CN114534508B - Selective permeable membrane for natural gas denitrification process and preparation method thereof - Google Patents

Selective permeable membrane for natural gas denitrification process and preparation method thereof Download PDF

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CN114534508B
CN114534508B CN202011328638.XA CN202011328638A CN114534508B CN 114534508 B CN114534508 B CN 114534508B CN 202011328638 A CN202011328638 A CN 202011328638A CN 114534508 B CN114534508 B CN 114534508B
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abs resin
layer
resin support
sio
support body
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CN114534508A (en
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叶帆
赵毅
姚彬
赵德银
靳永红
李休萍
钟荣强
陈伟
黎志敏
任广欣
姚丽蓉
李鹏
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/105—Removal of contaminants of nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a selective permeation membrane for a natural gas denitrification process and a preparation method thereof, and relates to the technical field of membranes. The preparation method comprises the following steps: preparing an ABS resin support precursor; (2) Carrying out pore-forming and removing on the ABS resin support body precursor obtained in the step (1) to obtain an ABS resin support body; (3) And (3) depositing a protective layer on one surface of the ABS resin support body obtained in the step (2), and preparing a methane selective permeable membrane on the other surface of the ABS resin support body to obtain the selective permeable membrane for the natural gas denitrification process. The prepared selective permeation membrane has the advantages of simple preparation method, large artificial design margin of material parameters, good weather resistance and mechanical property and stable performance for a long time.

Description

Selective permeation membrane for natural gas denitrification process and preparation method thereof
Technical Field
The invention relates to the technical field of membranes, in particular to a selective permeation membrane for a natural gas denitrification process and a preparation method thereof.
Background
The natural gas is used as a high-quality fuel and an important chemical raw material, the application of the natural gas increasingly draws attention of people, and the trend of accelerating the development of the natural gas industry is in the world at present. However, natural gas produced in many oil and gas fields often contains a large amount of nitrogen, and natural gas with high nitrogen content has low calorific value and large energy consumption in the gathering and transportation process, and cannot be directly used as fuel. Therefore, denitrification of natural gas is an important condition for making full use of natural gas. The current industrial denitrification process for natural gas comprises: cryogenic cooling, solvent absorption, pressure swing adsorption and selective adsorption. The selective adsorption technology has the advantages of large operation flexibility, low investment, low energy consumption and the like, and has wide application prospect in the field of natural gas energy.
The current selective separation membrane usually adopts a structure of a multi-layer composite membrane, which comprises a lower support layer and an upper selective permeation membrane. The upper permselective membrane has a selective permeation function for CH4 or N2 gas, but the permselective membrane is often a polymer, the mechanical strength of the polymer is low, and in the permselective separation of natural gas, the pressure difference of about 10MPa needs to be borne on both sides of the whole permselective membrane, so that the resinous polymer is difficult to maintain a form sufficient for normal operation under such a large pressure difference. Therefore, a support structure, which is usually a porous polymer material or an inorganic material having a certain mechanical strength, is additionally provided below the upper permselective membrane. Thereby simultaneously providing the whole selective separation membrane with selective permeability and mechanical strength.
However, the above selective separation membrane has the following disadvantages: 1) The bottom layer mechanical support material is usually made of a high polymer material, the high polymer material is not stable enough in property, and is easy to generate property deterioration when contacting untreated natural gas for a long time, so that the mechanical strength and the weather resistance of the whole support material are reduced; 2) At present, a small amount of inorganic material supporting materials are reported, but the process is often complex, and the pore diameter is difficult to control; 3) In addition, under the condition of long-term use, the bonding performance interface of the mechanical support material and the polymer material also has the risk of stripping, so that the effect of selective separation is deteriorated.
In view of the above, the present application provides a selectively permeable membrane for a natural gas denitrification process and a preparation method thereof, which solve the above problems in the prior art, and achieve simple preparation method, large material parameter artificial design margin, and stable performance that can be maintained for a long time.
Disclosure of Invention
The invention aims to provide a selective permeation membrane for a natural gas denitrification process and a preparation method thereof, wherein the preparation is simple, the material parameters have large artificial design margin, and the obtained selective permeation membrane can keep stable performance for a long time.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in the present invention, the ABS resin refers to acrylonitrile-butadiene-styrene copolymer;
SBS refers to styrene-butadiene-styrene block copolymers;
the through hole is a hole penetrating up and down.
