WO2020087761A1 - 一种石脑油中提取有机硫化物的聚氨酯/聚偏氟乙烯复合膜及其制备方法 - Google Patents
一种石脑油中提取有机硫化物的聚氨酯/聚偏氟乙烯复合膜及其制备方法 Download PDFInfo
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- WO2020087761A1 WO2020087761A1 PCT/CN2018/125985 CN2018125985W WO2020087761A1 WO 2020087761 A1 WO2020087761 A1 WO 2020087761A1 CN 2018125985 W CN2018125985 W CN 2018125985W WO 2020087761 A1 WO2020087761 A1 WO 2020087761A1
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- Prior art keywords
- polyvinylidene fluoride
- polyurethane
- film
- fluoride composite
- composite membrane
- Prior art date
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 57
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 47
- 239000004814 polyurethane Substances 0.000 claims abstract description 47
- 239000012528 membrane Substances 0.000 claims description 39
- 238000005266 casting Methods 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 150000003568 thioethers Chemical class 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000005373 pervaporation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
-
- 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
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- 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
- B01D69/12—Composite membranes; Ultra-thin 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
- B01D71/5211—Polyethylene glycol or polyethyleneoxide
-
- 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
- B01D71/54—Polyureas; Polyurethanes
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Definitions
- the present invention relates to the technical field of composite membrane material processing, in particular to a polyurethane / polyvinylidene fluoride composite membrane for extracting organic sulfides from naphtha and a preparation method thereof.
- sulfide contained in naphtha include elemental sulfur, hydrogen sulfide, thiol, thioether, and thiophene.
- Organic sulfide is the main component.
- the traditional treatment process is hydrodesulfurization, which has high cost and harsh operating conditions.
- Organic sulfides are hydrotreated to become hydrogen sulfide, which can only be recycled and discharged after a complicated tail gas treatment process, resulting in huge waste.
- Polyurethane has strong chemical stability, strong solvent resistance, strong hydrophobic organic affinity, and other properties, is an ideal material for film making, when it is directly used in naphtha to extract sulfur-containing organic compounds , The permeation flux is low, which affects the extraction rate of sulfur-containing organic compounds.
- the present invention provides a polyurethane / polyvinylidene fluoride composite membrane for extracting organic sulfides from naphtha and a preparation method thereof.
- a polyurethane / polyvinylidene fluoride composite membrane from which organic sulfides are extracted from naphtha is composed of an active layer and a support layer, wherein the active layer is a polyurethane cast film and the support layer is a polyvinylidene fluoride film , And the active layer is coated on the support layer to prepare a polyurethane / polyvinylidene fluoride composite film.
- the thickness of the active layer is 20 ⁇ 3 (Vm, the thickness of the support layer is 110 ⁇ 120-.
- a method for preparing a polyurethane / polyvinylidene fluoride composite membrane for extracting organic sulfides from naphtha which is characterized in that the preparation steps are as follows:
- step b The film casting solution filtered in step b is left still for 2 to 5 hours to remove air bubbles, and the prepared polyurethane film casting solution is used as an active layer;
- step (2) The casting film solution defoamed in step (2) is coated on the polyvinylidene fluoride film obtained in step (1) with a doctor blade, and after coating, it is placed in a blast oven to remove the active layer Tetrahydrofuran to obtain polyurethane / polyvinylidene fluoride composite membrane.
- step (1) the mass ratio of polyvinylidene fluoride, polyethylene glycol, and N-methylpyrrolidone is 1: 0.1 ⁇ 0.2: 5 ⁇ 8.
- step (1) it is necessary to scrape the film on the non-woven fabric, when scraping the film, adjust the thickness of the scraper to 100 ⁇ 200 [xm °
- the thickness of the polyvinylidene fluoride film prepared in step (1) is 110-120-.
- step (2) the mass ratio of the polyurethane, tetrahydrofuran and polyethylene glycol is 2: 0.1 ⁇ 0.2: 12.
- step (3) the blade thickness is adjusted to 200 to 30 (Vm when the film is scraped, and the temperature of the blast oven is controlled to be 40 to 50 ° C during drying.
- the average molecular weight of the polyethylene glycol in steps (1) and (2) is 200.
- the beneficial effect of the present invention is that the composite membrane is a polyvinylidene fluoride ultrafiltration membrane as a support layer, polyvinylidene fluoride has strong mechanical properties, is a good support for pervaporation membrane, polyurethane is selected as According to the dissolution-diffusion theory, the active layer of the composite membrane has a strong affinity for organic sulfides in naphtha, and has advantages such as excellent solvent resistance and flexibility.
