WO2015100900A1 - 一种高强度的中空纤维分子筛膜及其制备方法 - Google Patents

一种高强度的中空纤维分子筛膜及其制备方法 Download PDF

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Publication number
WO2015100900A1
WO2015100900A1 PCT/CN2014/077166 CN2014077166W WO2015100900A1 WO 2015100900 A1 WO2015100900 A1 WO 2015100900A1 CN 2014077166 W CN2014077166 W CN 2014077166W WO 2015100900 A1 WO2015100900 A1 WO 2015100900A1
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molecular sieve
hollow fiber
membrane
carrier
channel
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English (en)
French (fr)
Chinese (zh)
Inventor
顾学红
刘德忠
时振洲
张春
王学瑞
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Nanjing Tech University
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Nanjing Tech University
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Priority to EP14877023.3A priority Critical patent/EP3090798B1/en
Priority to JP2016522199A priority patent/JP6158437B2/ja
Priority to US14/898,472 priority patent/US10427107B2/en
Publication of WO2015100900A1 publication Critical patent/WO2015100900A1/zh
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    • 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
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
    • 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
    • B01D69/08—Hollow fibre 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2181—Inorganic additives
    • B01D2323/21817—Salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance

Definitions

  • the present invention relates to a high-strength hollow fiber molecular sieve membrane and a preparation method thereof, and belongs to the field of inorganic membrane preparation.
  • BACKGROUND OF THE INVENTION Membrane separation technology is an efficient and energy-saving new separation technology widely used in petrochemical, food, pharmaceutical, energy, electronics and environmental protection fields.
  • this separation technology has played a significant advantage in solving major problems such as resource shortage, energy shortage and environmental pollution.
  • the requirements for the membrane material itself have become more severe, and the application range of the inexpensive organic polymeric membrane has been limited.
  • the inorganic membrane material has the advantages of high temperature resistance, high mechanical strength, good chemical stability, and the like, and is widely used in the field of membrane technology.
  • the molecular sieve membrane As an important component of the inorganic membrane material, the molecular sieve membrane has a regular and uniform pore structure in addition to some common features of the inorganic membrane, so that it has excellent catalytic performance and separation selectivity in membrane separation and membrane. Catalysis and ion exchange have broad application prospects.
  • the pore size of the zeolite molecular sieve membrane is generally less than 1 nm, and the effective separation between different molecules can be achieved by the molecular sieve effect or the pore adsorption property of the pore. More and more molecular sieve membranes are used in pervaporation membrane separation processes, such as NaA, MFI, T-type zeolite membranes, etc. Among them, NaA zeolite membranes are the most widely studied.
  • the NaA zeolite membrane material is highly hydrophilic, and its pore diameter is 0.42 nm, which is larger than the kinetic diameter of water molecules (0.29 nm) and smaller than the kinetic diameter of general organic molecules. Therefore, the membrane material is suitable for organic dehydration systems.
  • the water has a very high permeability selectivity.
  • the NaA molecular sieve membrane pervaporation dehydration unit has been successfully applied to industrial applications.
  • the carrier form of the NaA molecular sieve membrane material is mainly single-tube type, and its flux and packing density (30 250 m 2 /m 3 ) are low. The high investment cost of equipment limits the further development of its industrialization process.
  • the single-channel ceramic hollow fiber tube wall is thin, which can reduce the transmembrane resistance and significantly increase the permeation flux of the NaA zeolite membrane. Therefore, in order to increase the packing density and separation efficiency of the membrane module and to reduce the production cost, a single-channel ceramic hollow fiber carrier is introduced into the preparation of the NaA molecular sieve membrane.