Firstly, the invention provides a preparation method of a selective permeable membrane for a natural gas denitrification process, which comprises the following steps:
(1) Preparing an ABS resin support precursor;
(2) Carrying out pore-forming and removing on the ABS resin support body precursor obtained in the step (1) to obtain an ABS resin support body;
(3) And (3) depositing a protective layer on one surface of the ABS resin support body obtained in the step (2), and preparing a methane selective permeable membrane on the other surface of the ABS resin support body to obtain the selective permeable membrane for the natural gas denitrification process.
Wherein, in the step (1), the ABS resin support precursor comprises ABS resin and nano-particles capable of preventing the ABS resin from being etched; the nano-particles capable of preventing ABS resin from being etched are SiO 2 At least one of nanoparticles and silicon nitride particles, more preferably SiO 2 And (3) nanoparticles.
Preferably, the ABS resin support precursor comprises a silicon wafer and SiO 2 Layer, ABS resin layer and SiO 2 And (3) nanoparticles.
Further preferably, in the step (1), the ABS resin support precursor is prepared according to the following method:
a. preparation of SiO on the upper surface of a silicon wafer 2 Laminating to obtain a laminated material 1;
b. in SiO 2 Forming an ABS resin layer on the upper surface of the layer to obtain a laminated material 2;
c. coating SiO on the upper surface of the ABS resin layer 2 And (4) nano particles to obtain the ABS resin support body precursor.
Preferably, in step a, the preparation of SiO 2 Methods of the layer include, but are not limited to, thermal oxidation, CVD.
Preferably, in step a, the SiO is 2 The thickness of the layer is 800-1000 μm.
Preferably, the following steps are further included between step a and step b: the roughness of the upper surface of the silicon dioxide layer is increased to 5-30 μm, preferably using the following method: the laminated material 1 is placed in a plasma vacuum processing cavity, working gas is introduced into the plasma vacuum processing cavity, a radio frequency power supply is turned on to excite the surface of the silicon dioxide layer of the silicon wafer to generate plasma, the plasma is close to the surface of the silicon dioxide, and high-energy particles bombard the surface of the material, so that the upper surface of the silicon dioxide layer is a rough surface; further preferably, the working gas comprises 78-82% by volume of argon, 15-17% by volume of nitrogen and 2-5% by volume of oxygen, the gas flow rate being 1000-1500sccm.
Preferably, in the step b, the method for forming the ABS resin layer includes, but is not limited to: and (6) hot pressing and coating. The hot pressing method comprises the following steps: uniformly arranging sheets or particles of ABS resin on the silicon dioxide layer, integrally heating the silicon wafer, the silicon dioxide layer and the ABS resin to the ABS resin melting temperature, and then drying and cooling to solidify the ABS resin material on the silicon dioxide layer into a layer; or directly bonding the molded ABS resin layer or sheet material on the surface of the silicon dioxide layer by means of hot pressing.
The coating method comprises the following steps: and uniformly spraying, blade-coating or smearing the molten ABS resin on the surface of the silicon dioxide layer.
Preferably, in the step b, the thickness of the ABS resin layer is 1.5-3.5mm, and more preferably 2-3mm.
Preferably, the following steps are further included between step b and step c: the roughness of the laminate 2 is controlled to 1 μm or less, more preferably 0.5 to 1 μm; the following steps are preferably adopted: firstly, preparing a mixed solution of 20-25% by volume of dimethylformamide, 15-30% by volume of alcohol and the balance of deionized water, mixing abrasive particles (with the particle size of 20-50 nm) in the mixed solution by a dispersion method and a mechanical stirring mode, adding a dispersing agent (the volume of the mixed solution is 5% by volume of the dispersing agent, and the dispersing agent is sodium polyacrylate or ammonium polyacrylate) to obtain a polishing solution, carrying out chemical mechanical polishing on the ABS resin layer by the polishing solution, wherein the polishing area is per square centimeter during polishing, the flow rate of the polishing agent is 10-50mL/min, the rotating speed of a polishing disc is 600-1000 r/min, and the pressure of the polishing disc is controlled below 50 MPa.
