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WO2016163296A1 - Matériau de séparation de sulfure d'hydrogène, et membrane de séparation de sulfure d'hydrogène - Google Patents

Matériau de séparation de sulfure d'hydrogène, et membrane de séparation de sulfure d'hydrogène Download PDF

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Publication number
WO2016163296A1
WO2016163296A1 PCT/JP2016/060618 JP2016060618W WO2016163296A1 WO 2016163296 A1 WO2016163296 A1 WO 2016163296A1 JP 2016060618 W JP2016060618 W JP 2016060618W WO 2016163296 A1 WO2016163296 A1 WO 2016163296A1
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Prior art keywords
hydrogen sulfide
sulfide separation
water
separation membrane
amine
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English (en)
Japanese (ja)
Inventor
亜由美 青木
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a hydrogen sulfide separation material for separating hydrogen sulfide from a gas containing hydrogen sulfide and a hydrogen sulfide separation membrane obtained from the hydrogen sulfide separation material.
  • Patent Document 1 describes a hydrogen sulfide separation membrane using a selectively permeable thin film of a cured polysulfide polymer.
  • an object of the present invention is to provide a hydrogen sulfide separation material useful for producing a hydrogen sulfide separation membrane having excellent hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity).
  • the present invention includes the following inventions [1] to [7].
  • [1] A hydrogen sulfide separator comprising a water-absorbing polymer and an amine carrier.
  • a hydrogen sulfide separation membrane comprising the hydrogen sulfide separator according to any one of [1] to [4] and a porous membrane.
  • a hydrogen sulfide separator including the hydrogen sulfide separation membrane according to [5].
  • Hydrogen sulfide is separated by bringing the hydrogen sulfide separation material according to any one of [1] to [4] or the hydrogen sulfide separation membrane according to [5] into contact with a mixed gas containing hydrogen sulfide.
  • the hydrogen sulfide separation material of the present invention is used, a hydrogen sulfide separation membrane excellent in hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity) can be produced.
  • the water-absorbing polymer contained in the hydrogen sulfide separating material of the present invention has a hydrophilic group and a three-dimensional network structure, and represents a swelled body containing water.
  • the water-absorbing polymer is preferably a polymer having a crosslinked structure, that is, a crosslinked polymer.
  • the crosslinked polymer may be formed by a chemical reaction using a crosslinking agent or may be formed by physical interaction.
  • the hydrophilic group as used herein represents an atomic group containing a polar group or a dissociating group capable of interacting with water.
  • a hydroxyl group, a carboxyl group, a vinyl group, an amino group, a cyano group, an oxyethylene group examples include carbonyl group, sulfo group, phosphono group, sulfonylimide group, phenolic hydroxyl group and the like.
  • the hydrophilic group is preferably an ion exchange group, and examples of the ion exchange group include a sulfo group, a carboxyl group, a phosphono group, a sulfonylimide group, and a phenolic hydroxyl group. Protons of these ion exchange groups may be partially or wholly exchanged with metal ions or quaternary ammonium ions to form salts.
  • the water-absorbing polymer usually contains an alkali metal.
  • the amount of alkali metal contained in the water-absorbing polymer preferably satisfies the condition represented by the following formula (1).
  • X 1 Number of moles of alkali metal contained in the water-absorbing polymer
  • X 2 Equivalent number of ion-exchange groups contained in the water-absorbing polymer
  • Y Average atomic weight of alkali metal contained in the water-absorbing polymer
  • Z Water-absorbing property Polymer mass
  • the number of equivalents of ion-exchange groups in the water-absorbing polymer represented by X 2 the number of moles of ion-exchange groups in the water-absorbing polymer, multiplied by the absolute value of the valence of the ion-exchange group Is.
  • the number of equivalents of ion exchange groups contained in the water-absorbing polymer is 2 mol
  • 1 mol of COO ⁇ is contained in the water-absorbing polymer.
  • the equivalent number of ion exchange groups contained in the water-absorbing polymer is 1 mol.
  • the left side of the above formula (1) represents the mass ratio (mass%) of the alkali metal contained in the water-absorbing polymer, excluding the alkali metal that can bind to the ion exchange group. This value is preferably 0 or less from the viewpoint of maintaining high hydrogen sulfide separation performance.
  • the alkali metal includes an alkali metal atom (alkali metal ion) contained in the alkali metal compound. It is preferable not to contain an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali metal hydroxide or the like other than an ion exchange group to which an alkali metal ion is bonded.
