JP2002159822A - Method for separating hydrocarbon by separation membrane - Google Patents
Method for separating hydrocarbon by separation membraneInfo
- Publication number
- JP2002159822A JP2002159822A JP2000355672A JP2000355672A JP2002159822A JP 2002159822 A JP2002159822 A JP 2002159822A JP 2000355672 A JP2000355672 A JP 2000355672A JP 2000355672 A JP2000355672 A JP 2000355672A JP 2002159822 A JP2002159822 A JP 2002159822A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- polyimide resin
- containing polyimide
- hydrocarbon
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は、炭化水素を含む混
合物から特定炭化水素を分離する方法に関する。さらに
詳しくは、石油精製工業や石油化学工業等にて発生する
炭化水素を含む混合物から不飽和炭化水素、芳香族炭化
水素等を分離、濃縮する方法に関する。[0001] The present invention relates to a method for separating a specific hydrocarbon from a mixture containing the hydrocarbon. More specifically, the present invention relates to a method for separating and concentrating unsaturated hydrocarbons, aromatic hydrocarbons, and the like from a mixture containing hydrocarbons generated in a petroleum refining industry, a petrochemical industry, or the like.
【0002】[0002]
【従来の技術】石油精製工業や石油化学工業にて、膜を
利用して炭化水素を含む混合物から特定炭化水素を分離
する方法は、科学的及び経済的観点から永年研究されて
おり、これまでにいくらかの検討例が報告されている。
例えば、米国特許第2958656号明細書は、炭化水
素混合物、即ち、ナフサを非ポーラス型セルロースエー
テル膜に供給し、その一部を膜透過させ、洗浄ガス又は
洗浄液を使用して膜の透過側から透過物を除去すること
により、不飽和化合物と飽和化合物と芳香族化合物を分
離する方法を開示している。米国特許第2930754
号明細書は、ガソリンの沸点範囲の温度で留出してくる
混合物の一部を非ポーラス型セルロースエーテル膜に選
択的に透過させ、その透過物を洗浄ガス又は洗浄液を使
用して膜の透過側から除去することにより、不飽和炭化
水素や芳香族化合物等の炭化水素を分離する方法を開示
している。2. Description of the Related Art In the petroleum refining industry and the petrochemical industry, methods for separating specific hydrocarbons from hydrocarbon-containing mixtures using membranes have been studied for many years from a scientific and economic viewpoint. Some examples have been reported.
For example, U.S. Pat. No. 2,958,656 discloses that a hydrocarbon mixture, i.e., naphtha, is supplied to a non-porous cellulose ether membrane, a portion of which is permeated through the membrane, and the permeate side of the membrane is cleaned using a cleaning gas or cleaning liquid. A method for separating unsaturated compounds, saturated compounds and aromatic compounds by removing permeate is disclosed. U.S. Pat. No. 2,930,754
The specification discloses that a portion of a mixture distilled at a temperature in the boiling range of gasoline is selectively permeated through a non-porous cellulose ether membrane, and the permeate is passed through the permeate side of the membrane using a cleaning gas or a cleaning liquid. Discloses a method of separating hydrocarbons such as unsaturated hydrocarbons and aromatic compounds by removing the hydrocarbons.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、従来提
案の膜による炭化水素の分離方法は、分離膜の多くが芳
香族炭化水素、不飽和炭化水素、飽和炭化水素等に対す
る耐性、あるいは特定炭化水素に対する分離能が未だ十
分ではなく、あるいは、膜透過した炭化水素を除去また
は回収するための洗浄ガスまたは洗浄液が必要であり、
装置が複雑となる上、経済的にも問題がある。そのた
め、炭化水素を含む混合物からの特定炭化水素の膜分離
法は、性能面、作業性、コスト面の問題から広く工業的
規模で普及していないのが現状である。However, in the conventional method for separating hydrocarbons using a membrane, most of the separation membranes are resistant to aromatic hydrocarbons, unsaturated hydrocarbons, saturated hydrocarbons, or the like, or have specific hydrocarbons. The separation power is not yet sufficient, or a cleaning gas or cleaning liquid is required to remove or recover hydrocarbons permeated through the membrane,
The device becomes complicated and there is an economical problem. Therefore, at present, the membrane separation method of specific hydrocarbons from a mixture containing hydrocarbons is not widely used on an industrial scale due to problems in performance, workability, and cost.
【0004】本発明はこれらの問題点を解決するために
なされたものであって、炭化水素に対して高い耐性を有
し、炭化水素を含む混合物中の特定の不飽和炭化水素、
芳香族炭化水素等に対して高い分離能を有し、性能面、
コスト面共に実用的に満足できる炭化水素を含む混合物
からの特定炭化水素の膜分離方法を提供することを目的
とする。[0004] The present invention has been made to solve these problems, and has a high resistance to hydrocarbons, a specific unsaturated hydrocarbon in a mixture containing hydrocarbon,
It has high separation ability for aromatic hydrocarbons, etc.
It is an object of the present invention to provide a method for membrane separation of a specific hydrocarbon from a mixture containing a hydrocarbon, which is practically satisfactory both in terms of cost.
