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CN-117448619-B - Gold-containing composite film with sulfur resistance, preparation method and application thereof

CN117448619BCN 117448619 BCN117448619 BCN 117448619BCN-117448619-B

Abstract

The invention relates to the field of palladium-based alloy materials, and discloses a gold-containing composite film with sulfur resistance, a preparation method and application thereof, wherein the composite film comprises a composite palladium-based alloy material, a silicon-aluminum molecular sieve modified by hydrophobic groups and an oxide of VIB group metal, which are sequentially attached to the surface of the composite palladium-based alloy material, wherein the composite palladium-based alloy material contains Pd, cu and Au, the molar ratio of Pd, cu and Au is 100 (58-95): 9-37, the crystal structure of the composite palladium-based alloy material is face-centered cubic close-packed, and the lattice parameter k is 0.4098-4286nm. The composite membrane has higher structural stability and sulfur resistance, can be applied to the hydrogen separation and purification process after the industrial hydrogen production and the reforming hydrogen production of the sulfur-containing acid-containing gas field, can obtain higher-purity hydrogen and higher hydrogen recovery rate, and has longer service life.

Inventors

  • ZHAO CHENYANG
  • SUN BING
  • LIU YUJIA
  • FENG JUNJIE
  • ZHU HONGWEI
  • JIN YAN
  • JIANG JIE

Assignees

  • 中国石油化工股份有限公司
  • 中石化安全工程研究院有限公司

Dates

Publication Date
20260505
Application Date
20220718

Claims (20)