  • the water-absorbing polymer contained in the hydrogen sulfide separation material of the present invention includes natural polymers (polysaccharides, microorganisms, animals), semi-synthetic polymers (cellulose, starch, alginic acid) and synthetic polymers (vinyl).
  • natural polymers polysaccharides, microorganisms, animals
  • semi-synthetic polymers cellulose, starch, alginic acid
  • synthetic polymers vinyl
  • a synthetic polymer typified by polyvinyl alcohol described below, or a natural polymer or semi-synthetic polymer made from plant-derived cellulose or the like as appropriate. it can.
  • Plant polysaccharide-based natural polymers include gum arabic, ⁇ -carrageenan, ⁇ -carrageenan, ⁇ -carrageenan, guar gum (Squalon Supercol, etc.), locust bean gum, pectin, tragacanth, corn starch (National Starch & Chemical Co Purity-21, etc.) and phosphorylated starch (National Starch & Chemical Co., National 78-1898, etc.).
  • microbial polysaccharide-based natural polymers examples include xanthan gum (such as Keltrol T from Kelco) and dextrin (such as Nadex 360 from National Starch & Chemical Co.).
  • animal-based natural polymers include gelatin (such as Crodyne B419 from Croda), casein, sodium chondroitin sulfate (such as Cromoist CS from Croda), and the like.
  • Cellulose semi-synthetic polymers include ethyl cellulose (ICI Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), methyl cellulose (Henkel Viscontran, etc.), nitrocellulose (Isopropyl Wet, etc. from Hercules), and cationized cellulose (Crodacel QM, etc. from Croda).
  • starch-based semi-synthetic polymer include phosphorylated starch (National Starch &Chemical's National 78-1898, etc.).
  • alginic acid-based semi-synthetic polymer examples include sodium alginate (such as Keltone manufactured by Kelco) and propylene glycol alginate.
  • Other classifications of natural or semi-synthetic polymers include cationized guar gum (such as Hi-care 1000 from Alcolac) and sodium hyaluronate (such as Hyalure from Lifecare Biomedial). Any of these water-absorbing polymers may be a commercially available product, for example, a product provided by a manufacturer described in parentheses in addition to the name of each compound.
  • acrylic synthetic polymers include polyacrylic acid, sodium polyacrylate, polyacrylic acid copolymer, polyacrylamide, polyacrylamide copolymer, polydiethylaminoethyl (meth) acrylate quaternary salt or copolymer thereof, etc.
  • vinyl-based synthetic polymer examples include polyvinyl pyrrolidone, a polyvinyl pyrrolidone copolymer, and polyvinyl alcohol.
  • polymers include polyethylene glycol, polypropylene glycol, polyisopropylacrylamide, polymethyl vinyl ether, polyethylene imine, polyallylamine, polyvinyl amine, nafion, polystyrene sulfonic acid or copolymers thereof, naphthalene sulfonic acid condensate salt, polyvinyl Sulfonic acid or copolymer thereof, polyacrylic acid or copolymer thereof, acrylic acid or copolymer thereof, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid or copolymer thereof , Etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethyla Down condensates, Hofmann degradation product of polyacrylamide, such as water-soluble polyester are exe
  • water-soluble polyesters (Plus Coat Z-221, Z-446, Z-561, Z-450, Z-565, Z, manufactured by Kyoyo Chemical Co., Ltd.) -850, Z-3308, RZ-105, RZ-570, Z-730, RZ-142: all are trade names).
  • the water-absorbing polymer contained in the hydrogen sulfide separator is preferably a saponified product of polyacrylic acid, polyvinyl alcohol, vinyl alcohol-polyacrylic acid copolymer, and a saponified product of polyvinyl alcohol, vinyl alcohol-polyacrylic acid copolymer. Is more preferable.
  • the content of the water-absorbing polymer contained in the hydrogen sulfide separating material of the present invention depends on the type of the water-absorbing polymer and amine-based carrier contained in the hydrogen sulfide separating material of the present invention.
  • the content is preferably 5% by mass to 99% by mass, more preferably 7.5% by mass to 90% by mass, and still more preferably 10% by mass to 85% by mass with respect to the total content.
  • the water absorbing polymer contained in the hydrogen sulfide separating material of the present invention may be used alone or in combination of two or more.