【0005】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明の炭化水素の選択的分離方法は、炭化水素を
含む混合物を、ガラス転位温度が200〜280℃の範
囲にあり、且つ繰り返し分子単位構造内の主鎖部分にメ
タ結合を有するフッ素含有ポリイミド樹脂を主成分とす
る膜の一方の面に接触させ、この膜を通して、特定炭化
水素を選択的に透過させ分離することを特徴とする。In order to achieve the above object, a method for selectively separating hydrocarbons according to the present invention is characterized in that a mixture containing hydrocarbons is mixed with a glass transition temperature in the range of 200 to 280 ° C. It is characterized by contacting one surface of a film mainly composed of a fluorine-containing polyimide resin having a meta bond in the main chain portion in the molecular unit structure, and selectively permeating and separating specific hydrocarbons through this film. I do.
【0006】本発明においては、フッ素含有ポリイミド
樹脂を構成する繰り返し分子単位構造内に少なくとも一
つの−CF3基を有することが好ましい。In the present invention, it is preferable that at least one --CF 3 group is contained in the repeating molecular unit structure constituting the fluorine-containing polyimide resin.
【0007】また本発明においては、フッ素含有ポリイ
ミド樹脂が実質的に下記式(化4)で表される繰り返し
単位を主成分とすることが好ましい。In the present invention, it is preferable that the fluorine-containing polyimide resin contains a repeating unit substantially represented by the following formula (4) as a main component.
【0008】[0008]
【化4】 Embedded image
【0009】(但し、繰り返し単位構造内の主鎖部分に
メタ結合を有し、A1とA2は芳香族、脂環族もしくは脂
肪族炭化水素基からなる4価の有機基を示し、R1とR2
は2価の芳香族、脂肪族または脂肪族炭化水素基または
これらの炭化水素基が2価の有機結合基で結合された2
価の有機基を示し、A1,A2,R1,R2の内少なくとも
一つは、−CF3基を一つ以上有する有機基であり、
m,nは正の自然数で重合度を示す。) また本発明においては、フッ素含有ポリイミド樹脂が実
質的に下記式(化5)または(化6)で表される繰り返
し単位を主成分とすることが好ましい。(However, A 1 and A 2 each have a tetravalent organic group comprising an aromatic, alicyclic or aliphatic hydrocarbon group having a meta bond in the main chain portion in the repeating unit structure. 1 and R 2
Is a divalent aromatic, aliphatic or aliphatic hydrocarbon group or a divalent organic bonding group in which these hydrocarbon groups are bonded.
A organic group having a valence of at least one of A 1 , A 2 , R 1 , and R 2 is an organic group having at least one —CF 3 group;
m and n are positive natural numbers and indicate the degree of polymerization. In the present invention, the fluorine-containing polyimide resin preferably contains a repeating unit substantially represented by the following formula (5) or (6) as a main component.
【0010】[0010]
【化5】 Embedded image
【0011】(但し、m,nは正の自然数で重合度を示
す。)(However, m and n are positive natural numbers and indicate the degree of polymerization.)
【0012】[0012]
【化6】 Embedded image
【0013】(但し、m,nは正の自然数で重合度を示
す。)(However, m and n are positive natural numbers and indicate the degree of polymerization.)
【0014】[0014]
【発明の実施の形態】本発明者らは、炭化水素を含む混
合物を、フッ素含有ポリイミド樹脂から成る膜の一方の
面に接触させ、この膜を通して、特定炭化水素を選択的
に透過させ高度に分離する方法を見いだし、本発明に至
ったものである。フッ素含有ポリイミドの多くは、耐熱
性、気体分離性等に優れた膜分離材料として知られてい
る。例えば、特開平5−7749号公報、米国特許第3
822202号、米国特許第3899309号、米国特
許第4532041号、米国特許第4645824号、
米国特許第4705540号、米国特許第471739
3号、米国特許第4717394号、米国特許第483
8900号、米国特許第4897092号、米国特許第
4932982号、米国特許第4929405号、米国
特許第4981497号、米国特許第5042992号
各明細書等には含フッ素系の芳香族ポリイミドが開示さ
れている。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors contact a mixture containing a hydrocarbon with one side of a film made of a fluorine-containing polyimide resin, and selectively permeate a specific hydrocarbon through this film to obtain a high degree. A method for separation has been found, and the present invention has been achieved. Many fluorine-containing polyimides are known as membrane separation materials having excellent heat resistance and gas separation properties. For example, Japanese Patent Application Laid-Open No. 5-7749, U.S. Pat.
No. 822202, U.S. Pat. No. 3,899,309, U.S. Pat. No. 4,532,041, U.S. Pat. No. 4,645,824,
U.S. Pat. No. 4,705,540, U.S. Pat.
No. 3, US Pat. No. 4,717,394, US Pat.
No. 8,900, U.S. Pat. No. 4,897,092, U.S. Pat. No. 4,932,982, U.S. Pat. No. 4,929,405, U.S. Pat. No. 4,981,497, U.S. Pat. .