Preferably, the thickness of the ABS resin layer after polishing is controlled to be 100-150 μm, and the ABS resin layer is too thin to obtain enough mechanical strength and too thick to facilitate gas passage.
Preferably, in step c, the coating SiO 2 Methods for nanoparticle layers include, but are not limited to, liquid film methods, coating methods.
The liquid membrane method specifically comprises the following steps:
mixing a hydrophobing agent, a dispersing agent, ethylene glycol and deionized water to obtain a mixed solution; mixing SiO 2 Adding nanoparticles into the above mixed solution, heating for dewateringProcessing; placing the laminated material 2 into the mixed solution, and heating for hydrophobic treatment; placing the laminated material into a carrier of LB film drawing instrument, placing the carrier into water, and subjecting the hydrophobic treated SiO to water repellent treatment 2 Slowly pouring the granules on the surface of water of the film drawing instrument, and adjusting the side pressure of the film drawing instrument to ensure that the SiO is coated on the surface of the film drawing instrument 2 A single layer is formed on the liquid surface, and then the laminated material is pulled up at a low speed, preferably at a pulling speed of less than 0.02m/min. SiO after pulling 2 The particles are uniformly distributed on the upper surface of the ABS resin layer, and due to the action of gravity, the nano particles are closely arranged on the surface of the ABS resin layer, namely a close-packed structure is formed.
SiO as described above 2 The nano particles, the hydrophobic agent and the dispersing agent can be common materials which can be obtained on the market; preferably, the dispersant is a water-repellent dispersant, and the SiO is 2 Both the nanoparticles and the laminate 2 are heated at 70-90 deg.C for 0.2-0.8 hr, preferably at 80 deg.C for 0.5 hr.
The coating method specifically comprises the following steps:
putting laminated material 2 into a plasma vacuum processing cavity, making the surface of an ABS resin layer upward, arranging a shielding cover at a position 3-8cm above the ABS resin layer, completely covering the ABS resin layer with the shielding cover, wherein the shielding cover is of a screening structure and is provided with through hole openings of an array arrangement part, and through holes of the screening structure are arranged according to the following rules: the diameter of each through hole is the same, but the through hole pitch (adjacent hole center distance) satisfies: di = ri 2 K (d 0), where di is the distance between the hole currently being calculated and its radially outer hole, ri is the distance of the hole from the center of the wafer, k is a constant, typically 500mm, and d0 is the distance between the centermost hole and its radially outer hole, i.e., the density of openings decreases as the screen structure is closer to the center of the circle, such that the plasma roughening process is less intense at the plasma treatment closer to the center of the laminate and vice versa. The roughness of the surface of the ABS resin layer material after the plasma roughening treatment is characterized by small center and large periphery. The roughness Ra of the obtained ABS resin layer is 10-20 μm at the center and 80-100 μm at the periphery. The water repellent agent,Mixing a dispersing agent, ethylene glycol and deionized water to obtain a mixed solution; mixing SiO 2 Placing the nano particles into the mixed solution, heating and carrying out hydrophobic treatment; placing the laminated material 2 into the mixed solution, and heating for hydrophobic treatment; subjecting the hydrophobic treated SiO 2 Adding the nanoparticles into the photoresist solution, siO 2 The volume percentage of the nanoparticles is about 30-50%, too high a content affects the formation of a monolayer, and too low a content results in incomplete coverage of the surface. The roughness of the upper surface of the laminated material is higher at the position farther away from the center of the circle, and SiO is higher 2 In the spin coating process of the nano particles, the centrifugal force applied to the nano particles is larger as the nano particles are farther away from the circle center, so that the roughness of the upper surface of the laminated material is set to be higher as the nano particles are farther away from the circle center, the friction force applied to the nano particles is larger as the upper surface of the laminated material is farther away from the circle center, the distribution gradient of the centrifugal force is overcome, and the nano particles can be more uniformly distributed on the surface. The viscosity of the photoresist solution is controlled to be 150-200Pa, so that the photoresist solution can be uniformly kept on the surface of the ABS resin while being fully dispersed. Drying the laminated material, controlling the temperature at about 100 ℃ for 2 hours to ensure that SiO is formed 2 The nano particles are fixed on the surface of the ABS resin layer.