  • a single-channel ceramic hollow fiber carrier is introduced into the preparation of the NaA molecular sieve membrane.
  • the present invention aims to provide a high-strength hollow fiber molecular sieve membrane in order to improve the deficiencies of the prior art.
  • Another object of the present invention is to provide a preparation method of the above hollow fiber molecular sieve membrane to solve the use process of the hollow fiber molecular sieve membrane.
  • the strength problem in the medium, and the prepared zeolite membrane has excellent permeation properties at the same time.
  • a high-strength hollow fiber molecular sieve membrane characterized in that a carrier carrying a high-strength molecular sieve membrane is a multi-channel hollow fiber configuration.
  • the invention also provides a method for the above high-strength hollow fiber molecular sieve membrane, the specific steps of which are as follows:
  • Seed solution configuration molecular sieve seed particles and water are arranged in a molecular sieve suspension with a mass fraction of 0.5-5%, and water glass is added to the molecular sieve suspension to be ultrasonically treated to obtain a sufficiently dispersed seed crystal.
  • the molecular sieve seed particles have an average particle size of 50 nm to 3 ⁇ m; and the amount of water glass added to the molecular sieve seed suspension is 0 to 25% of the molecular sieve suspension mass fraction.
  • the multi-channel hollow fiber configuration in step (2) is 3 to 9 channels; the multi-channel hollow fiber configuration has an outer diameter of 2.0-4.0 mm, a channel diameter of 0.6-1.2 mm, and an average pore diameter of 0.6-1.5 ⁇ m.
  • the porosity of the carrier is 30 70%.
  • the carrier of the multi-channel hollow fiber configuration is made of one or more of alumina, titania, yttria-stabilized zirconia (YSZ) or silica.
  • the molecular sieve membrane prepared by the invention may be either an outer membrane or an inner membrane.
  • the molecular sieve seed particles are one of NaA, T type, MFI type or CHA type molecular sieves.
  • a high-strength multi-channel hollow fiber carrier is selected, and a uniform seed layer is obtained by adding water glass to the seed liquid to increase the viscosity of the seed liquid, and then a molecular sieve film is prepared by hydrothermal synthesis.
  • the multi-channel hollow fiber molecular sieve membrane carrier selected by the invention is a multi-channel hollow fiber. Compared with the single-channel hollow fiber, the high mechanical property is the same condition.
  • the breaking load of the multi-channel hollow fiber is a single-channel hollow fiber. More than double, the breakage rate of the hollow fiber during use can be effectively reduced.
  • the carrier micro-structure of the multi-channel hollow fiber molecular sieve membrane selected by the invention has strong controllability, and can meet different requirements for pore size and porosity and other related parameters in the application process.
  • the multi-channel hollow fiber molecular sieve membrane prepared by the invention can be a multi-channel hollow fiber outer membrane or a multi-channel hollow fiber inner membrane, which can realize effective membrane area regulation in the unit assembly.
  • the multi-channel hollow fiber NaA molecular sieve membrane prepared by the invention is used for separating 10% water/ethanol (75 °C), and the permeate water flux is as high as 12.8 kg ⁇ h -1 , which is much higher than the tubular NaA molecular sieve.
  • Membrane permeate water flux is also higher than the permeate flux of the previously reported hollow fiber molecular sieve membrane.
  • FIG. 2 is a four-channel hollow fiber NaA molecular sieve membrane of Example 1 (a) surface topography and (b) cross-sectional micro-morphology;
  • FIG. 3 is a seven-channel hollow fiber T-type molecular sieve membrane of Example 5 (a) surface microscopic shape;
  • Fig. 4 is a three-channel hollow fiber ⁇ molecular sieve membrane of Example 7 (a) surface micro-morphology (b) cross-section micro-morphology;
  • Figure 5 is the operating temperature for the four channels of Example 2. The effect of hollow fiber NaA molecular sieve membrane on pervaporation performance. detailed description