【0015】本発明に用いる膜を構成する樹脂は、不飽
和炭化水素、芳香族炭化水素等の特定炭化水素の分離性
能に寄与する樹脂であって、そのガラス転位温度が20
0〜280℃の範囲にあり、且つ繰り返し分子単位構造
内の主鎖部分にメタ結合を有するフッ素含有ポリイミド
樹脂を主成分とする。ここで主成分とは、70モル%以
上をいう。また好ましい重量平均分子量は20,000〜800,
000の範囲である。The resin constituting the membrane used in the present invention is a resin that contributes to the separation performance of specific hydrocarbons such as unsaturated hydrocarbons and aromatic hydrocarbons, and has a glass transition temperature of 20%.
The main component is a fluorine-containing polyimide resin having a temperature in the range of 0 to 280 ° C. and having a meta bond in the main chain portion in the repeating molecular unit structure. Here, the main component means 70 mol% or more. The preferred weight average molecular weight is 20,000 to 800,
000 range.
【0016】均質ポリマーへの気体の透過性は、気体の
ポリマーへの溶解過程とポリマー中での拡散過程により
決定され、具体的には、ポリマーへの溶解度係数とポリ
マー中における気体の拡散係数の積で表されることがよ
く知られている。このため、混合気体を溶解性あるいは
拡散性の差を利用して、個別成分に分離することが可能
となる。炭素数C3以上の炭化水素を透過させる場合
は、一般的に膜素材高分子が透過成分により可塑化さ
れ、その結果、高分子の自由体積が増大し、拡散性の向
上がみられる。この際、ポリイミドなどのガラス状高分
子の場合、過度に可塑化されると、自由体積の増大率が
大きくなり、その結果、特定透過成分を分子サイズの違
いを利用して篩い分けるといった分離機能が低下する。
このような過度の可塑化はポリイミドの熱運動性や3次
元の分子構造に強く関係している。本発明者らは、この
点に着眼し、鋭意検討した結果、ガラス転位温度が20
0〜280℃の範囲にあり、且つ繰り返し分子単位構造
内の主鎖部分にメタ結合を有するフッ素含有ポリイミド
を主成分とする樹脂を膜素材として用いた場合に、炭化
水素による極端な可塑化を抑えることができ、特定炭化
水素に対して高い分離能を有する分離膜が得られること
を見いだした。The gas permeability of a homogeneous polymer is determined by the process of dissolving the gas in the polymer and the process of diffusion in the polymer. Specifically, the solubility coefficient of the gas in the polymer and the diffusion coefficient of the gas in the polymer are determined. It is well known that it is expressed as a product. For this reason, it becomes possible to separate the mixed gas into individual components by utilizing the difference in solubility or diffusivity. When a hydrocarbon having a carbon number of C3 or more is allowed to permeate, generally, the polymer of the membrane material is plasticized by the permeating component, and as a result, the free volume of the polymer is increased and the diffusivity is improved. At this time, in the case of a glassy polymer such as polyimide, if it is excessively plasticized, the rate of increase in free volume increases, and as a result, a separation function such as sieving a specific permeated component using a difference in molecular size. Decrease.
Such excessive plasticization is strongly related to the thermal mobility and three-dimensional molecular structure of polyimide. The present inventors have focused on this point and conducted intensive studies. As a result, the glass transition temperature was 20 ° C.
Extreme plasticization due to hydrocarbons occurs when a resin in the range of 0 to 280 ° C. and containing a fluorine-containing polyimide as a main component having a meta bond in a main chain portion in a repeating molecular unit structure is used as a film material. It has been found that a separation membrane which can be suppressed and has a high separation ability for specific hydrocarbons can be obtained.
【0017】本発明において、ガラス転位温度とは、一
般的な走査型示差熱量測定法に準じて測定される。上述
のフッ素含有ポリイミド樹脂にガラス転位温度が200
℃未満のものを用いると、炭化水素の溶解に有効なフッ
素含有ポリイミドの未緩和体積が過度に減少し、その結
果、炭化水素の透過性が過度に低下する恐れがあるため
好ましくない。また、ガラス転位温度が280℃を超え
ると、分子鎖の剛直性が過度に増大し、その結果、分子
鎖充填性が悪くなり、炭化水素により過度に可塑化しや
すくなる恐れがあるため好ましくない。また、上述の主
鎖へのメタ結合の導入は、フッ素含有ポリイミド分子の
屈曲性を増大させ、その結果、樹脂形成の際に分子鎖の
高率的な充填が可能となると考えられ、炭化水素により
可塑化しにくくなる傾向があるため好ましい。In the present invention, the glass transition temperature is measured according to a general scanning differential calorimetry. The above-mentioned fluorine-containing polyimide resin has a glass transition temperature of 200.
It is not preferable to use a material having a temperature lower than 0 ° C., because the unrelaxed volume of the fluorine-containing polyimide effective for dissolving the hydrocarbon is excessively reduced, and as a result, the permeability of the hydrocarbon may be excessively reduced. On the other hand, if the glass transition temperature exceeds 280 ° C., the rigidity of the molecular chain is excessively increased, and as a result, the packing of the molecular chain is deteriorated, and there is a possibility that the polymer may be excessively easily plasticized. In addition, the introduction of a meta bond into the main chain described above increases the flexibility of the fluorine-containing polyimide molecule, and as a result, it is considered that high-efficiency filling of the molecular chain is possible during resin formation, and hydrocarbons are considered. This is preferred because it tends to be less plasticized.