- the prepared composite membrane has high separation efficiency, and can extract more than 80% of organic sulfides in naphtha;
- the polyurethane / polyvinylidene fluoride composite membrane prepared by the present invention can be used for the extraction of organic sulfides in naphtha, which can significantly improve the extraction rate of organic sulfides.
- the mass ratio is 1: 0.15: 6.54, that is, 45.883g polyvinylidene fluoride, 7.058g polyethylene glycol, 300gN-A Put pyrrolidone in a round-bottom flask, stir for 12h in a 50 ° C water bath, filter and defoam after complete dissolution, adjust the blade thickness of the film scraper to 10 (Vm, scrape the film on the non-woven fabric, and scrape it well
- the membrane is immersed in deionized water for 72h, and then placed in a 60 ° C oven to dry, to obtain 110 ⁇ 12 (Vm polyvinylidene fluoride membrane, that is, the support layer; [0034] 2.
- the mass ratio is 2: 0.1: 12, which is 2g Polyurethane, O. lg polyethanol, 12g tetrahydrofuran are added to the Erlenmeyer flask
- the prepared film casting liquid was filtered with a 300 mesh copper mesh, and then the filtered film casting liquid was allowed to stand for 2 hours to remove air bubbles to prepare a polyurethane film casting liquid as an active layer.
- the prepared film casting liquid was filtered with a 300 mesh copper mesh, and then the filtered film casting liquid was allowed to stand for 2 hours to remove air bubbles, and a polyurethane film casting liquid was prepared as an active layer.
- the prepared film casting solution was filtered with a 300 mesh copper mesh, and then the filtered film casting solution was allowed to stand for 2 hours to remove air bubbles, and a polyurethane film casting solution was prepared as an active layer.
