CN111171856A - Application of carbon molecular sieve membrane to C4-C6Process for separating n-isoparaffin - Google Patents
Application of carbon molecular sieve membrane to C4-C6Process for separating n-isoparaffin Download PDFInfo
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- CN111171856A CN111171856A CN201811343663.8A CN201811343663A CN111171856A CN 111171856 A CN111171856 A CN 111171856A CN 201811343663 A CN201811343663 A CN 201811343663A CN 111171856 A CN111171856 A CN 111171856A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
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Abstract
The invention discloses a carbon molecular sieve membrane for C4‑C6A method for separating n-isoparaffin, comprising the steps of: (1) sealing the carbon molecular sieve membrane in the membrane component; (2) the membrane component is arranged in the heat conductor to maintain constant temperature; (3) introducing a saturated vapor mixture of normal isoparaffin into the raw material side; (4) applying a pressure difference across the membrane; (5) the components on the permeation side are carried by the purge gas and collected or condensed in a collector; (6) the components on the permeation side are subjected to online or offline gas chromatography to detect the composition and the concentration of each component. The present invention is directed to C4‑C6The existing membrane separation method has the problems of low performance and short service life, and a high-efficiency carbon molecular sieve membrane is developed and used for C4‑C6The separation application of n-isoparaffin. Has important significance for the efficient separation and the optimized utilization of petroleum-based platform compounds.
Description
Technical Field
The invention belongs to the field of inorganic membrane materials, and particularly relates to a carbon molecular sieve membrane for C4-C6A process for separating n-isoparaffin.
Background
The carbon molecular sieve membrane is prepared by pyrolysis and carbonization of a polymer membrane material under certain conditions, and is a novel inorganic membrane material. CMSMs have higher thermochemical stability and ultrahigh gas separation selectivity, do not have the plasticizing phenomenon of a polymer membrane, are typical membrane types which successfully break through the upper limit of Robeson, and are considered to be one of the most promising gas separation membrane materials in the field of gas membrane separation (Burns R.L., KorosW.J.J.Membr.Sci.,2003,211: 299-309). Most carbon molecular sieve membranes with separation performance have a short-range ordered turbostratic carbon structure, and the pore channels of the materials are formed by stacking defects among microcrystals. Carbon molecular sieves are generally considered to have a distribution of "slit-shaped" (slit-like) pore structures.
A great deal of patent and literature reports at present show that the carbon molecular sieve membrane has unique advantages in the aspect of permanent small molecule gas (such as hydrogen, carbon dioxide, nitrogen, methane and the like) separation. The patent (CN 107635646) discloses a method for manufacturing a carbon molecular sieve membrane with selective permeability between permanent small molecule gases, such as hydrogen (carbon dioxide, nitrogen) and methane. The use of carbon molecular sieve membranes for the sieving of permanent small molecule gas carbon dioxide and methane is reported in the literature (Kiyono m., Williams p.j., Koros w.j.carbon,2010,48:4432-4441.) and the use of carbon molecular sieve membranes for the efficient separation of permanent small molecule gas oxygen from nitrogen is reported in the literature (Jiao w.m., Ban y.j., shiz.x., et al, chem.commun.,2016,52: 13779-13782.). Unfortunately, the separation application of carbon molecular sieve membrane mainly focuses on permanent small molecule gas, and is very limited, and has no relation to the separation of n-isoparaffin with carbon number above 4.
N-isoparaffins containing 4 to 6 carbon atoms (i.e. C)4-C6N-isoparaffins) are important products in petroleum cracking processes, and are also well known petroleum-based platform compounds. Wherein, the normal paraffin can be used as raw material for preparing ethylene by cracking, and the isoparaffin can be used as anti-explosion component of gasoline. However, C4-C6The physical and chemical properties of the n-isoparaffin are very close, and the energy consumption of the traditional separation method is extremely high. The membrane separation method has low energy consumption and high efficiency, and is a very competitive separation method. However, C4-C6The normal isoparaffin has larger molecular size and extremely low saturated vapor pressure, and is often adsorbed and condensed on a membrane material, so that the blockage of micropores is extremely serious, and the conventional membrane separation method is often low in performance and short in service life. If a high-efficiency membrane separation method can be developed based on a carbon molecular sieve membrane, important industrial application value is generated for the optimized utilization of petroleum-based platform compounds.
The invention content is as follows:
the invention aims to break through the defects of the prior art and provide a carbon molecular sieve membrane for C4-C6The application of n-isoparaffin separation is disclosed.