【0018】本発明においては、前記従来の技術で説明
した公知のフッ素含有ポリイミド樹脂を主成分とする膜
を適用することができる。In the present invention, it is possible to apply the known film containing a fluorine-containing polyimide resin as a main component, which has been described in the related art.
【0019】本発明に用いられるフッ素合有ポリイミド
樹脂は、前記一般式(化4)で表される繰り返し分子構
造単位を主成分とすることが好ましい。−CF3基を一
つ以上有する4価の有機基としては、特に限定されない
が、例えば、下記式(化7)で表される4価の有機基な
どが好ましく用いられる。The fluorine-containing polyimide resin used in the present invention preferably contains a repeating molecular structural unit represented by the general formula (Formula 4) as a main component. The tetravalent organic group having one or more —CF 3 groups is not particularly limited. For example, a tetravalent organic group represented by the following formula (Formula 7) is preferably used.
【0020】[0020]
【化7】 Embedded image
【0021】R1あるいはR2の2価の有機基は特に限定
されないが、フェニレンを主鎖に含む構造が好ましく用
いられる。具体的には、下記式(化8)〜(化15)で
表される2価の有機基等が好ましく用いられる。The divalent organic group of R 1 or R 2 is not particularly limited, but a structure containing phenylene in the main chain is preferably used. Specifically, divalent organic groups represented by the following formulas (Formula 8) to (Formula 15) are preferably used.
【0022】[0022]
【化8】 Embedded image
【0023】[0023]
【化9】 Embedded image
【0024】[0024]
【化10】 Embedded image
【0025】[0025]
【化11】 Embedded image
【0026】[0026]
【化12】 Embedded image
【0027】[0027]
【化13】 Embedded image
【0028】[0028]
【化14】 Embedded image
【0029】[0029]
【化15】 Embedded image
【0030】本発明に用いられるフッ素合有ポリイミド
樹脂は50モル%以下であればフッ素合有ポリイミド樹
脂以外のポリスルホン、ポリエーテルスルホンなどのポ
リマーとの共重合体、もしくは混合物であってもよい。The fluorine-containing polyimide resin used in the present invention may be a copolymer or a mixture with a polymer such as polysulfone or polyethersulfone other than the fluorine-containing polyimide resin as long as it is 50 mol% or less.
【0031】本発明で用いられるフッ素合有ポリイミド
樹脂は、テトラカルボン酸二無水物とジアミン成分を用
いて、例えば、米国特許第3959350号明細書に記
載されているような公知の重合方法で得られる。例え
ば、テトラカルボン酸二無水物とジアミン化合物をほぼ
等モル量を用い、極性溶媒中、約80℃以下の温度、好
ましくは、0〜60℃で撹件し、ポリアミック酸を重合
する。ここで用いられる極性溶媒は特に限定されない
が、N一メチルピロリドン、ピリジン、ジメチルアセト
アミド、ジメチルホルムアミド、ジメチルスルホキシ
ド、テトラメチル尿素、フェノール、クレゾールなどが
好適に用いられる。The fluorine-containing polyimide resin used in the present invention can be obtained by a known polymerization method, for example, as described in US Pat. No. 3,959,350, using a tetracarboxylic dianhydride and a diamine component. Can be For example, a tetracarboxylic dianhydride and a diamine compound are used in approximately equimolar amounts and stirred in a polar solvent at a temperature of about 80 ° C. or lower, preferably 0 to 60 ° C., to polymerize the polyamic acid. The polar solvent used here is not particularly limited, but N-methylpyrrolidone, pyridine, dimethylacetamide, dimethylformamide, dimethylsulfoxide, tetramethylurea, phenol, cresol and the like are preferably used.
【0032】得られたポリアミック酸の極性溶媒溶液に
トリメチルアミン、トリエチルアミン、ピリジン等の第
3級アミン化合物、無水酢酸、塩化チオニル、カルボジ
イミドなどのイミド化促進剤を添加し、5〜150℃の
温度で撹件し、イミド化する。イミド化反応を行う際、
イミド化促進剤を添加することなく、上記ポリアミック
酸溶液を100〜400℃、好ましくは、120〜30
0℃で加熱してイミド化してもよい。A tertiary amine compound such as trimethylamine, triethylamine and pyridine, and an imidization accelerator such as acetic anhydride, thionyl chloride and carbodiimide are added to the obtained polar solvent solution of polyamic acid. Stir and imidize. When performing an imidation reaction,
Without adding an imidization accelerator, the polyamic acid solution is heated at 100 to 400 ° C, preferably at 120 to 30 ° C.
It may be imidized by heating at 0 ° C.
【0033】イミド化反応後、重合時の極性溶媒やイミ
ド化促進剤を除去するために、多量のアセトン、アルコ
ールまたは水等の溶液に滴下し精製することにより、膜
材料として好適なポリイミド樹脂が得られる。After the imidization reaction, in order to remove the polar solvent and the imidization accelerator during the polymerization, a large amount of a solution such as acetone, alcohol or water is dropped and purified to obtain a polyimide resin suitable as a film material. can get.