SiO as described above 2 The nano particles, the hydrophobic agent and the dispersing agent can be common materials which can be obtained on the market; preferably, the dispersant is a water-resistant dispersant, and the SiO is 2 Both the nanoparticles and the laminate 2 are heated at 70-90 deg.C for 0.2-0.8 hr, preferably at 80 deg.C for 0.5 hr.
Preferably, in step c, the SiO is 2 The nanoparticle layer is a single layer coating.
Preferably, in the step (2), the pore-forming is a pore-forming by dry etching, and the dry etching includes, but is not limited to, plasma etching, reactive Ion Etching (RIE), and the like. For example, the RIE method is used to form the holes, and the process is: placing the ABS resin support precursor obtained in step (1) into RIE equipment, wherein the reaction gas has a percentage of 10% CF 4 、60％O 2 And 30% Ar, air pressure is controlled at 5-10 × 10 -6 Pa, reaction bias 20Kw, time control in 15-20min.
In pore forming, as shown in FIG. 3, the spherical SiO is densely arranged 2 A plurality of gaps 5 which are arranged like an array are formed among the nano particles 4, the ABS resin layer at the gaps 5 is etched, and through holes like an array are formed in the ABS resin layer.
Due to the energy distribution of etching and the diameter-depth ratio of the holes, the through holes are formed into a horn shape with a large upper part and a small lower part, and the separation of gas is facilitated.
The nano particles with different particle diameters are selected according to the size of the required through holes and the arrangement density of the holes, namely the arrangement density of the holes and the aperture of the filtering through holes are flexibly adjusted by changing the size of the nano particles.
Preferably, siO having various average particle diameters can be used 2 The nano particles are arranged like a single layer, so that the design and the manufacture of different apertures are realized, and various impurities with different molecular diameters are respectively filtered.
In the step (2), the removing refers to removing the nanoparticles which can prevent the ABS resin from being etched in the ABS resin support body precursor. Preferably, the method may be performed by: placing the ABS resin support precursor after pore forming in a dilute hydrofluoric acid solution for soaking reaction, wherein hydrofluoric acid is used for ABS and SiO 2 Selective etching of (2) to SiO between the ABS resin and the silicon wafer 2 Layer and SiO 2 And (3) corroding the nano particles, finally peeling off the ABS resin layer with the holes, and cleaning and drying the ABS resin thin layer to obtain the ABS resin support body.
Preferably, in the step (3), the material of the protective layer is alumina.
Preferably, in the step (3), the deposition of the protective layer is realized by using an atomic layer deposition technology (ALD), and the protective layer is deposited on the large-opening corresponding surface of the trumpet-shaped through hole and inside the through hole. Taking alumina as an example, the method specifically comprises the following steps:
the upper surface of the ABS resin support body is upward (namely the large-opening corresponding surface is upward), and a gas precursor trimethyl aluminum is introduced; introducing reaction gas ozone; introducing a cleaning gas nitrogen; the above 3 steps are one cycle, and 5 to 10 cycles are performed to form alumina of about 5 to 10 atomic layer thickness. Preferably, the flow rate of the trimethylaluminum is 100-150sccm, and the introduction time is 0.8-1.5s, and more preferably 1s; the ozone is introduced into the reactor at a flow rate of 80-100sccm for 4-6s, preferably 5s; the nitrogen gas is introduced at a flow rate of 100 to 200sccm for 8 to 12 seconds, and more preferably 10 seconds.
The thickness and the density of the alumina layer are controlled by the process parameters, the thickness of the alumina layer is controlled below 1nm, the nanoscale through holes of the supporting layer are not blocked, the thickness and the density are sufficient, and the chemical stability of the ABS resin is improved.
Preferably, in the step (3), the material of the methane selective permeable membrane is a methane selective permeable membrane of SBS material. The preparation process specifically comprises the following steps:
mixing cyclohexane, n-butyllithium, tetrahydrofuran and styrene, carrying out polymerization reaction, and then adding 1, 3-butadiene and styrene for reaction again to obtain a product; and curing and drying the product to form a sheet, and then laminating the sheet to an ABS resin support or melting and coating the sheet to the ABS resin support. The polymerization temperature is preferably 50 to 70 ℃ and more preferably 60 ℃.