- polyethylene glycol to polyurethane can increase the spacing between polyurethane molecular chains, and polyethylene glycol also has a good affinity for organic sulfides, in improving the permeation flux At the same time, less sulfur enrichment factor is lost to avoid the trade-off effect of the permeation flux and enrichment factor often encountered when the pervaporation membrane is modified, so it can significantly improve the removal from naphtha The extraction rate of sulfur-containing organic compounds.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
一种石脑油中提取有机硫化物的聚氨酯/聚偏氟乙烯复合膜,涉及复合膜材料加工技术领域,由活性层和支撑层组成,活性层为聚氨酯铸膜,支撑层为聚偏氟乙烯膜,且活性层涂覆于支撑层上制得聚氨酯/聚偏氟乙烯复合膜,同时公开了该聚氨酯/聚偏氟乙烯复合膜的制备方法。有益效果是,所制得的聚氨酯/聚偏氟乙烯复合膜,可用于石脑油中有机硫化物的提取,分离效率高、装置简单、操作方便、条件温和,且该复合膜基本不改变原料油品辛烷值等性质,能显著提高有机硫化物得到提取率。
Description
一种石脑油中提取有机硫化物的聚氨酯 /聚偏氟乙烯复合 膜及其制备方法 技术领域
[0001] 本发明涉及复合膜材料加工技术领域, 尤其涉及一种石脑油中提取有机硫化物 的聚氨醋 /聚偏氟乙烯复合膜及其制备方法。
背景技术
[0002] 目前, 随着世界各国对环境保护的日益重视及环保法规的日益严格, 生产清洁 油品已成为世界范围内的重要研究课题。 石脑油中所含硫化物的存在形式有元 素硫、 硫化氢、 硫醇、 硫醚以及噻吩等, 有机硫化物是其中的主要组成部分。 传统的处理工艺为加氢脱硫, 该工艺成本高, 操作条件苛刻, 有机硫化物经加 氢处理后变成硫化氢, 要经过复杂的尾气处理工艺后才能回收利用和排放, 造 成巨大的浪费。
[0003] 随着膜分离技术的发展与应用, 越来越多的膜分离过程应用于实际的化工生产 过程中, 其中, 渗透汽化技术具有环境友好、 经济性好、 易于放大等优点, 收 到各国研究者的重视, 将其用于油品中有机硫化物的提取, 操作简单, 不需对 原料预处理, 不发生化学反应, 避免了硫化氢的产生, 不仅可降低油品中的硫 含量, 提取出的噻吩等有机硫化物经过简单的提纯过程后, 还可作为制造医药 、 农药、 染料等化工产品的重要原料, 具有很好的环境效益和经济价值。
[0004] 聚氨酯有较强的化学稳定性、 较强的耐溶剂性、 较强的疏水亲有机物等性能, 是制膜的理想材料, 将其直接用于石脑油中提取含硫有机化合物时, 渗透通量 较低, 影响含硫有机化合物提取率。
发明概述
技术问题
问题的解决方案
技术解决方案
[0005] 解决上述技术问题, 本发明提供一种石脑油中提取有机硫化物的聚氨醋 /聚偏 氟乙烯复合膜及其制备方法。
[0006] 为实现上述目的, 本发明采用下述技术方案:
[0007] 一种石脑油中提取有机硫化物的聚氨醋 /聚偏氟乙烯复合膜, 由活性层和支撑 层组成, 其中, 活性层为聚氨酯铸膜, 支撑层为聚偏氟乙烯膜, 且所述活性层 涂覆于所述支撑层上制得聚氨醋 /聚偏氟乙烯复合膜。
[0008] 进一步地, 所述活性层的厚度为 20~3(Vm, 支撑层的厚度为 110~120—。
[0009] 一种石脑油中提取有机硫化物的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特 征在于, 制备步骤如下:
[0010] ( 1) 支撑层准备
[0011] 将一定质量比的聚偏氟乙烯、 聚乙二醇、 N-甲基吡咯烷酮加入圆底烧瓶中, 圆 底烧瓶放置于 50~60°C恒温水浴中 12~24h, 待完全溶解后依次进行过滤、 脱气、 刮膜和干燥处理;
[0012] 将刮好的膜放入去离子水中 48~72h, 除去 N-甲基吡咯烷酮后, 再放入鼓风烘箱 中干燥, 温度控制在 50~60°C, 得到聚偏氟乙烯膜, 作为支撑层;
[0013] (2) 活性层准备
[0014] a、 将一定质量比的聚氨酯、 聚乙二醇、 四氢呋喃加入圆底烧瓶中, 待其完全 溶解, 形成均相铸膜液;
[0015] b、 将 a制得的均相铸膜液用 300目的不锈钢过滤网进行过滤;
[0016] c 将经步骤 b过滤后的铸膜液静止 2~5h, 脱除气泡, 制得的聚氨酯铸膜液作为 活性层;
[0017] (3) 复合膜制备
[0018] 将步骤 (2) 脱泡后的铸膜液用刮刀涂覆在步骤 ( 1) 所得的聚偏氟乙烯膜上, 涂覆后, 放入鼓风烘箱中, 脱除活性层内的四氢呋喃, 得到聚氨醋 /聚偏氟乙烯 复合膜。
[0019] 进一步地, 步骤 ⑴ 中, 聚偏氟乙烯、 聚乙二醇、 N-甲基吡咯烷酮的质量比 为 1:0.1~0.2:5~8。