【0034】また、イミド化促進剤を添加することな
く、イミド化反応を行う場合は、ポリアミック酸溶液を
多量のアセトン、またはアルコール等の溶液に滴下して
得られたポリアミック酸粉末やポリアミック酸溶液から
溶媒を蒸発させて得られたポリアミック酸の固体(蒸発
の際、沈殿剤等を加えてポリアミック酸粉末を形成さ
せ、濾別してもよい)を100〜400℃に加熱してイ
ミド化することにより、膜材料として好適なポリイミド
樹脂が得られる。When the imidization reaction is carried out without adding an imidization accelerator, a polyamic acid powder or a polyamic acid solution obtained by dropping a polyamic acid solution into a large amount of a solution of acetone or alcohol is used. By heating the solvent to 100-400 ° C. to imidize the solid of polyamic acid obtained by evaporating the solvent from the mixture (in the case of evaporation, a polyamic acid powder may be formed by adding a precipitant or the like and filtered). Thus, a polyimide resin suitable as a film material is obtained.
【0035】本発明で用いられる膜の製膜法は、特に限
定されないが、例えば、上述のフッ素含有ポリイミド樹
脂を適正な溶媒に溶解して製膜液を調製し、製膜液をガ
ラス、金属、プラスチック等の平滑な表面を有する平板
や管、あるいは、不織布等の多孔質支持体上に一定の厚
さで流延し、次いで、加熱処理することにより得る方法
(乾式製膜法)、および、上記製膜液をガラス、金属、
プラスチック等の平板や管、あるいは、織布、不織布等
の多孔質支持体上に一定の厚さで流延し、凝固液(製膜
液中のフッ素含有ポリイミド樹脂は溶解しないが、製膜
液中の有機溶媒と相溶性のある溶媒)に浸漬するか、ま
たは、製膜液を同心円状の多重構造のノズルから押し出
し、上記凝固液に浸漬して中空糸状非対称膜を調製し、
その後、膜を乾燥する方法(湿式製膜法)をとることが
できる。The method for forming the film used in the present invention is not particularly limited. For example, a film-forming solution is prepared by dissolving the above-mentioned fluorine-containing polyimide resin in an appropriate solvent, and the film-forming solution is made of glass or metal. A method of casting a plate or tube having a smooth surface such as plastic or the like, or a porous support such as a non-woven fabric with a constant thickness, followed by heat treatment (dry film forming method), and , The above-mentioned film forming solution is made of glass, metal,
It is cast to a certain thickness on a porous support such as a plastic or other flat plate or tube, or a woven or non-woven fabric, and a coagulation solution (the fluorine-containing polyimide resin in the film formation solution does not dissolve, but the film formation solution A solvent that is compatible with the organic solvent in) or extrude the film-forming solution from a concentric multi-layered nozzle, and immerse in the coagulation solution to prepare a hollow fiber-like asymmetric membrane,
Thereafter, a method of drying the film (wet film forming method) can be employed.
【0036】フッ素含有ポリイミド樹脂の溶媒として
は、特に限定されないが、N−メチル−2−ピロリド
ン、ジメチルアセトアミド、ジメチルホルムアミド、ジ
メチルスルホキシド、ジエチレングリコールジメチルエ
ーテル、1,2−ジメトキシメタン等が挙げられる。The solvent for the fluorine-containing polyimide resin is not particularly restricted but includes N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, diethylene glycol dimethyl ether, 1,2-dimethoxymethane and the like.
【0037】製膜液のポリイミド溶液濃度は3〜40重
量%、好ましくは10〜30重量%である。また、製膜
液を調整する場合に必要に応じて、膨潤剤、分散剤、増
粘剤等を加えてもよい。製膜液を流延する手段として
は、例えば、ドクターナイフ、ドクタープレート、アプ
リケーター等を利用することができる。The polyimide solution concentration of the film forming solution is 3 to 40% by weight, preferably 10 to 30% by weight. When adjusting the film forming solution, a swelling agent, a dispersant, a thickener, and the like may be added as necessary. As a means for casting the film-forming solution, for example, a doctor knife, a doctor plate, an applicator or the like can be used.
【0038】製膜液流延後の加熱処理は、製膜液中の溶
媒を十分に除去できる温度で、且つポリイミド樹脂のガ
ラス転移点以下であることが望ましい。The heat treatment after the casting of the film-forming solution is preferably carried out at a temperature at which the solvent in the film-forming solution can be sufficiently removed and at a temperature not higher than the glass transition point of the polyimide resin.
【0039】上記湿式製膜法において、上記有機溶媒を
浸漬し除去する際に用いられる凝固液は用いるフッ素含
有ポリイミド樹脂を溶解しないが、製膜液中の溶媒と相
溶性を有する溶媒であれば、とくに限定されないが、水
やエタノール、メタノール、イソプロピルアルコール等
のアルコール類およびこららの混合液が用いられ、特に
水が好適に用いられる。製膜液中の有機溶媒を浸漬除去
する際の凝固液の温度は特に限定されないが、好ましく
は0〜50℃の温度で行われる。In the above-mentioned wet film-forming method, the coagulating liquid used for immersing and removing the above-mentioned organic solvent does not dissolve the fluorine-containing polyimide resin used, but any solvent having a compatibility with the solvent in the film-forming liquid. Although not particularly limited, water, alcohols such as ethanol, methanol, and isopropyl alcohol, and a mixture thereof are used, and water is particularly preferably used. The temperature of the coagulation liquid at the time of immersing and removing the organic solvent in the film forming liquid is not particularly limited, but is preferably at a temperature of 0 to 50 ° C.