Preferably, in the step (3), the methane selective permeable membrane is prepared on the corresponding surface of the small opening of the trumpet-shaped through hole.
Preferably, in the step (3), the thickness of the methane permselective membrane is 1 to 5 μm.
In another aspect, the present application also provides a selectively permeable membrane for a selective denitrification process of natural gas, prepared according to the above method.
The permselectivity membrane structure is shown in fig. 2, and comprises an ABS resin support body 1, a protective layer 2, and a methane permselectivity membrane 3 on the ABS resin support body 1, wherein the ABS resin support body 1 has through holes arranged in an array; the protective layer 2 covers the large-opening corresponding surface of the through hole and the inside of the through hole, and the methane selective permeable membrane 3 is arranged on the small-opening corresponding surface of the through hole.
Preferably, the ABS resin support 1 has a thickness of 100 to 150 μm, the protective layer 2 has a thickness of less than 1nm, and the methane-permselective membrane 3 has a thickness of 1 to 5 μm.
Compared with the prior art, the invention has the following beneficial effects:
(1) The selective permeation membrane for the selective denitrification process of the natural gas, which is prepared by the invention, has good weather resistance and mechanical property, and can keep stable performance for a long time;
(2) The preparation method is simple and convenient, and the design margin of material parameters is large;
(3) The ABS resin support body is provided with horn-shaped through holes, the methane selective permeable membrane is combined on one side with a smaller opening, gas can be filtered through the horn mouth and then contacts the selective permeable membrane, and the selection ratio of the whole membrane is improved.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
FIG. 2 is a schematic structural diagram of a permselective membrane prepared according to the present invention;
FIG. 3 is a schematic representation of SiO 2 Schematic diagram of the close packed state of the nanoparticles.
Detailed Description
The present invention will be further described with reference to specific examples, which are intended to illustrate various embodiments of the present invention. In the interest of clarity, not all features of an actual implementation are described. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. It will of course be appreciated that in the development of any such actual embodiment, numerous implementation-specific details are set forth in order to achieve the developer's specific goals. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
In order to make the objects and features of the present invention more comprehensible, embodiments of the present invention are described in detail below with reference to the accompanying drawings. It is to be noted that the drawings are in a very simplified form and are all used in a non-precise ratio for the purpose of facilitating and clearly aiding in the description of the embodiments of the invention.
The experimental procedures in the following examples were carried out in a conventional manner unless otherwise specified, and materials, reagents and the like used in the following examples were commercially available unless otherwise specified.
Example 1
A preparation method of a selective permeable membrane for a natural gas denitrification process comprises the following steps:
(1) Preparing an ABS resin support precursor, wherein the ABS resin support precursor comprises a silicon wafer and SiO 2 Layer, ABS resin layer, siO 2 A nanoparticle;
(2) Subjecting the ABS resin support precursor obtained in step (1) to a RIE apparatus to gouge, wherein the reaction gas content is 10% by volume CF 4 、60％O 2 And 30% Ar, air pressure is controlled at 5-10 × 10 -6 Pa, reaction bias voltage of 20Kw, time control in 15-20min; as shown in FIG. 3, the densely packed spherical SiO 2 A plurality of gaps 5 which are arranged like an array are formed among the nano particles 4, the ABS resin layer at the gaps 5 is etched, and through holes like an array are formed on the ABS resin layer;
placing the ABS resin support precursor after pore forming in a dilute hydrofluoric acid solution for soaking reaction, wherein hydrofluoric acid is used for ABS and SiO 2 Selective etching of (3) to SiO between the ABS resin and the silicon wafer 2 Layer and SiO 2 Corroding the nano particles, finally peeling off the ABS resin layer with the holes, and cleaning and drying the ABS resin thin layer to obtain the ABS resin support body;
(3) The upper surface of the ABS resin support body is upward (namely the large-opening corresponding surface is upward), a gas precursor trimethylaluminum is introduced, the flow rate is 120sccm, and the introduction time is 1s; introducing reaction gas ozone for 5s; introducing a cleaning gas of nitrogen for 10s; the above 3 steps are a period, 7 periods are executed, and alumina with the thickness of about 7 atomic layers is formed on the corresponding surface of the large opening of the horn-shaped through hole and the inside of the through hole.