[0020] 进一步地, 步骤 ( 1) 中, 需要在无纺布上刮膜, 刮膜时, 调整刮刀厚度为 100
〜 200[xm°
[0021] 进一步地, 步骤 ⑴ 所制备的聚偏氟乙烯膜的厚度为 110~120—。
[0022] 进一步地, 步骤 (2) 中, 所述聚氨酯、 四氢呋喃和聚乙二醇的质量比为 2:0.1~ 0.2: 12。
[0023] 进一步地, 步骤 (3) 中, 刮膜时调整刮刀厚度为 200~30(Vm, 干燥时控制鼓 风烘箱温度为 40~50°C。
[0024] 进一步地, 步骤 (1) 和 (2) 中的聚乙二醇的平均分子量为 200。
发明的有益效果
有益效果
[0025] 本发明的有益效果是, 该复合膜是以聚偏氟乙烯超滤膜为支撑层, 聚偏氟乙烯 具有较强的机械性能, 是渗透气化膜良好的支撑体, 选用聚氨酯作为复合膜的 活性层, 根据溶解 -扩散理论, 聚氨酯对石脑油中的有机硫化物具有较强的亲和 力, 且具有优良的耐溶剂性、 柔韧性等优势。
[0026] 将本发明制得的聚氨醋 /聚偏氟乙烯复合膜用于石脑油中有机硫化物的提取时 , 具有以下优点:
[0027] 1、 所制得的复合膜分离效率高, 可提取石脑油中 80%以上的有机硫化物;
[0028] 2、 装置简单, 操作方便, 条件温和;
[0029] 3、 基本不改变原料油品辛烷值等性质;
[0030] 综上, 本发明所制得的聚氨醋 /聚偏氟乙烯复合膜可用于石脑油中有机硫化物 的提取, 显著提高有机硫化物得到提取率。
发明实施例
本发明的实施方式
[0031] 下面对本发明实施例中的技术方案进行清楚、 完整地描述, 显然, 所描述的实 施例仅是本发明一部分实施例, 而不是全部的实施例。 基于本发明中的实施例 , 本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例 , 都属于本发明保护的范围。
[0032] 实施例 1
[0033] 1、 将质量比为 1:0.15:6.54, 即 45.883g聚偏氟乙烯, 7.058g聚乙二醇, 300gN-甲
基吡咯烷酮放入圆底烧瓶中, 在 50°C水浴中搅拌 12h, 完全溶解后过滤、 脱泡, 将刮膜机刮刀厚度调整为 10(Vm, 在无纺布上刮膜, 将刮好的膜浸入去离子水中 72h, 随后放入 60°C烘箱干燥, 得到 110~12(Vm的聚偏氟乙烯膜, 即支撑层; [0034] 2、 将质量比为 2:0.1: 12, 即 2g聚氨酯、 O. lg聚乙醇、 12g四氢呋喃加入锥形瓶中
, 在室温下溶解, 得到铸膜液;
[0035] 将制得的铸膜液用 300目的铜网过滤, 然后将过滤的铸膜液静置 2h以脱除气泡 , 制得聚氨酯铸膜液作为活性层。
[0036] 3、 调整刮刀厚度为 30(Vm, 将步骤 2得到的铸膜液涂覆在步骤 1得到的聚偏氟 乙烯支撑层上, 所得到的膜放入 40°C鼓风烘箱中, 除去四氢呋喃, 得到聚氨醋 / 聚偏氟乙烯复合膜。
[0037] 实施例 2
[0038] 1、 将质量比为 1:0.1:5.97, 即 50.285g聚偏氟乙烯、 5.145g聚乙二醇、 300gN-甲 基吡咯烷酮放入圆底烧瓶中, 在 50°C水浴中搅拌 12h, 完全溶解后过滤、 脱泡, 将刮膜机刮刀厚度调整为 10(Vm, 在无纺布上刮膜, 将刮好的膜浸入去离子水中 72h, 随后放入 60°C烘箱干燥, 得到 110~12(Vm的聚偏氟乙烯膜, 即支撑层; [0039] 2、 将质量比为 2:0.15: 12, 即 2g聚氨酯、 0.15g聚乙二醇、 12g四氢呋喃加入锥形 瓶中, 在室温下溶解, 得到铸膜液;
[0040] 将制得的铸膜液用 300目的铜网过滤, 然后将过滤的铸膜液静置 2h以脱除气泡 , 制得聚氨酯铸膜液作为活性层。
[0041] 3、 调整刮刀厚度为 25(Vm, 将步骤 2得到的铸膜液涂覆在步骤 1得到的聚偏氟 乙烯支撑层上, 所得到的膜放入 40°C鼓风烘箱中, 除去四氢呋喃, 得到聚氨醋 / 聚偏氟乙烯复合膜。
[0042] 实施例 3
[0043] 1、 将质量比为 1:0.2:7.41, 即 47.241g聚偏氟乙烯、 9.365g聚乙二醇、 350gN-甲 基吡咯烷酮放入圆底烧瓶中在 50°C水浴中搅拌 12h, 完全溶解后过滤、 脱泡, 将 刮膜机刮刀厚度调整为 10(Vm, 在无纺布上刮膜, 将刮好的膜浸入去离子水中 72 h, 随后放入 60°C烘箱干燥, 得到 110~12(Vm的聚偏氟乙烯膜, 即支撑层;
[0044] 2、 将质量比为 2:0.2: 12, 即 2g聚氨酯、 0.2g聚乙二醇、 12g四氢呋喃加入锥形瓶
中, 在室温下溶解, 得到铸膜液;