  • Example 1 Four-channel A1 2 0 3 hollow fiber was selected as a carrier (Fig. 1 (a)), and its porosity was 54%, and the average pore diameter was 0.9 ⁇ . The outer diameter is 3.4 mm and the channel diameter is 0.9 mm. The four-point hollow fiber with a span of 4 cm in the three-point bending strength test of the carrier had a breaking load of 17 N.
  • the NaA molecular sieve seed particles with an average particle diameter of 80 nm were sufficiently dispersed in water to prepare a seed suspension with a mass fraction of 1%, and water glass was added to the molecular sieve seed suspension, and the amount of the molecular sieve suspension was added. 5% of the mass fraction, fully stirred to obtain a dispersed seed solution.
  • the dried carrier is immersed in the seed solution and dried to obtain a four-channel hollow fiber carrier seeded on the outer surface (Fig. 2).
  • Example 2 A four-channel A1 2 3 hollow fiber was selected as a carrier having a porosity of 50%, an average pore diameter of 1.2 ⁇ m, an outer diameter of 3.0 mm, a channel diameter of 0.8 mm, and a span of 4 cm in a three-point bending strength test.
  • the hollow fiber breaking load is 19 N.
  • the NaA molecular sieve seed particles with an average particle diameter of 220 nm were sufficiently dispersed in water to prepare a seed suspension with a mass fraction of 3%, and water glass was added to the molecular sieve seed suspension, and the amount of the molecular sieve suspension was added. 10% of the mass fraction, fully stirred to obtain a dispersed seed solution.
  • the dried carrier is immersed in a seed solution and dried to obtain a four-channel hollow fiber carrier seeded with an inner surface.
  • Example 3 A four-channel A1 2 3 hollow fiber was selected as a carrier (Fig. 1 (b)), and its porosity was 45%, the average pore diameter was 0.9 ⁇ , the diameter was 3.2 mm, and the channel diameter was 0.8 mm.
  • the three-point bending strength test has a span of 4 cm and a breaking load of 21 N.
  • the NaA molecular sieve seed particles with an average particle diameter of 2 ⁇ are sufficiently dispersed in water to prepare a seed suspension having a mass fraction of 5%, and water glass is added to the molecular sieve seed suspension, and the amount of the molecular sieve suspension is added. 20% of the mass fraction, fully stirred to obtain a dispersed seed solution.
  • the pervaporation performance of the multi-channel NaA zeolite membrane prepared by the present invention was characterized, and the permeation performance of the membrane was evaluated by the permeate flux (J) and the separation factor ( ⁇ ).
  • the mass of the permeate side water is expressed in the formula (1), unit Kg; ⁇ represents the effective membrane area, the unit m 2 ; t represents the permeation time, the unit h.
  • ⁇ represents the content of the permeate side water, and represents the content of the organic matter on the permeate side, where ⁇ represents the content of the raw material water, and indicates the content of the organic matter measured by the raw material.
  • the permeation performance of the multi-channel hollow fiber NaA zeolite membrane was characterized by pervaporation ethanol dehydration separation experiments.
  • the feed liquid is continuously agitated under the action of a magnetic stirrer to make the temperature and concentration of the feed liquid uniform.
  • a single multi-channel hollow fiber membrane sealed at one end was placed in a liquid tank, and the other end was connected to a vacuum system to maintain a vacuum system pressure of less than 200 Pa, and liquid nitrogen condensation was used to trap the permeate product.
  • the multi-channel hollow fibers of Examples 1, 2 and 3 The pervaporation results of the NaA molecular sieve membrane for separation of 90 wt.% ethanol/water system at 75 ° C are listed in Table 1.
  • the fracture load of the carrier is greater than 17 N
  • the separation factor of the prepared NaA zeolite membrane is greater than 10,000
  • the permeate flux is greater than 8.0 kg ⁇ h -
  • Seven-channel YSZ hollow fiber was selected, with a porosity of 65%, an average pore diameter of 1.4 ⁇ , an outer diameter of 3.8 mm, and a channel diameter of 1.0 mm.