  1. 1. A gold-containing composite film with sulfur resistance is characterized by comprising a composite palladium-based alloy material and a hydrophobic group modified silicon-aluminum molecular sieve and an oxide of a group VIB metal which are sequentially attached to the surface of the composite palladium-based alloy material, wherein the composite palladium-based alloy material is Pd, cu and Au, the molar ratio of Pd, cu and Au is 100 (58-95) (9-37), the crystal form structure of the composite palladium-based alloy material is face-centered cubic close-packed, the lattice parameter k is 0.4098-4286nm, the half-peak width of a characteristic peak at2θ=40 o ±1 o is smaller than or equal to 0.0524,2 θ=46 o ±1 o , the half-peak width of a characteristic peak at 0.0873,2 θ=69 o ±1 o is smaller than or equal to 0.1222,2 θ=83 o ±1 o , and the half-peak width of a characteristic peak at 0.1396,2 θ=87 o ±1 o is smaller than or equal to 0.1571 in an XRD spectrum of the composite palladium-based alloy material; The crystal phase structure of the composite palladium-based alloy material is carried out on an X-ray diffractometer, and the experimental conditions are that a CuK α ray, lambda= 0.1543 nm, tube pressure of 40 kV, current of 40 mA and diffraction angle 2 theta scanning range of 10-90 o are adopted; The half-peak width test method of the composite palladium-based alloy material comprises the step of obtaining the radian value of the half-peak width according to the test result of an X-ray diffractometer and by combining HighScore Plus software analysis.
  2. 2. The composite membrane of claim 1, wherein the composite palladium-based alloy material has a thickness of 0.5-30 μm.
  3. 3. The composite membrane of claim 1, wherein the composite palladium-based alloy material has a thickness of 5-15 μιη.
  4. 4. The composite film according to claim 1 or 2, wherein the composite film has a water contact angle of 90 o or more; and/or, the composite membrane is a tubular membrane; And/or the composite membrane further comprises a support body, wherein the composite palladium-based alloy material is attached to the support body, and the thickness of the support body is 0.1-20mm.
  5. 5. The composite film according to claim 1 or 2, wherein the composite film has a water contact angle of 105 o or more.
  6. 6. The composite membrane of claim 1 or 2, wherein the composite membrane further comprises a support, the composite palladium-based alloy material being attached to the support, the support having a thickness of 2-5mm.
  7. 7. The composite membrane of claim 1 or 2, wherein the ratio of peak areas of peaks in the 29 Si MAS nuclear magnetic resonance spectrum of the hydrophobic group modified silica-alumina molecular sieve having chemical shifts around-113 ppm and-103 ppm is 6 to 12; And/or the hydrophobic groups in the hydrophobic group modified silicon aluminum molecular sieve are provided by at least one of polymethylhydrosiloxane, vinyltriethoxysilane, 3-aminopropyl triethylsilane, N-diethyltrimethylsilane, 3-aminopropyl trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyl triethoxysilane, N-diethyl-3- (trimethoxysilyl) propylamine, 1- [3- (trimethoxysilyl) propyl ] urea, (3-chloropropyl) trimethoxysilane, 3-chloropropyl triethoxysilane; And/or the hydrophobic group modified silicon aluminum molecular sieve is at least one of a hydrophobic group modified ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-34, 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, SAPO-31, SAPO-34, SAPO-44, RUB-13, MCM-68, Y molecular sieve and mordenite; And/or the thickness of the silicon-aluminum molecular sieve modified by the hydrophobic group is 2-125 mu m; And/or the silicon-aluminum molar ratio of the silicon-aluminum molecular sieve modified by the hydrophobic group is (5-100) 1, the average grain diameter is 100-350nm, the average pore diameter is 0.35-280nm, the specific surface area is 75-800m 2 /g, and the crystallinity is more than or equal to 90%.
  8. 8. The composite membrane of claim 1 or 2 wherein the hydrophobic groups in the hydrophobic group modified silicoaluminomolecular sieve are provided by at least one of polymethylhydrosiloxane, vinyltriethoxysilane, 3-aminopropyl triethylsilane, N-diethyltrimethylsilane, 3-aminopropyl trimethoxysilane.
  9. 9. The composite membrane according to claim 1 or 2, wherein the hydrophobic group modified silicoaluminomolecular sieve has a thickness of 15-50 μm.
  10. 10. The composite membrane according to claim 1 or 2, wherein the silicon to aluminum molar ratio of the hydrophobic group modified silicon to aluminum molecular sieve is (10-40): 1.
  11. 11. The composite membrane according to claim 1 or 2, wherein the average particle diameter of the hydrophobic group-modified aluminosilicate molecular sieve is 150-200nm.
  12. 12. A composite membrane according to claim 1 or 2, wherein the average pore size of the hydrophobic group modified aluminosilicate molecular sieve is from 0.85 to 55nm.
  13. 13. The composite membrane according to claim 1 or 2, wherein the specific surface area of the hydrophobic group modified silicoaluminomolecular sieve is 100-550m 2 /g.
  14. 14. The composite membrane according to claim 1 or 2, wherein the crystallinity of the hydrophobic group modified silicoaluminomolecular sieve is 95-99%.
  15. 15. The composite membrane according to claim 1 or 2, wherein the average particle size of the oxides of group VIB metals is 10-750nm.
  16. 16. The composite membrane according to claim 1 or 2, wherein the group VIB metal oxide is present in an amount such that the molar ratio between group VIB metal and Pd is 0.01-0.5.
  17. 17. A method of making a gold-containing composite film having sulfur resistance, the method comprising: (1) Pd, cu and Au are deposited on the support, and then the support on which the Pd, cu and Au are deposited is subjected to alloying treatment, wherein the mol ratio of the Pd, cu and Au is 100 (58-95): 9-37; The alloying treatment is carried out by performing heat treatment under 380-580 ℃ and pressure greater than 0.2MPa in an activating atmosphere, and then reducing the temperature to below 230 ℃ at a rate greater than 35 ℃ per minute, wherein the gas for providing the activating atmosphere optionally comprises alkaline gas; (2) Placing the alloyed material into a solution of a precursor containing a silicon-aluminum molecular sieve, and sequentially carrying out hydrothermal crystallization, drying and roasting to obtain a composite film precursor; (3) Modifying the composite film precursor with hydrophobic groups; (4) Depositing an oxide of a group VIB metal on the surface of the product modified by the hydrophobic group obtained in the step (3).
  18. 18. The method according to claim 17, wherein the alloying treatment is performed by reducing the temperature to 180-230 ℃ at a rate of 40-65 ℃ per minute after treating the alloy in an activating atmosphere at a temperature of 400-500 ℃ and a pressure of 0.24-0.35MPa for 4-6 hours; And/or, the content of the alkaline gas in the gas providing the activation atmosphere is 20% by volume or more; And/or the alkaline gas is selected from at least one of ethylenediamine, NH 3 、PH 3 and N 2 H 4 ; And/or the total thickness of Pd, cu and Au deposited on the support is 0.5-30 μm; and/or the thickness of the support body is 0.1-20mm.
  19. 19. The method of claim 17, wherein the total thickness of Pd, cu and Au deposited on the support is 5-15 μm.
  20. 20. The method of claim 17, wherein the support has a thickness of 2-5mm.