Cyclohexane (5.4 kg), n-butyllithium (7 mmol), tetrahydrofuran (300 mmol) and styrene (100 g) were mixed, and polymerization was carried out at 60 ℃, and then 1, 3-butadiene (450 g) and styrene (100 g) were added to carry out reaction again to obtain a product; and curing and drying the product to form a sheet, and then pressing the sheet to the corresponding surface of the small opening of the horn-shaped through hole of the ABS resin support body to obtain the selective transmission membrane.
Wherein the content of the first and second substances,
in the step (1), the ABS resin support precursor is prepared according to the following method:
a. preparing SiO on the upper surface of a silicon chip by a thermal oxidation method 2 Laminating to obtain a laminated material 1;
the laminated material 1 is placed in a plasma vacuum treatment cavity, working gas is introduced into the plasma vacuum treatment cavity, a radio frequency power supply is turned on to excite the upper side of the surface of a silicon dioxide layer of a silicon wafer to generate plasma, the plasma is close to the surface of the silicon dioxide, and high-energy particles bombard the surface of the material, so that the upper surface of the silicon dioxide layer is a rough surface; the working gas comprises 80% of argon, 16% of nitrogen and 4% of oxygen in percentage by volume, the gas flow is 1200sccm, and the surface roughness after treatment is 12-15 mu m.
b. Uniformly coating ABS resin in a molten state (170-180 ℃) on SiO 2 Layer on the upper surface of SiO 2 Forming an ABS resin layer on the upper surface of the layer to obtain a laminated material 2;
the following steps are preferably adopted: firstly, preparing a mixed solution of 20-25% by volume of dimethylformamide, 15-30% by volume of alcohol and the balance of deionized water, mixing abrasive particles (with the particle size of 20-50 nm) in the mixed solution by a dispersion method and a mechanical stirring mode, adding a dispersing agent (5% by volume of sodium polyacrylate or ammonium polyacrylate in the mixed solution) to obtain a polishing solution, and carrying out chemical mechanical polishing on the ABS resin layer by the polishing solution, wherein the flow rate of the polishing agent is 10-50mL/min, the rotating speed of a polishing disc is 600-1000 r/min, the pressure of the polishing disc is controlled below 50MPa, and the roughness of the laminated material 2 is controlled at 0.5-1 mu m.
c. Mixing a hydrophobing agent, a dispersing agent, ethylene glycol and deionized water to obtain a mixed solution; mixing SiO 2 Adding the nanoparticles into the above mixture, and adding at 80 deg.CHeating for 0.5h, and performing hydrophobic treatment; putting the laminated material 2 into the mixed solution, heating at 80 ℃ for 0.5h, and performing hydrophobic treatment; placing the laminated material into a carrier of LB film drawing instrument, placing the carrier into water, and subjecting the hydrophobic treated SiO to water repellent treatment 2 Slowly pouring the granules on the surface of water of the film drawing instrument, and adjusting the side pressure of the film drawing instrument to ensure that the SiO is coated on the surface of the film drawing instrument 2 A single layer is formed on the liquid surface, and then the laminated material is pulled up at a low speed, preferably at a pulling speed of less than 0.02m/min. SiO after pulling 2 The particles are uniformly distributed on the upper surface of the ABS resin layer, and due to the action of gravity, the nano particles are closely arranged on the surface of the ABS resin layer, namely a close-packed structure is formed, so that the ABS resin support body precursor, the SiO 2 The nanoparticle layer is a single layer coating.
The parameters of the resulting permselective membrane are shown in table 1:
table 1.
Figure BDA0002795081090000091
Example 2
In this example, the parameters of the selectively permeable membrane were set as shown in table 2, which is different from example 1:
table 2.
Figure BDA0002795081090000092
Example 3
In this example, the parameters for setting the permselective membrane are shown in table 3, which is different from example 1:
table 3.