The purpose of the invention is realized by the following technical scheme that the carbon molecular sieve membrane is used for C4-C6A method for separating n-isoparaffin, comprising the steps of:
(1) sealing the carbon molecular sieve membrane in the membrane component;
the membrane component is made of stainless steel, the upper half part of the membrane component is provided with a raw material side air inlet and a interception side air outlet, the lower half part of the membrane component is provided with a sweeping side air inlet and a permeation side air outlet, the interior of the membrane component is used for packaging a membrane, and the whole membrane component is arranged in the heat conductor; the gas outlet of the permeation side is connected with a gas chromatograph for detecting the content of the components of the permeation side.
(2) The membrane component is arranged in the heat conductor to maintain constant temperature;
wherein the temperature of the heat conductor is-20 to 200 ℃.
(3) Introducing a saturated vapor mixture of normal isoparaffin into the raw material side;
wherein the n-isoparaffin mixture is one of n-butane/isobutane, n-pentane/isopentane, n-pentane/neopentane, n-hexane/2-methylpentane, n-hexane/3-methylpentane, n-hexane/2, 3-dimethylbutane, and n-hexane/2, 2-dimethylbutane mixtures; the mass concentration ratio of the n-alkane to the iso-alkane is y:1, and y is 0.005-0.995.
The invention is not limited to the generation mode of saturated vapor, and can be generated by the modes of reducing pressure of a compressed liquid steel cylinder, heating or carrying inert gas and the like.
(4) Applying a pressure difference across the membrane;
wherein the pressure difference can be realized by applying pressure on one side or both sides of the feed side or the permeation side, and the pressure on the feed side is 0-1000000 Pa; the pressure applied to the permeation side is 0.01 to 100000 Pa.
(5) The components on the permeation side are carried by the purge gas and collected or condensed in a collector;
wherein the purge gas is Ar, He or N2One of (1), purge gasThe flow rate is 0.1-200 mL/min; the condensation temperature is-300-20 ℃.
(6) The components on the permeation side are subjected to online or offline gas chromatography to detect the composition and the concentration of each component.
The carbon molecular sieve membrane is a self-supporting symmetrical membrane, and the effective thickness of the membrane layer is 0.1-100 mu m.
The carbon molecular sieve membrane is a support membrane, and the effective thickness of the membrane layer is 0.01-10 mu m.
The carbon molecular sieve membrane is prepared from one of polysulfone, polyethersulfone, polyimide, polyetherimide, polyaryletherketone, polybenzimidazole, polycarbonate, polyphenylene sulfide, polylactic acid or polymethyl methacrylate.
It is another object of the present invention to provide a self-supporting and supported carbon molecular sieve membrane for C4-C6The separation application of n-isoparaffin. The invention has the advantages that: the carbon molecular sieve membrane is applied to the separation of n-isoparaffin containing 4-6 carbon atoms, and has important significance for the efficient separation and optimized utilization of petroleum-based platform compounds.
Drawings
FIG. 1 is a schematic cross-sectional view of a membrane module;
FIG. 2C4-C6A schematic diagram of a normal isoparaffin saturated vapor mixture separation device;
wherein: 1 is the membrane, 2 is the sealed O circle of silicon rubber, 3 is stainless steel membrane module, 4 is raw materials side gas inlet, 5 is holding back the side gas outlet, 6 is sweeping side gas inlet, 7 is the infiltration side gas outlet, 8 is the heat conduction ware, 9 is detection terminals such as gas chromatography or mass spectrum, 10 is gaseous A, 11 is gaseous B, 12 is sweep gas C.
Detailed Description
The following examples and drawings are provided to further illustrate the embodiments of the present invention, but the embodiments of the present invention are not limited thereto.
C4-C6The normal isoparaffin saturated vapor mixture separation device is schematically shown in figures 1 and 2, and the interior of the device is provided with a membrane component 3 for C4-C6Separating saturated vapor mixture of n-isoparaffin, placing membrane module inIn the heat conducting device 8, the outside is a gas chromatograph 9, and the gas chromatograph is connected with a permeation side outlet of the membrane component and is used for detecting the content of components on the permeation side. The membrane 1 is fixed in the middle of a stainless steel membrane component 3 through a silicon rubber sealing O ring 2, the upper half part of the membrane is provided with a raw material side air inlet 4 and a interception side air outlet 5, the lower half part of the membrane is provided with a sweeping side air inlet 6 and a permeation side air outlet 7, and the whole membrane component is arranged in a heat conductor 8; the gas outlet 7 on the permeation side is connected with a gas chromatograph 9 for detecting the content of the components on the permeation side.
Example 1.
Polyetherimide self-supporting carbon molecular sieve membrane synthesis
0.8g of polyetherimide was dissolved in 10g of tetrahydrofuran solvent and stirred well. And (3) blade-coating a polyetherimide film on a flat monocrystalline silicon sheet. The surface was dried rapidly at 70 ℃. And peeling the film off the silicon wafer. A5 cm × 5cm size self-supporting membrane was obtained. The film is carbonized in a high temperature furnace. Introducing Ar into the furnace for protection, wherein the flow rate is 80mL/min, the carbonization temperature is 450-650 ℃, and the carbonization time is 2-10 h.