【0040】また、本発明における膜の形状は特に限定
されないが、チューブ状(中空糸状を含む)、平膜状の
ものが好適に用いられる。The shape of the membrane in the present invention is not particularly limited, but a tube (including a hollow fiber) or a flat membrane is preferably used.
【0041】[0041]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれらの実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.
【0042】(実施例1)5,5’-2,2’-トリフルオロ-1
-(トリフルオロメチル)エチリデン-ビス-1,3-イソベ
ンゾフランジオン(6FDA)0.0761mo1と、3,4’-ジアミノ
ジフェニルエーテル(34’DPE)0.0761mo1および溶媒とし
てN-メチル-2-ピロリドン(NMP)を加え、窒素雰囲気下
室温で撹絆し、ポリアミック酸溶液を調製した。この
際、ポリアミック酸溶液は、ポリアミック酸10wt%以内
とした。次いで、このポリアミック酸溶液に無水酢酸0.
305mo1を少量のピリジンとともに添加し、窒素雰囲気下
室温で撹拝し、イミド化反応を行った。反応終了後、室
温まで冷却し、重合液を過剰量の水中に高速撹揮下、滴
下し沈澱精製させた。さらにメタノールで精製し、下記
式(化16)で表される繰り返し分子構造単位から成る
フッ素含有ポリイミド樹脂を得た。Example 1 5,5'-2,2'-trifluoro-1
-(Trifluoromethyl) ethylidene-bis-1,3-isobenzofurandione (6FDA) 0.0761mol and 3,4'-diaminodiphenylether (34'DPE) 0.0761mol and N-methyl-2-pyrrolidone (NMP ) And stirred at room temperature under a nitrogen atmosphere to prepare a polyamic acid solution. At this time, the content of the polyamic acid solution was adjusted to 10 wt% or less of the polyamic acid. Then, acetic anhydride was added to this polyamic acid solution at a concentration of 0.1%.
305 mol was added together with a small amount of pyridine, and the mixture was stirred at room temperature under a nitrogen atmosphere to perform an imidization reaction. After completion of the reaction, the mixture was cooled to room temperature, and the polymerization solution was dropped into an excess amount of water under high-speed stirring to precipitate and purify. Further purification with methanol yielded a fluorine-containing polyimide resin comprising a repeating molecular structural unit represented by the following formula (Formula 16).
【0043】[0043]
【化16】 Embedded image
【0044】(但し、mは正の自然数で重量平均分子量
90,000) 次に、前記(化16)で表される繰り返し分子構造単位
から成るフッ素合有ポリイミド18重量部を希釈し、有
機溶媒としてNMPを82重量部を加え、100℃で6
時間撹伴し溶解した。その後、濾過し、静置して十分に
脱泡し、製膜液を調製した。製膜液をアプリケータを用
いガラス板上に、幅20cm、厚さ300μmで流延
し、110℃で1時間、150℃で3時間、200℃で
3時間、さらに真空下にて200℃で72時間加熱処理
を施し、厚さ20−40μmのフッ素合有ポリイミド樹
脂より成る均質膜を得た。このフッ素含有ポリイミド樹
脂は繰り返し分子単位構造内の主鎖部分にメタ結合を有
するもので、また、10℃/分の昇温速度で走査型示差
熱量測定をおこなったところ、ガラス転位温度は237
℃であった。したがって、上記フッ素含有ポリイミド樹
脂は、本発明の条件を満足するものであった。次に、得
られた均質膜について、25℃、供給圧力2atmに
て、プロピレン/プロパン50/50mol%混合ガス
を供給した時の定常状態における分離性能、透過性能評
価結果を後にまとめて表1に示す。(Where m is a positive natural number and weight average molecular weight)
90,000) Next, 18 parts by weight of a fluorine-containing polyimide comprising a repeating molecular structural unit represented by the above formula (Chem. 16) was diluted, and 82 parts by weight of NMP was added as an organic solvent.
The mixture was stirred for a period of time to dissolve. Thereafter, the mixture was filtered, allowed to stand, and sufficiently defoamed to prepare a film forming solution. The film-forming solution was cast on a glass plate using an applicator at a width of 20 cm and a thickness of 300 μm, and was heated at 110 ° C. for 1 hour, 150 ° C. for 3 hours, 200 ° C. for 3 hours, and further under vacuum at 200 ° C. A heat treatment was performed for 72 hours to obtain a homogeneous film made of a fluorine-containing polyimide resin having a thickness of 20 to 40 μm. This fluorine-containing polyimide resin has a meta bond in the main chain portion in the repeating molecular unit structure. When the scanning differential calorimetry is performed at a heating rate of 10 ° C./min, the glass transition temperature is 237.
° C. Therefore, the above-mentioned fluorine-containing polyimide resin satisfied the conditions of the present invention. Next, with respect to the obtained homogeneous membrane, the separation performance and permeation performance evaluation results in a steady state when a propylene / propane 50/50 mol% mixed gas was supplied at 25 ° C. and a supply pressure of 2 atm are summarized in Table 1 below. Show.