Description

Gold-containing composite film with sulfur resistance, preparation method and application thereof Technical Field The invention relates to the field of palladium-based alloy materials, in particular to a gold-containing composite film with sulfur resistance, a preparation method and application thereof. Background Compared with hydrogen separation and purification technologies such as pressure swing adsorption and low-temperature distillation, the membrane separation technology has the advantages that trace impurities such as N 2、Ar、He、CO2 and the like remained in hydrogen can be completely removed, the selectivity of the dense metal palladium membrane to hydrogen can reach 100% theoretically, and the corresponding hydrogen purity can reach 100%, which is a product purity standard which is difficult to reach by other separation technologies. Therefore, the palladium membrane separation technology is a hydrogen separation and purification technology with great application prospect. However, since metallic palladium or palladium alloy films form hydrides when they are in contact with H 2 at low temperatures, "hydrogen embrittlement" occurs, which damages the integrity and compactness of pure palladium or palladium alloy films, while at high temperatures, the grains on the surface of palladium films rearrange and sinter, which leads to pinholes and defects in the palladium films, and even to cracking of the palladium films. Therefore, in order to ensure long-term stability of the use of the palladium membrane, it is necessary to provide a suitable and stable palladium membrane use temperature, and a suitable operating temperature of the palladium membrane is 350 to 500 ℃. Meanwhile, when the palladium membrane separation technology is applied to the separation of industrial hydrogen-rich production or the separation and purification scene after reforming hydrogen production of sulfur-containing gas fields, compared with hydrogen, trace sulfur compounds such as hydrogen sulfide, methyl sulfide and the like are more easily adsorbed on the surface of a palladium membrane and are aggregated, pd 4 S structures appear in a palladium membrane phase after long time, so that the mechanical strength of a membrane material is reduced, and finally the defect of the palladium membrane is caused to influence the separation effect of the palladium membrane. Therefore, the separation and purification system of the palladium membrane applied to the sulfur-containing hydrogen has the following problems that 1) after the ultrathin palladium membrane dissolves hydrogen at low temperature (< 573K), the palladium membrane is easy to crack due to severe change of lattice parameters, and the traditional palladium membrane separation technology is not suitable for a low-temperature separation environment. 2) Along with the increase of the concentration of sulfur-containing compounds in a system to be separated, the separation efficiency of the palladium membrane surface is reduced due to sulfuration poisoning, and the low-temperature environment aggravates the reduction of the mechanical strength and the defect exposure of the palladium membrane, and finally the separation and purification efficiency of hydrogen is influenced. The prior art mixes nano palladium suspension with certain particle size and MoS 2 particles to prepare composite modification liquid (or prepares modification liquid with MoS 2), and can realize stable operation under the atmosphere of sulfur-chlorine pollutants by means of high specific surface area and high activity of nano palladium and preferential adsorption and decomposition of sulfur-chlorine pollutants, the hydrogen permeability of a palladium membrane is not affected, the prior art can keep the high hydrogen permeability and high selectivity of the palladium membrane, and the method has the characteristics of simple process, convenient operation, small investment, good repeatability and the like. However, the binding force between the palladium membrane and the MoS 2 particles in the prior art is insufficient, the composite modification liquid prepared by mixing the nano palladium suspension and the MoS 2 particles is difficult to uniformly cover the surface of the palladium membrane, 100% decomposition of sulfur-containing pollutants is realized, and the exposed palladium membrane part is often more easily poisoned by sulfides preferentially to change the structure, so that defects are formed. In addition, moS 2 has low decomposition efficiency on sulfur-containing compounds, and the decomposed H 2 S still exists on the surface of the palladium membrane in the form of an S simple substance, and further causes the palladium membrane to be vulcanized and poisoned after the interaction with the palladium membrane for a long time. Disclosure of Invention The invention aims to solve the problems that a palladium membrane is easy to be hydrogen embrittled and sulfur-poisoned in the hydrogen separation proce