  • the 4 cm long four-channel hollow fiber has a breaking load of 22 N.
  • the T-type molecular sieve seed particles having an average particle diameter of 2 ⁇ m were sufficiently dispersed in water to prepare a seed suspension having a mass fraction of 5%, and the mixture was sufficiently stirred to obtain a dispersed seed solution.
  • the dried carrier is immersed in a seed solution, and dried to obtain a seeded seven-channel hollow fiber carrier.
  • Three-channel Ti0 2 hollow fiber was selected, with a porosity of 30%, an average pore diameter of 0.6 ⁇ , an outer diameter of 2.4 mm, and a channel diameter of 0.6 mm.
  • Three-point bending strength test The 4 cm long four-channel hollow fiber has a breaking load of 26 N.
  • the cerium molecular sieve seed particles having an average particle diameter of 50 nm were sufficiently dispersed in water to prepare a seed suspension having a mass fraction of 1%, and the mixture was sufficiently stirred to obtain a dispersed seed liquid.
  • the dried support is immersed in a seed solution and dried to obtain a seeded four-channel hollow fiber support.
  • tetrapropylammonium hydroxide: tetraethyl orthosilicate: 1:3.2: 560 (molar ratio) the synthetic liquid of MFI molecular sieve membrane is prepared, and the multi-channel hollow fiber carrier crystallized on the outer surface is put into the prepared synthesis.
  • the synthesis of the MFI molecular sieve membrane and the synthesis of the ruthenium molecular sieve outer membrane were the same as in Example 7.
  • Comparative Example 1 The Journal of the American Chemical Society (2009, 131(20): 6910-6911) reported that Professor Wang Zhengbao of Zhejiang University studied dip-coating on a single-channel alumina hollow fiber with a porosity of 50%.
  • the NaA zeolite membrane was prepared by coating the combined seed coating method.
  • the flux was 9.0 kg 'm ⁇ h.
  • the porosity of the first embodiment of the present invention was 54 %.
  • the permeate water flux of the NaA zeolite membrane prepared on the four-channel alumina hollow fiber is as high as US kg ⁇ h. It can be seen that the permeability of the NaA zeolite membrane produced on the four-channel hollow fiber carrier is higher than that of the single channel hollow. Fiber carrier.
  • Patent CN200910193335.9 reported the method for synthesizing NaA zeolite membrane on the surface of ⁇ - ⁇ 1 2 3 hollow fiber by Yuan Wenhui et al., but the single channel alumina hollow fiber NaA zeolite membrane prepared by the method, the separation at 60 ° C 90wt.% ethanol / The water permeation flux is only 1.95 ⁇ 0.35 kg-m" 2 -!!- 1 , and the permeate water flux of the four-channel alumina hollow fiber NaA zeolite membrane of Example 2 of the present invention is 6.2 kg under the same conditions. ⁇ h- 1 (see Figure 5) is 2 to 3 times.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Water Supply & Treatment (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Inorganic Fibers (AREA)
PCT/CN2014/077166 2013-12-31 2014-05-09 一种高强度的中空纤维分子筛膜及其制备方法 Ceased WO2015100900A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP14877023.3A EP3090798B1 (en) 2013-12-31 2014-05-09 High-strength hollow fiber molecular sieve membrane and preparation method therefor
JP2016522199A JP6158437B2 (ja) 2013-12-31 2014-05-09 高強度の中空糸型分子ふるい膜及びその製造方法
US14/898,472 US10427107B2 (en) 2013-12-31 2014-05-09 High-strength hollow fiber zeolite membrane and its preparation method

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CN201310754315.0 2013-12-31
CN201310754315.0A CN103657436B (zh) 2013-12-31 2013-12-31 一种高强度的中空纤维分子筛膜及其制备方法

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WO (1) WO2015100900A1 (enExample)

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JP6670764B2 (ja) * 2015-01-30 2020-03-25 日本碍子株式会社 分離膜構造体
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US9943808B2 (en) * 2016-02-19 2018-04-17 King Fahd University Of Petroleum And Minerals Aluminum oxide supported gas permeable membranes
CN105749764B (zh) * 2016-04-22 2018-05-25 南京工业大学 一体式多根陶瓷中空纤维分子筛膜制备方法
CN106378013B (zh) * 2016-11-10 2020-02-07 南京工业大学 一种多级孔道分子筛膜的制备方法及其应用
CN107335342B (zh) * 2017-09-06 2018-06-26 钱才英 一种中空纤维t型分子筛膜的合成装置及合成方法
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CN112156657A (zh) * 2020-10-09 2021-01-01 上海工程技术大学 一种全氟聚合物中空纤维复合膜的制备方法
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