  • the content of the water-absorbing polymer referred to here represents the content of the absolutely dry polymer.
  • the completely dry polymer as used herein refers to a polymer in which the water-absorbing polymer is maintained at a temperature equal to or higher than the boiling point of water, and the mass change is almost eliminated and the change with time of the mass converges to a substantially constant value.
  • the carrier is a substance that reacts reversibly with hydrogen sulfide
  • the amine carrier contained in the hydrogen sulfide separation material of the present invention is an amine compound that reacts reversibly with hydrogen sulfide.
  • Examples of the reversible reaction between hydrogen sulfide and an amine carrier include, for example, one or more selected from the group consisting of a reaction represented by the following reaction formula (2) and a reaction represented by the following formula (3): Reaction.
  • each R independently represents a monovalent group.
  • An amine compound is considered to be excellent as a hydrogen sulfide separation carrier because it absorbs a large amount of hydrogen sulfide per carrier.
  • sulfur oxide ions such as thiosulfate ions, sulfate ions, and sulfite ions are generated from hydrogen sulfide, causing an irreversible reaction with the carriers, thereby reducing the number of carriers that react reversibly with hydrogen sulfide.
  • an amine compound is used as a carrier, the amount of sulfur oxide ions generated from hydrogen sulfide is small even in an oxygen-mixed environment.
  • amine carrier examples include amino acids such as glycine, alanine, serine, proline, taurine, diaminopropionic acid, 2-aminopropionic acid, 2-aminoisobutyric acid, and 3,4-dihydroxyphenylalanine; Saponified amino acids saponified using an alkali metal compound, etc .; heterocyclic compounds such as pyridine, histamine, histidine, piperazine, imidazole, triazine, xanthosine, 2-methylpiperazine, cis-2,6-dimethylpiperazine, acetaldehyde ammonia trimer Amine compounds (also called hetero compounds); monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, methyldiethanolamine, diglycolamine, ⁇ , ⁇ -hydroxy Alkanolamines such as minoethyl ether, 3-amino-1-propanol, N- (3-hydroxypropyl) ethylenediamine, dipropy
  • Preferred amine carriers include amino acids having acid groups such as glycine, histidine and 2-aminoisobutyric acid; heterocyclic amine compounds such as histamine, histidine, piperazine and xanthosine; monoethanolamine, diethanolamine, triethanolamine, diethanolamine Alkanolamines such as isopropanolamine, methyldiethanolamine, diglycolamine, ⁇ , ⁇ -hydroxyaminoethyl ether and the like, and more preferable amine carriers include heterocyclic amine compounds, and more preferable amine carriers. Is piperazine.
  • an amine carrier having a boiling point of 50 ° C. or higher is preferable, and an amine carrier having a boiling point of 80 ° C. or higher is more preferable.
  • the amine carrier has such a boiling point, when the hydrogen sulfide separation membrane is produced using the hydrogen sulfide separator, the amine carrier is less likely to volatilize.
  • the content of the amine carrier contained in the hydrogen sulfide separation material of the present invention depends on the type of the water absorbent polymer and the amine carrier, but is 15% by mass to 750% by mass with respect to the content of the water absorbent polymer. It is a range. From the viewpoint of hydrogen sulfide permeability (permeance), the content of the amine carrier is preferably 15% by mass or more with respect to the content of the water-absorbing polymer, and when the content is 750% by mass or less, the film is easy to handle. Is preferable. Moreover, the amine carrier contained in the hydrogen sulfide separator of the present invention may be used alone or in combination of two or more.
  • the hydrogen sulfide separating material of the present invention contains an amine carrier, but may further contain a carrier other than the amine carrier.
  • carriers other than amine carriers include known carriers, but alkali metal compounds are considered not to be excellent as hydrogen sulfide separation carriers because the number of absorbed hydrogen sulfides per carrier number is small.
  • sulfur oxide ions such as thiosulfate ions, sulfate ions, and sulfite ions are generated from hydrogen sulfide, causing an irreversible reaction with the alkali metal compound, thereby causing an alkali that reacts reversibly with hydrogen sulfide.
  • the number of carriers of the metal compound may decrease.
  • the solvent water or an organic solvent can be used, and water is particularly preferable.
  • the amount of the solvent used is preferably an amount that can be present as a homogeneous solution when the obtained hydrogen sulfide separator is subjected to Step B described later.
  • the order of mixing in step A is not particularly limited, and the mixing temperature is preferably in the range of 5 ° C to 90 ° C.
