO₂/Al₂O₃ ceramic support using vacuum suction. Graphene dissolved in DMF at 0.001 mg/mL, ultrasonicated, support immersed and vacuum held at 1000 Pa for 12 hours, dried at 40°C. Single-component gas characterization showed H₂/N₂ ideal selectivity of 67, H₂/CO₂ of 85, H₂/CH₄ of 139.
4 materials1 process step
Aminated graphene membrane prepared on the surface of a 19-channel TiO₂/Al₂O₃ tubular ceramic support. Aminated graphene dissolved in ethyl alcohol at 0.03 mg/mL, ultrasonicated, vacuum held at 2000 Pa for 5 hours, dried at 25°C. CO₂/N₂ ideal selectivity of 35 and CO₂/CH₄ of 72.
3 materials1 process step
Oxidized graphene membrane prepared on a single tubular hollow fiber Al₂O₃ support. Oxidized graphene dissolved in water at 0.1 mg/mL, ultrasonicated, vacuum held at 100 Pa for 3 hours, dried at 50°C. Methanol/water pervaporation showed max. separation factor of 42.
3 materials1 process step
Carboxylated graphene membrane prepared on a honeycomb ZnO₂ ceramic support. Hydroxylated graphene dissolved in DMSO at 1 mg/mL, ultrasonicated, vacuum held at 500 Pa for 1 hour, dried at 30°C. Ethyl alcohol/water pervaporation showed max. separation factor of 63.
Layer stacks claimed or described, ordered top of device to substrate.
tubular graphene composite membrane
Materials described outside the worked examples.
tubular ceramic membrane
graphene material
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
H2/N2 ideal selectivity | 67 dimensionless | graphene |
H2/CO2 ideal selectivity | 85 dimensionless |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 6
solvent
ZnO
Al₂O₃
TiO₂
ZrO₂
methyl alcohol
CH₃OH
sulfhydrylated graphene
carboxylated graphene
H2/CH4 ideal selectivity | 139 dimensionless | graphene |
CO2/N2 ideal selectivity | 35 dimensionless | aminated graphene |
CO2/CH4 ideal selectivity | 72 dimensionless | aminated graphene |
methanol/water pervaporation max. separation factor | 42 dimensionless | oxidized graphene |
ethyl alcohol/water pervaporation max. separation factor | 63 dimensionless | hydroxylated graphene |
Temperature | ≤ 40 °C | — |
Temperature | ≤ 25 °C | — |
Temperature | ≤ 50 °C | — |
Temperature | ≤ 30 °C | — |
Duration | 1–12 hours | — |
Pressure | 100–2000 Pa | — |
Cited non-patent literature · 3
solvent
ZnO
Al₂O₃
TiO₂
ZrO₂
methyl alcohol
CH₃OH
sulfhydrylated graphene
carboxylated graphene
H2/CH4 ideal selectivity | 139 dimensionless | graphene |
CO2/N2 ideal selectivity | 35 dimensionless | aminated graphene |
CO2/CH4 ideal selectivity | 72 dimensionless | aminated graphene |
methanol/water pervaporation max. separation factor | 42 dimensionless | oxidized graphene |
ethyl alcohol/water pervaporation max. separation factor | 63 dimensionless | hydroxylated graphene |
Temperature | ≤ 40 °C | — |
Temperature | ≤ 25 °C | — |
Temperature | ≤ 50 °C | — |
Temperature | ≤ 30 °C | — |
Duration | 1–12 hours | — |
Pressure | 100–2000 Pa | — |
Cited non-patent literature · 3
solvent
ZnO
Al₂O₃
TiO₂
ZrO₂
methyl alcohol
CH₃OH
sulfhydrylated graphene
carboxylated graphene
H2/CH4 ideal selectivity | 139 dimensionless | graphene |
CO2/N2 ideal selectivity | 35 dimensionless | aminated graphene |
CO2/CH4 ideal selectivity | 72 dimensionless | aminated graphene |
methanol/water pervaporation max. separation factor | 42 dimensionless | oxidized graphene |
ethyl alcohol/water pervaporation max. separation factor | 63 dimensionless | hydroxylated graphene |
Temperature | ≤ 40 °C | — |
Temperature | ≤ 25 °C | — |
Temperature | ≤ 50 °C | — |
Temperature | ≤ 30 °C | — |
Duration | 1–12 hours | — |
Pressure | 100–2000 Pa | — |
Cited non-patent literature · 3
solvent
ZnO
Al₂O₃
TiO₂
ZrO₂
methyl alcohol
CH₃OH
sulfhydrylated graphene
carboxylated graphene
H2/CH4 ideal selectivity | 139 dimensionless | graphene |
CO2/N2 ideal selectivity | 35 dimensionless | aminated graphene |
CO2/CH4 ideal selectivity | 72 dimensionless | aminated graphene |
methanol/water pervaporation max. separation factor | 42 dimensionless | oxidized graphene |
ethyl alcohol/water pervaporation max. separation factor | 63 dimensionless | hydroxylated graphene |
Temperature | ≤ 40 °C | — |
Temperature | ≤ 25 °C | — |
Temperature | ≤ 50 °C | — |
Temperature | ≤ 30 °C | — |
Duration | 1–12 hours | — |
Pressure | 100–2000 Pa | — |
Cited non-patent literature · 3