[0045] 将制得的铸膜液用 300目的铜网过滤, 然后将过滤的铸膜液静置 2h以脱除气泡 , 制得聚氨酯铸膜液作为活性层。
[0046] 3、 调整刮刀厚度为 20(Vm, 将步骤 2得到的铸膜液涂覆在步骤 1得到的聚偏氟 乙烯支撑层上, 所得到的膜放入 40°C鼓风烘箱中, 除去四氢呋喃, 得到聚氨醋 / 聚偏氟乙烯复合膜。
[0047] 1、 聚氨醋 /聚偏氟乙烯复合膜处理石脑油
[0048] 将实施例 1、 2和 3制得的聚氨醋 /聚偏氟乙烯复合膜进行石脑油中有机硫化物的 提取实验, 用三种聚氨醋 /聚偏氟乙烯复合膜来处理不同的石脑油中硫含量, 得 到渗透通量和富集液中硫含量数据, 具体实验结果如表一所示:
[0049] 表一
[0050] 结果显示, 在该实验条件下, 三种实施例制得的复合膜的渗透通量都能达到 1~ 2 kg«m-2«h-l以上, 硫富集因子 (富集液中硫含量 /石脑油中硫含量) 都在 3.00左 右, 对硫化物的提取效果好。
[0051] 2、 聚氨醋 /聚偏氟乙烯复合膜寿命
[0052] 此外, 对实施例 1、 2和 3制得的聚氨醋 /聚偏氟乙烯复合膜进行寿命测试, 石脑 油中硫含量为 1300mg/L、 进料流量为 90mL/min, 连续运行 100h后, 得到的实验 数据如表二所示:
[0053] 表二
[0054] 实验结果显示, 该实验条件下, 渗透通量均在 1.00 kg*m-2*h-l以上, 硫富集因 子均维持在 3.00以上。
[0055] 本发明中, 在聚氨酯中加入聚乙二醇, 可以增大聚氨酯分子链之间的间距, 且 聚乙二醇对有机硫化物也具有良好的亲和性, 在提高渗透通量的同时损失较少 的硫富集因子, 避免渗透汽化膜改性时经常遇到的渗透通量和富集因子此消彼 长的“trade-off’效应, 因而能显著地提高从石脑油中提取含硫有机化合物的提取 率。
[0056] 当然, 上述说明并非是对本发明的限制, 本发明也并不仅限于上述举例, 本技 术领域的技术人员在本发明的实质范围内所做出的变化、 改型、 添加或替换, 也应属于本发明的保护范围。
Claims
( 1) 支撑层准备
将一定质量比的聚偏氟乙烯、 聚乙二醇、 N-甲基吡咯烷酮加入圆底烧 瓶中, 圆底烧瓶放置于 50~60°C恒温水浴中 12~24h, 待完全溶解后依 次进行过滤、 脱气、 刮膜和干燥处理;
将刮好的膜放入去离子水中 48~72h, 除去 N-甲基吡咯烷酮后, 再放 入鼓风烘箱中干燥, 温度控制在 50~60°C, 得到聚偏氟乙烯膜, 作为 支撑层;
(2) 活性层准备
a、 将一定质量比的聚氨醋、 聚乙二醇、 四氢呋喃加入圆底烧瓶中, 待其完全溶解, 形成均相铸膜液;
b、 将 a制得的均相铸膜液用 300目的不锈钢过滤网进行过滤; c 将经步骤 b过滤后的铸膜液静止 2~5h, 脱除气泡, 制得的聚氨酯铸 膜液作为活性层;
(3) 复合膜制备
将步骤 (2) 脱泡后的铸膜液用刮刀涂覆在步骤 ( 1) 所得的聚偏氟乙 烯膜上, 涂覆后, 放入鼓风烘箱中, 脱除活性层内的四氢呋喃, 得到 聚氨醋 /聚偏氟乙烯复合膜。
[权利要求 4] 如权利要求 3所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在
于, 步骤 ⑴ 中, 聚偏氟乙烯、 聚乙二醇、 N-甲基吡咯烷酮的质量 比为 1:0.1~0.2:5~8。
[权利要求 5] 如权利要求 4所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在 于, 步骤 (1) 中, 需要在无纺布上刮膜, 刮膜时, 调整刮刀厚度为 1
00〜 200[xm。
[权利要求 6] 如权利要求 3所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在 于, 步骤 ⑴ 所制备的聚偏氟乙烯膜的厚度为 110~120—。
[权利要求 7] 如权利要求 3所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在 于, 步骤 (2) 中, 所述聚氨酯、 四氢呋喃和聚乙二醇的质量比为 2:0. 1~0.2:12。
[权利要求 8] 如权利要求 3所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在 于, 步骤 (3) 中, 刮膜时调整刮刀厚度为 200~30(Vm, 干燥时控制 鼓风烘箱温度为 40~50°C。
[权利要求 9] 如权利要求 3所述的聚氨醋 /聚偏氟乙烯复合膜的制备方法, 其特征在 于, 步骤 (1) 和 (2) 中的聚乙二醇的平均分子量为 200。
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