Example 2.
Polyimide supported carbon molecular sieve membrane synthesis
1.2g of polyimide was dissolved in 10g N, N-dimethylformamide solvent and stirred well. Dipping-pulling coating on the surface of the alumina carrier. The speed of immersing the carrier into the solution in the dipping and pulling process is 3000 mu m/s, the residence time in the solution is 30s, and the pulling speed is 17 mu m/s. The film is carbonized in a high temperature furnace. Introducing Ar into the furnace for protection, wherein the flow rate is 100mL/min, the carbonization temperature is 500-600 ℃, and the carbonization time is 2 h.
Example 3
Polyetherimide self-supporting carbon molecular sieve membrane separation of butane/isobutane mixture
And (3) uniformly coating high-temperature-resistant AB glue on the back side edge of the self-supporting carbon molecular sieve membrane, and firmly bonding the self-supporting carbon molecular sieve membrane with a porous stainless steel support carrier to be used as a support, namely a membrane unit. The membrane unit was sealed in a stainless steel membrane assembly with an O-ring and placed in a 50 ℃ heat conductor to maintain a constant temperature. The volume ratio of the raw material side to the raw material side is 1: 1, i.e., 50mL/min each of the two gases. The raw material side was pressurized at 50000 Pa. He is introduced into the permeation side for purging, and the flow rate is 10 mL/min. And (4) enabling the component escaping from the permeation side of the He entrained membrane to enter a gas chromatography to detect the component and the content of the permeant on line. FIG. 2 is a schematic diagram of a butane/isobutane mixture separation apparatus. Table 1 lists the butane/isobutane separation performance of carbon molecular sieve membranes prepared from polyetherimide as a precursor at different pyrolysis temperatures. Table 2 lists the butane-/isobutane separation performance of carbon molecular sieve membranes prepared at different pyrolysis times. It can be seen that the carbon molecular sieve membranes prepared at different carbonization temperatures and different carbonization times have different microstructures, thereby affecting the permeability and selectivity of the membrane.
TABLE 1 separation performance of butane-/isobutane with carbon molecular sieve membranes prepared at different pyrolysis temperatures
GPU＝10-6cm3·cm-2·s-1·cmHg-1
TABLE 2 butane/isobutane separation performance of carbon molecular sieve membranes prepared at different pyrolysis times
GPU＝10-6cm3·cm-2·s-1·cmHg-1
Example 4
Polyetherimide self-supporting carbon molecular sieve membrane separation on n-hexane/2, 3-dimethylbutane mixture
And (3) uniformly coating high-temperature-resistant AB glue on the back side edge of the self-supporting carbon molecular sieve membrane, and firmly bonding the self-supporting carbon molecular sieve membrane with a porous stainless steel support carrier to be used as a support, namely a membrane unit. The membrane unit was sealed in a stainless steel membrane assembly with an O-ring and placed in a 75 ℃ heat conductor to maintain a constant temperature. The volume ratio of the raw material side to the raw material side is 1: the mixed vapor of n-hexane and 2, 3-dimethylbutane in the amount of 1, and the two gases are 50mL/min each. The raw material side is pressurized by 50kPa, and He is introduced into the permeation side for purging, wherein the flow rate is 10 mL/min. And (4) enabling the component escaping from the permeation side of the He entrained membrane to enter a gas chromatography to detect the component and the content of the permeant on line. Table 3 lists the permeability of carbon molecular sieve membranes to n-hexane and 2, 3-dimethylbutane single components. The permeability of the carbon molecular sieve membranes carbonized at several temperatures to 2, 3-dimethylbutane single-component is 0, and the ideal separation coefficient of n-hexane/2, 3-dimethylbutane is infinity.
TABLE 3 comparison of single-component permeability of carbon molecular sieve membranes carbonized at different temperatures
GPU＝10-6cm3·cm-2·s-1·cmHg-1
Example 5
Separation of butane/isobutane mixture by polyimide supported carbon molecular sieve membrane
The supported carbon molecular sieve membrane is sealed in a stainless steel membrane component by an O ring and is placed in a heat conductor at 30 ℃ to maintain constant temperature. The volume ratio of the raw material side to the raw material side is 1: 1, i.e., 50mL/min each of the two gases. The raw material side was pressurized at 50000 Pa. He is introduced into the permeation side for purging, and the flow rate is 10 mL/min. And (4) enabling the component escaping from the permeation side of the He entrained membrane to enter a gas chromatography to detect the component and the content of the permeant on line. Table 4 lists the butane/isobutane separation performance of the carbon molecular sieve membranes prepared at different pyrolysis temperatures. It can be seen that the carbon molecular sieve membranes prepared at different temperatures have different microstructures, thereby affecting the permeability and selectivity of the carbon molecular sieve membranes.