【0045】(実施例2)実施例1において、3,4’-ジ
アミノジフェニルエーテルのかわりに、3,3’-ジアミノ
ジフェニルメタン(33’DDM)を用いた以外は同様にして
下記式(化17)で表される繰り返し分子単位構造から
成るフッ素含有ポリイミド樹脂による均質膜を得た。Example 2 The procedure of Example 1 was repeated, except that 3,3′-diaminodiphenylmethane (33′DDM) was used instead of 3,4′-diaminodiphenylether. A homogeneous film made of a fluorine-containing polyimide resin having a repeating molecular unit structure represented by the following formula was obtained.
【0046】[0046]
【化17】 Embedded image
【0047】(但し、mは正の自然数で重量平均分子量
140,000) このフッ素含有ポリイミド樹脂は繰り返し分子単位構造
内の主鎖部分にメタ結合を有するもので、また、10℃
/分の昇温速度で走査型示差熱量測定をおこなったとこ
ろ、ガラス転位温度は217℃であった。したがって、
上記フッ素含有ポリイミド樹脂は、本発明の条件を満足
するものであった。次に、この均質膜について、実施例
1と同様にして、25℃、供給圧力2atmにて、プロ
ピレン/プロパン50/50mol%混合ガスを供給した時
の定常状態におけるの分離性能、透過性能評価結果を後
にまとめて表1に示す。(Where m is a positive natural number and weight average molecular weight)
140,000) This fluorine-containing polyimide resin has a meta bond in the main chain portion in the repeating molecular unit structure, and has a temperature of 10 ° C.
When the scanning differential calorimetry was performed at a heating rate of / min, the glass transition temperature was 217 ° C. Therefore,
The above-mentioned fluorine-containing polyimide resin satisfied the conditions of the present invention. Next, in the same manner as in Example 1, the separation performance and permeation performance evaluation results in the steady state when a propylene / propane 50/50 mol% mixed gas was supplied at 25 ° C. and a supply pressure of 2 atm in the same manner as in Example 1. Are summarized in Table 1 below.
【0048】(比較例1)実施例1において、3,4’-ジ
アミノジフェニルエーテルのかわりに、4,4’-ジアミノ
ジフェニルメタン(44’DDM)を用いた以外は同様にして
下記式(化18)で表される繰り返し分子単位構造から
成るフッ素含有ポリイミド樹脂による均質膜を得た。Comparative Example 1 The procedure of Example 1 was repeated, except that 4,4′-diaminodiphenylmethane (44′DDM) was used instead of 3,4′-diaminodiphenylether. A homogeneous film made of a fluorine-containing polyimide resin having a repeating molecular unit structure represented by the following formula was obtained.
【0049】[0049]
【化18】 Embedded image
【0050】(但し、mは正の自然数で重量平均分子量
120,000) このフッ素含有ポリイミド樹脂について10℃/分の昇
温速度で走査型示差熱量測定を実施したところ、ガラス
転位温度は286℃であった。したがって、このフッ素
含有ポリイミド樹脂は本発明の条件を満足するものでは
なかった。次に、この均質膜について、実施例1と同様
にして、25℃、供給圧力2atmにて、プロピレン/
プロパン50/50mol%混合ガスを供給した時の定
常状態におけるの分離性能、透過性能評価結果を後にま
とめて表1に示す。(Where m is a positive natural number and weight average molecular weight
120,000) Scanning differential calorimetry at a heating rate of 10 ° C./min for this fluorine-containing polyimide resin revealed a glass transition temperature of 286 ° C. Therefore, this fluorine-containing polyimide resin did not satisfy the conditions of the present invention. Next, this homogeneous film was treated in the same manner as in Example 1 at 25 ° C. and a supply pressure of 2 atm.
Table 1 summarizes the separation performance and permeation performance evaluation results in the steady state when a 50/50 mol% mixed gas of propane was supplied.
【0051】[0051]
【表1】 [Table 1]
【0052】表1に示した通り、本発明の実施例品は、
比較例品と比べて、プロピレンの分離係数が高く、特定
炭化水素に対する分離能が高いことが確認された。As shown in Table 1, the product of the embodiment of the present invention
It was confirmed that the separation coefficient of propylene was higher and the separation ability for specific hydrocarbons was higher than that of the comparative example product.
【0053】[0053]
【発明の効果】本発明は、ガラス転位温度が所定範囲内
にあり、主鎖にメタ結合を有するフッ素含有ポリイミド
樹脂から膜を調製することで、炭化水混合物中の特定炭
化水素に対して高度な分離能を有する膜が得られ、この
膜を用いて、性能面、コスト面においても実用的に満足
しうる炭化水素を含む混合物からの特定炭化水素の分離
方法を提供することができる。According to the present invention, by preparing a film from a fluorine-containing polyimide resin having a glass transition temperature within a predetermined range and having a meta bond in a main chain, a high degree of specific hydrocarbon in a hydrocarbon mixture can be obtained. By using this membrane, it is possible to provide a method for separating a specific hydrocarbon from a hydrocarbon-containing mixture which is practically satisfactory in performance and cost.