  • the obtained hydrogen sulfide separating agent may be dried after step A.
  • the hydrogen sulfide separation membrane of the present invention has the hydrogen sulfide separation material of the present invention and a porous membrane.
  • the hydrogen sulfide separation material of the present invention is usually carried on a porous membrane.
  • porous membrane either a hydrophilic porous membrane or a hydrophobic porous membrane can be used.
  • a laminate of a hydrophilic porous membrane and a hydrophobic porous membrane can also be used.
  • the hydrogen sulfide separating material supplied to Step B preferably contains water as a solvent, and more preferably an aqueous solution.
  • Application in the step B can be performed by an industrially usual method such as application by a coater (also referred to as a doctor blade) or application by brush coating.
  • the thickness of the hydrogen sulfide separating material layer (the layer containing the hydrogen sulfide separating material) can be controlled by adjusting the amount and amount ratio of the amine carrier and the water-absorbing polymer.
  • the thickness of the hydrogen sulfide separation material layer is preferably in the range of 25 ⁇ m or more and 200 ⁇ m or less because the hydrogen sulfide permeation performance of the hydrogen sulfide separation membrane and the mechanical durability of the hydrogen sulfide separation membrane are excellent.
  • the heat treatment in the process D is usually performed by a heating means such as a thermostatic bath or a hot plate.
  • the heat treatment temperature is preferably in the range of 80 ° C to 160 ° C.
  • the heat treatment time is preferably in the range of 10 minutes to 4 hours, although it depends on the heat treatment temperature.
  • the hydrogen sulfide separation membrane of the present invention can be a hydrogen sulfide separation membrane module.
  • the hydrogen sulfide separation device of the present invention includes a hydrogen sulfide separation membrane or a hydrogen sulfide separation membrane module, and has means for separating hydrogen sulfide.
  • the hydrogen sulfide separation membrane of the present invention can be used more suitably by modularization.
  • module types include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
  • the hydrogen sulfide separation membrane of the present invention may be used, for example, in a gas separation / recovery device as a membrane / absorption hybrid method used in combination with an absorbing solution described in JP-A-2007-297605.
  • the mixed gas containing hydrogen sulfide preferably contains water.
  • the relative humidity of the mixed gas is preferably 30% RH to 100% RH, more preferably 50% RH to 100% RH, and still more preferably 70% RH to 100% RH.
  • the hydrogen sulfide separation material of the present invention or the hydrogen sulfide separation membrane of the present invention preferably contains water.
  • the mixed gas containing hydrogen sulfide preferably contains 5 ppm to 50% of hydrogen sulfide, more preferably 5 ppm to 20%, and even more preferably 5 ppm to 1%.
  • the method for separating hydrogen sulfide of the present invention can selectively separate hydrogen sulfide even from a mixed gas containing hydrogen sulfide at a low concentration.
  • the existing desulfurization process or chemical absorption method is used.
  • the hydrogen sulfide may be further separated and / or removed in combination with an acidic gas separation process such as By using it together with the existing desulfurization process and acid gas separation process, the load on the existing process can be reduced.
  • the field of application of the present invention is not particularly limited, for example, separation of acid gas containing hydrogen sulfide from biogas generated by anaerobic treatment method; petroleum refining; coal gasification power generation; dry desulfurization method, wet method in various chemical plants Pretreatment applications such as desulfurization, biodesulfurization, and amine absorption; and alternative applications are envisaged.
  • An anaerobic treatment method using anaerobic microorganisms is usually used for wastewater with a high concentration of organic components.
  • organic components are decomposed and biogas containing methane as a main component is generated.
  • Methane in biogas can be used for energy, and its use as a fuel gas for gas engines has been put to practical use. In the future, it is expected that methane in biogas will be used as fuel gas for solid oxide fuel cells.
  • Anaerobic microorganisms have different temperatures that are likely to be activated depending on the type.
  • Thermophilic bacteria produce a lot of biogas around 40 ° C
  • thermophilic bacteria produce a lot of biogas around 55 ° C.
  • the composition of biogas varies depending on drainage conditions, but the main components are 65% to 85% by volume of methane, 15% to 35% by volume of carbon dioxide, and 1000ppm to 6000ppm of hydrogen sulfide (parts per million by volume). included.