Figure BDA0002795081090000101
Example 4
In this example, the parameters for setting the permselective membrane are shown in table 4, which is different from example 1:
table 4.
Figure BDA0002795081090000102
Example 5
Unlike example 1, this example prepares SiO by the CVD method 2 Layers, the rest being the same.
Example 6
Unlike example 1, this example prepared an ABS resin layer by a hot press method, and the rest was the same.
Comparative example 1
The difference from embodiment 1 is that the thickness of the protective layer is 2nm, and the rest is the same.
Comparative example 2
The difference from example 1 is that the thickness of the ABS resin support was 200. Mu.m, and the rest was the same.
Result detection
1. Weather resistance test
The test method comprises the following steps: and (4) putting the prepared sample into natural gas denitrification equipment to work, and detecting the service life.
The test results are shown in table 5:
table 5.
Figure BDA0002795081090000103
Figure BDA0002795081090000111
2. Mechanical Property test
The test method comprises the following steps: GB/T8641-1988.
The test results are shown in table 6:
table 6.
Figure BDA0002795081090000112
3. Permselectivity test
The test method comprises the following steps: GB/T1038-2000.
The test results are shown in table 7:
table 7.
Figure BDA0002795081090000113
Figure BDA0002795081090000121
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a selective permeable membrane for a natural gas denitrification process is characterized by comprising the following steps:
(1) Preparing an ABS resin support precursor;
(2) Carrying out pore-forming and removing on the ABS resin support body precursor obtained in the step (1) to obtain an ABS resin support body;
(3) Depositing a protective layer on one surface of the ABS resin support body obtained in the step (2), and preparing a methane selective permeable membrane on the other surface of the ABS resin support body to obtain the selective permeable membrane for the natural gas denitrification process;
in the step (1), the ABS resin support precursor comprises ABS resin and nanoparticles capable of preventing the ABS resin from being etched, and the nanoparticles capable of preventing the ABS resin from being etched are SiO 2 At least one of nanoparticles and silicon nitride particles;
in the step (2), the removing means removing the nanoparticles capable of preventing the ABS resin from being etched in the ABS resin support precursor.
2. The method according to claim 1, wherein the reaction mixture is heated to a temperature higher than the melting point of the reaction mixtureIn the step (1), the ABS resin support precursor comprises a silicon wafer and SiO 2 Layer, ABS resin layer and SiO 2 And (3) nanoparticles.
3. The production method according to claim 2, wherein in the step (1), the ABS resin support precursor is produced according to the following method:
a. preparation of SiO on the upper surface of a silicon wafer 2 Laminating to obtain a laminated material 1;
b. in SiO 2 Forming an ABS resin layer on the upper surface of the layer to obtain a laminated material 2;
c. coating SiO on the upper surface of the ABS resin layer 2 And (4) nano particles to obtain the ABS resin support body precursor.
4. The method according to claim 3, wherein in step a, the SiO is prepared 2 The method of the layer is selected from a thermal oxidation method or a CVD method.
5. The method of claim 3, wherein in the step b, the method for forming the ABS resin layer is selected from hot pressing or coating.
6. The preparation method according to claim 1, wherein in the step (2), the pore-forming method is dry etching pore-forming, so that nanoparticles etched in the ABS resin are prevented from being densely arranged in a single layer on the surface of the ABS resin, and horn-shaped through holes arranged in an array are formed in arrangement gaps.
7. The method according to claim 1, wherein in the step (3), the material of the protective layer is alumina, and the methane-selective permeable membrane is a methane-selective permeable membrane of SBS material.
8. The method according to claim 1, wherein in the step (3), the method for depositing the protective layer is atomic layer deposition.
9. The permselective membrane for a natural gas denitrification process, prepared according to the preparation method of any one of claims 1 to 8, comprising an ABS resin support body, a protective layer and a methane permselective membrane, wherein the ABS resin support body is provided with horn-shaped through holes arranged in an array; the protective layer covers the corresponding surface of the large opening of the through hole and the inside of the through hole, and the methane selective permeable membrane is arranged on the corresponding surface of the small opening of the through hole; the thickness of the ABS resin support body is 100-150 μm, the thickness of the protective layer is less than 1nm, and the thickness of the methane selective permeable membrane is 1-5 μm.
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