フロントページの続き (72)発明者 宮崎 司 大阪府茨木市下穂積1丁目1番2号 日東 電工株式会社内 (72)発明者 池田 健一 大阪府茨木市下穂積1丁目1番2号 日東 電工株式会社内 Fターム(参考) 4D006 GA27 KA12 MA01 MA02 MA03 MB04 MC58X MC79X MC87 NA03 NA05 NA62 PB18 PB68 4J043 PA04 QB31 QC02 RA35 SA06 SB03 TA14 TA22 TB02 UA131 UA132 UA141 UA151 UB011 UB061 UB062 UB121 UB131 UB151 UB301 VA011 VA022 VA051 VA052 VA061 YA06 ZA12 ZB11 Continuing on the front page (72) Inventor Tsukasa Miyazaki 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Kenichi Ikeda 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko shares Company F-term (reference) 4D006 GA27 KA12 MA01 MA02 MA03 MB04 MC58X MC79X MC87 NA03 NA05 NA62 PB18 PB68 4J043 PA04 QB31 QC02 RA35 SA06 SB03 TA14 TA22 TB02 UA131 UA132 VAUA1 UA151 UB011 UB061 UB061 UB061 ZB11
Claims (4)
が200〜280℃の範囲にあり、且つ繰り返し分子単
位構造内の主鎖部分にメタ結合を有するフッ素含有ポリ
イミド樹脂を主成分とする膜の一方の面に接触させ、こ
の膜を通して、特定炭化水素を選択的に透過させ分離す
る炭化水素の選択的分離方法。A film comprising a hydrocarbon-containing mixture having a glass transition temperature in the range of 200 to 280 ° C. and a fluorine-containing polyimide resin having a meta bond in a main chain portion in a repeating molecular unit structure as a main component. And selectively permeating and separating a specific hydrocarbon through the membrane.
返し分子単位構造内に少なくとも一つの−CF3基を有
する請求項1記載の炭化水素の選択的分離方法。2. The method for selectively separating hydrocarbons according to claim 1, wherein the fluorine-containing polyimide resin has at least one --CF 3 group in a repeating molecular unit structure.
式(化1)で表される繰り返し単位を主成分とする請求
項1または2に記載の炭化水素の選択的分離方法。 【化1】 (但し、繰り返し単位構造内の主鎖部分にメタ結合を有
し、A1とA2は芳香族、脂環族もしくは脂肪族炭化水素
基からなる4価の有機基を示し、R1とR2は2価の芳香
族、脂肪族または脂肪族炭化水素基またはこれらの炭化
水素基が2価の有機結合基で結合された2価の有機基を
示し、A1,A2,R1,R2の内少なくとも一つは、−C
F3基を一つ以上有する有機基であり、m,nは正の自
然数で重合度を示す。)3. The method for selectively separating hydrocarbons according to claim 1, wherein the fluorine-containing polyimide resin contains a repeating unit substantially represented by the following formula (1) as a main component. Embedded image (However, a meta bond in the main chain portion of the repeating unit structure, A 1 and A 2 represents an aromatic tetravalent organic radical consisting of alicyclic or aliphatic hydrocarbon group, R 1 and R 2 represents a divalent aromatic, aliphatic or aliphatic hydrocarbon group or a divalent organic group in which these hydrocarbon groups are bonded by a divalent organic bonding group, and A 1 , A 2 , R 1 , At least one of R 2 is -C
An organic group having at least one F 3 group, where m and n are positive natural numbers and indicate the degree of polymerization. )
式(化2)または(化3)で表される繰り返し単位を主
成分とする請求項1〜3のいずれかに記載の炭化水素の
選択的分離方法。 【化2】 (但し、m,nは正の自然数で重合度を示す。) 【化3】 (但し、m,nは正の自然数で重合度を示す。)4. The selection of hydrocarbons according to claim 1, wherein the fluorine-containing polyimide resin is mainly composed of a repeating unit substantially represented by the following formula (2) or (3). Separation method. Embedded image (However, m and n are positive natural numbers and indicate the degree of polymerization.) (However, m and n are positive natural numbers and indicate the degree of polymerization.)
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JP2016175000A (en) * | 2015-03-18 | 2016-10-06 | 宇部興産株式会社 | Polyimide gas separation membrane and gas separation method |
CN106567191A (en) * | 2016-10-09 | 2017-04-19 | 华中科技大学 | Preparation of fluorinated polyimide electrostatic-spinning fiber film and application in oil-water separation |
JP2019534141A (en) * | 2016-11-04 | 2019-11-28 | ダウ グローバル テクノロジーズ エルエルシー | Method for producing improved polyimide separation membrane |
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JP2016175000A (en) * | 2015-03-18 | 2016-10-06 | 宇部興産株式会社 | Polyimide gas separation membrane and gas separation method |
CN106567191A (en) * | 2016-10-09 | 2017-04-19 | 华中科技大学 | Preparation of fluorinated polyimide electrostatic-spinning fiber film and application in oil-water separation |
JP2019534141A (en) * | 2016-11-04 | 2019-11-28 | ダウ グローバル テクノロジーズ エルエルシー | Method for producing improved polyimide separation membrane |
JP7160804B2 (en) | 2016-11-04 | 2022-10-25 | ダウ グローバル テクノロジーズ エルエルシー | Method for making improved polyimide separation membrane |
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