  • the separated methane gas contains carbon dioxide and moisture as compared with the biogas before separating the acidic gas containing hydrogen sulfide. Since the content is small, an improvement in efficiency when used as fuel gas is expected.
  • the hydrogen sulfide separated from the biogas by the hydrogen sulfide separation method using the hydrogen sulfide separation material or the hydrogen sulfide separation membrane of the present invention can be treated by a known hydrogen sulfide treatment method.
  • One of the methods for treating hydrogen sulfide separated from biogas by the hydrogen sulfide separation method using the hydrogen sulfide separation material or hydrogen sulfide separation membrane of the present invention is a method utilizing an aerobic waste water treatment process. It is done. By injecting the separated hydrogen sulfide into the aerobic wastewater treatment tank, the hydrogen sulfide is converted into sulfuric acid by the action of sulfur-oxidizing bacteria in the activated sludge.
  • the temperature of the mixed gas to be separated is relatively low, specifically in the range of 10 ° C. to 80 ° C., preferably 20 Since it can be used in the range of from 70 ° C. to 70 ° C., more preferably in the range of from 35 ° C. to 60 ° C., it is industrially preferable from the viewpoint of energy.
  • ⁇ Hydrogen sulfide permeability coefficient> A hydrogen sulfide separation membrane was sandwiched between the cells, a nitrogen / hydrogen sulfide mixed gas (a mixed gas containing nitrogen gas and hydrogen sulfide gas) was allowed to flow on the supply side, and nitrogen gas was allowed to flow on the permeate side.
  • the hydrogen sulfide gas concentration on the supply side was set to a predetermined concentration depending on conditions.
  • the temperature of the cell was set to a predetermined temperature depending on conditions.
  • Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions.
  • the flow rates of the hydrogen sulfide mixed gas and nitrogen gas were each set to 50 cc / min.
  • Hydrogen sulfide permeation coefficient [mol / m 2 / sec / kPa] indicates the concentration of hydrogen sulfide in the permeate side outlet gas (Gasek detector tube, for hydrogen sulfide measurement, detector tube name 4H, measurement range 10 ppm to 4000 ppm) ) was used to measure.
  • a nitrogen permeation coefficient [mol / m 2 / sec / kPa] was measured by an isobaric method using a gas permeation measuring apparatus (GTR Tech Co., Ltd., model: GTR-30XAF3SC).
  • the temperature of the cell sandwiching the hydrogen sulfide separation membrane was set to a predetermined temperature depending on the conditions. Nitrogen gas was allowed to flow on the supply side, and argon gas was allowed to flow on the permeate side. Each gas on the supply / permeation side was humidified through a bubbler heated to a predetermined temperature depending on conditions. The flow rates of nitrogen gas and argon gas were each set to 50 cc / min.
  • the back pressure was 0 kPaG on both the supply side and the permeation side.
  • ⁇ Hydrogen sulfide exposure method Each hydrogen sulfide carrier aqueous solution was exposed for 24 hours in an environment of 3.0% by volume hydrogen sulfide gas and 97% by volume air prepared by aeration of hydrogen sulfide gas at 60 ml / min for 720 seconds in an acrylic water tank of ⁇ 320 mm ⁇ 300 mm. .
  • the amount of generated sulfur oxide ions was quantified using an ion chromatograph (IXS-2000 manufactured by Dionex). As the column, IonPacAS17 manufactured by Nippon Dionex Co., Ltd. was used. The eluent used was potassium hydroxide 1 mmol / l (0-1.5 min), 1-20 mmol / l (1.5-5 min), 20-40 mmol / l (5-7 min) at a flow rate of 1.0 ml / min. It was measured. An electric conductivity detector with a suppressor was used as a detector. The thermostat temperature was 30 ° C.
  • Synthesis Example 1 Synthesis of Vinyl Acetate-Methyl Acrylate Copolymer 768 g of water and anhydrous sodium sulfate were added to a 2 L reaction vessel equipped with a stirrer, thermometer, N 2 gas introduction tube, reflux condenser and dropping funnel. 12 g was added and the system was replaced with N 2 gas. Thereafter, 1 g of partially saponified polyvinyl alcohol (saponification degree 88%) and 1 g of lauryl peroxide were added thereto, and the temperature was raised to an internal temperature of 60 ° C. Thereafter, 104 g (1.209 mol) of methyl acrylate and 155 g (1.802 mol) of vinyl acetate were simultaneously added dropwise thereto over 4 hours.