TABLE 4 butane/isobutane separation Performance on carbon molecular sieve membranes prepared at different pyrolysis temperatures
GPU＝10-6cm3·cm-2·s-1·cmHg-1
Example 6
Polyimide supported carbon molecular sieve membrane for separating mixture of n-hexane and 2, 3-dimethylbutane
The supported carbon molecular sieve membrane is sealed in the stainless steel membrane component by an O ring and is placed in a 75 ℃ heat conductor to maintain constant temperature. The volume ratio of the raw material side to the raw material side is 1: the mixed vapor of n-hexane and 2, 3-dimethylbutane in the amount of 1, and the two gases are 50mL/min each. The raw material side is pressurized by 50kPa, and He is introduced into the permeation side for purging, wherein the flow rate is 10 mL/min. And (4) enabling the component escaping from the permeation side of the He entrained membrane to enter a gas chromatography to detect the component and the content of the permeant on line. Table 5 lists the permeability of carbon molecular sieve membranes prepared at different carbonization temperatures to liquid phase n-hexane and 2, 3-dimethylbutane single components.
TABLE 5 comparison of single-component permeability of carbon molecular sieve membranes carbonized at different temperatures
GPU＝10-6cm3·cm-2·s-1·cmHg。
Claims (10)
1. Application of carbon molecular sieve membrane to C4-C6The method for separating the n-isoparaffin is characterized by comprising the following steps of:
(1) sealing the carbon molecular sieve membrane in the membrane component;
(2) the membrane component is arranged in the heat conductor to maintain constant temperature;
(3) introducing a saturated vapor mixture of normal isoparaffin into the raw material side;
(4) applying a pressure difference across the membrane;
(5) the components on the permeation side are carried by the purge gas and collected or condensed in a collector;
(6) the components on the permeation side are subjected to online or offline gas chromatography to detect the composition and the concentration of each component.
2. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating n-isoparaffin is characterized in that the membrane module in the step (1)The membrane is made of stainless steel, an O ring is sealed by silicon rubber and fixed in the middle of a stainless steel membrane component, a raw material side air inlet and a interception side air outlet are arranged on the upper half part of the membrane, a blowing side air inlet and a permeation side air outlet are arranged on the lower half part of the membrane, and the whole membrane component is arranged in a heat conductor; the gas outlet of the permeation side is connected with a gas chromatograph for detecting the content of the components of the permeation side.
3. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the n-isoparaffin is characterized in that the temperature of the heat conductor in the step (2) is-20-200 ℃.
4. A carbon molecular sieve membrane for use in C according to claim 14-C6The separation method of the n-isoparaffin is characterized in that the n-isoparaffin mixture in the step (3) is one of n-butane/isobutane, n-pentane/isopentane, n-pentane/neopentane, n-hexane/2-methylpentane, n-hexane/3-methylpentane, n-hexane/2, 3-dimethylbutane or n-hexane/2, 2-dimethylbutane mixture, and the mass concentration ratio of the n-paraffin to the isoparaffin is 0.005-0.995: 1.
5. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the n-isoparaffin is characterized in that the pressure difference between two sides of the membrane in the step (4) can be realized by applying pressure to one side of a raw material side or a permeation side or applying pressure to two sides simultaneously, and the pressure applied to the raw material side is 0-1000000 Pa; the pressure applied to the permeation side is 0.01 to 100000 Pa.
6. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the N-isoparaffin is characterized in that the purge gas in the step (5) is Ar, He or N2In the air-blowing device, the flow rate of the blowing gas is 0.1-200 mL/min.
7. A carbon molecular sieve membrane for use in C according to claim 14-C6A process for the separation of n-isoparaffins, characterized in thatIn the step (5), the condensation temperature is-300-20 ℃.
8. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the n-isoparaffin is characterized in that the carbon molecular sieve membrane is a self-supporting symmetrical membrane, and the effective thickness of the membrane layer is 0.1-100 mu m.
9. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the n-isoparaffin is characterized in that the carbon molecular sieve membrane is a support membrane, and the effective thickness of the membrane layer is 0.01-10 mu m.
10. A carbon molecular sieve membrane for use in C according to claim 14-C6The method for separating the normal isoparaffin is characterized in that the carbon molecular sieve membrane is prepared from one of polysulfone, polyethersulfone, polyimide, polyetherimide, polyaryletherketone, polybenzimidazole, polycarbonate, polyphenylene sulfide, polylactic acid or polymethyl methacrylate.
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Application publication date: 20200519 |