  • the internal temperature was kept at 60 ° C. at a stirring rotational speed of 600 rpm.
  • the mixture was stirred at an internal temperature of 65 ° C. for 2 hours, and the resulting mixture was dehydrated by centrifugation to obtain 288 g of vinyl acetate-methyl acrylate copolymer (containing 10.4% by mass water).
  • the obtained reaction mixture was washed with 600 g of methanol three times, filtered, and dried at 70 ° C. for 6 hours to obtain 308 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer.
  • 308 g of the cesium saponified product of the vinyl alcohol-acrylic acid copolymer was pulverized by a jet mill (LJ manufactured by Nippon Pneumatic Industry Co., Ltd.) to obtain 280 g of a cesium saponified product of a vinyl alcohol-acrylic acid copolymer in a fine powder form.
  • Example 3 The hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [ ⁇ ] of the hydrogen sulfide separation membrane shown in Example 2 are shown in Table 1.
  • the cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane.
  • the relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas.
  • the supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
  • Example 5 Production of Hydrogen Sulfide Separation Membrane
  • the hydrogen sulfide separation material obtained in Example 4 was prepared from a hydrophobic PTFE porous membrane (manufactured by Sumitomo Electric Fine Polymer, HP-010-50, film thickness 50 ⁇ m, pore diameter 0. It was applied on the surface of 1 ⁇ m).
  • the hydrophilic PTFE porous membrane after application of the hydrogen sulfide separator was dried at 90 ° C. for 1 hour and further thermally crosslinked at 120 ° C. for about 2 hours to obtain a hydrogen sulfide separation membrane.
  • the thickness of the hydrogen sulfide separation membrane after drying was 29 ⁇ m.
  • Example 7 Production of hydrogen sulfide separating material
  • Example 9 Table 3 shows the hydrogen sulfide permeability coefficient [mol / m 2 / sec / kPa] and the selectivity [ ⁇ ] of the hydrogen sulfide separation membrane shown in Example 8.
  • the cell temperature in the table indicates a set value of the temperature of the cell sandwiching the hydrogen sulfide separation membrane.
  • the relative humidity indicates a set value of the relative humidity of the supply side and permeation side gas.
  • the supply-side hydrogen sulfide concentration indicates the measured concentration of hydrogen sulfide in the supply-side gas.
  • the hydrogen sulfide separation material of the present invention is used, a hydrogen sulfide separation membrane excellent in hydrogen sulfide permeation performance (permeance) and hydrogen sulfide separation performance (selectivity) can be produced.

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Abstract

L'invention fournit un matériau de séparation de sulfure d'hydrogène utile dans la fabrication d'une membrane de séparation de sulfure d'hydrogène qui se révèle excellente en termes de performances de perméation de sulfure d'hydrogène (perméance) et de performances de séparation de sulfure d'hydrogène (séléctivité). Ce matériau de séparation de sulfure d'hydrogène contient un polymère absorbant l'eau et un entraîneur à base d'amine. En outre, ce matériau de séparation de sulfure d'hydrogène satisfait les conditions représentées dans la formule (1) suivante. （Ｘ１－Ｘ２）×Ｙ×１００／Ｚ ≦ ０．１ （１）Ｘ１ : nombre de moles de métaux alcalins contenus dans ledit polymère absorbant l'eau ; Ｘ２ : nombre d'équivalents de groupes d'échange d'ions contenus dans ledit polymère absorbant l'eau ; Y : masse atomique moyenne de métaux alcalins contenus dans ledit polymère absorbant l'eau ; et Z : masse dudit polymère absorbant l'eau
PCT/JP2016/060618 2015-04-07 2016-03-31 Matériau de séparation de sulfure d'hydrogène, et membrane de séparation de sulfure d'hydrogène Ceased WO2016163296A1 (fr)

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Cited By (2)

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WO2018147421A1 (fr) * 2017-02-09 2018-08-16 独立行政法人石油天然ガス・金属鉱物資源機構 Système d'élimination de sulfure d'hydrogène et procédé d'élimination de sulfure d'hydrogène
WO2018179531A1 (fr) 2017-03-31 2018-10-04 住友化学株式会社 Gel comprenant un produit de condensation de composé organique de silicium
KR20190129959A (ko) 2017-03-31 2019-11-20 스미또모 가가꾸 가부시키가이샤 유기 규소 화합물의 축합물을 포함하는 겔
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