AT515046A2 - Metal-organic frameworks, their production and use - Google Patents

Description

Coating of metal-organic frameworks, diesex: production and anticipation

The present invention relates to a coating on novel novel polymers. Metal-organic oilexchanger Metal-organic framework, M'OF) soft metallic Khotexipunktar: B and Verbindangselementan? ≫ bastehexs "MOF siiid microporous crystalline materials with defined pore size. The invention MOF consists of k.oor'dinativ unsaturated metal nodes B of at least one metal which is selected from a group containing Mg, Cu, 2n, hg, Fe, W, Mo, Cr, Ft and of organic Meiaminhas based molecules serve as connecting elements between the metallic nodes and a 2,4, S-tris-imino-1,3,5-triazine and / or 2,4-di-imiro-1,3,5-triarine moiety.

State of the art:

As occlusion enzymes in HOF, there are molecules with: two carboxylic acid groups such as 1, i "BenAldic & rborsäaref or 2,5-dihydroxy-1, i-benzaldecarboxylic acid, WO2012 / 122233A2 or molecules with two imine groups such as 2,4-bipyr .iäio 'used. Further, molecules with three carboxylic acid tows 02020.12 / 012i95 & 2) or imine groups or with four carbon acid-or-isrdr groups are used. Metal-organic frameworks are used for gas storage of hydrogen and methane and as catalysts for cur

Gastrennurg as aSb separation of

Carbon dioxide or olefin used in gas burning. For the diffusion of larger. Molecules with more than three carbon atoms will be HOF with a Porsnweite before; above 0, oil required, WO2013 / 112212 A3 teaches that a larger pore size in the MOF can be obtained by sorbing large organic molecules of ice linking units. However, in the Verditurgurg no triasin compounds are mentioned,

One problem with coatings made from MOP materials is that the layers are crystalline materials to the metal-organic frameworks, which can result in fractures under mechanical stress. The resulting giss serves as a tunnel for Gssreoleküle, whereby an effective gas separation is reduced.

In order to prevent costly MOB ~ absorber materials and to prevent fractions of the MOP crystal, metal-organic frameworks are mixed with polymers and subsequently: spun, The resulting mixtures of metal-organic frameworks and polymers are referred to as "mixed matrix membranes", examples for this purpose are described in% 0 020ΙΙ / 08Χ ?? δΰ & 2 for the separation of CO 2 from natural gas. Om the Efficieny d: t: € 02 Separation of the syllabus MO'2012 / 11 5δΒ0Α2 the use of Amico-substituted bonding molars for 1 eu cur Her position of the metal-organic frameworks bxw. Möröld / OoBSllAl teaches the use of metal-organic frameworks for the more efficient 'Kohbentiidkib *' at the metallic nodes ml t Mkydiami NEN,

A problem of mixed matrix membranes occurs due to the fact that the Mate 1 lg & cirx frameworks and the surrounding polymer matrices wipe out, causing the Matal1-organic frameworks to run in ·; Sin's biggest problem is the "mixed matrix membranes". is. the porosity of the used: Pöl.y «!« rraafcrix. To ensure efficient dittnsone through the metal-organic frameworks, a dense matrix of palymer must be used which does not permeate molecules through the polymer matrix. In addition, C02 and O2 in the gas flow cause the swelling of the polymer matrix used at pressures above 15%, which in turn causes the separation performance of the polymer membranes to be similar. the polymer matrix becomes porous and permeable.

Another problem with "Mixed Matrix Membranes" is the distribution of the metal-organic framework in the polystyrene matrix, which is restricted to less than 40 Gauss,%. More than 40% by weight of MC> F particles in the polymer matrix cause agglomeration of the MOE KristaJ.Ipariika.i, and in the aggiofaeratas: · there are cannulas which can prevent efficient gas separation. As a matter of course, scaffolds were generally used Cn3, BCT2, MOF-Sf2ir7, EIF-S and described in the literature.

Kux: T.re.anuug before ·· Olefins and alkanes continue to teach us the use of polymers containing ionic furfuclases and 5r1.it of coordinatively unsaturated silver or copper ions, thereby selectively reversing the double bond of the ethos) or propper * Pi ~ bond to the and silver ions snhsf'tet. Mlerings, at the same time, the metals do not shunt metal-organic fertilizers and the silver-silent ones are reduced by light and other influences, therefore they must be repeatedly oxidized with aqueous hydrogen peroxide solution. cheerful 1,3,3-Trissinvarbindngsn as compound-eluting .in metal-organic Prepared soft "described soft"; starting from. toxic cyanoic acid (2,4,6, trichloro-1,3,5-triazine), as described in hei et al, Xnorg, Chem, Comm * 10, 2007, 9X0-913 and Fan et al. Inarg, Cher., 49, 2o1, 11637-11642. These compounds contain, according to Beakticnan, of Cyenuric acid, with a short Karr) of 2, 4, 6 ~ 7: riosvin ~ I f 3, 5-Triaui "and no 2, 4, S-Tris-bsi.ro ™ 1,3, b-triarii groups. The described compounds have only amino groups on the triazine glycol of cyanuric acid, which results in different geometries in the preparation of metal-organic frameworks, in contrast to the inventive compositions Associationxetsent «& with a 2,9,6-T'ris-it ;; ino-i, 3,5-triazine or 2,4-.is-irino ~ 1.3.5-triazine nucleus.

Next is Kernegham in Can. J, 2hem. 69, 2'Dll, 5'77 ~ S82 microporous fine-base networks

TherephtirLäidehyd'ttntS Tetnekds H-aminophenyl} methane and its reaction with Bsaigsihrrsauhyärid. sasfia suitability for gas storage described, however, no coordinatively unsaturated detail Hnotenpuxäkt hsw. Metal " organic scaffold: described: ;, whereby the use as MOE membrane only efficient Olefin / Psraffin separation as well as catalysts not; given is.

One of the present invention surprisingly solves said problems by providing a continuous MOE coating of porous polymers with late-stable Matali-organic frameworks having a pore width greater than 1 nm aciweiseri and from bonding Elanteo & from the reaction of melanin with carboxy or imino-aldehydes and a coordinatively unsaturated metal knot lane: kt · S from Fe, Ag, tu. Mg, He, Mo, Wo, Cr, Pt, Pb. These novel MQFs contain verbic acid ethers and are obtained from the reaction of melamine with. Aldehydes and form at least two imino bonds on the triasin ring with the amino groups of the melamine resulting in a 2, 4, 6, --Trisimino-i, 3, o-triaaln nucleus and at least one, coordinatively unsaturated Met.ailknotsnpunkt B softer from the group consisting of Fe, Ag, Ca, Mg, 2n Mo, Wo, Cr, Ft, ? d is selected. The coordinatively unsaturated metal junction δ contains {at least one metellaton • softer selected from the group consisting of Fe, Ag, Cu, Mg, En Mo, Wo, Cr, Pt, Fd, where the coordinatively unsaturated metalato! M in the oxidation state M '% M + il, M " iV,

Mh 'and M'v:' can lie ahead. Preferably, the terminal nodes B are at least one metal of which group is preferably Ag, Cu, Mg, rn Mo ,. Where, Cr, Pt, Cd contains, wherein the coordinatively unsaturated metalaform M in the onidation step Μ * !,

Mv '', SktiM, M'v and CTv: · may be present. The Hetellknotenpunkte B are particularly preferably soft: at least one Hetaliatom which to de ·: Group consisting of the Fa, Ag, Cu, Mg, kn Mo, Wo, Cr, Fa, M, wherein the Metaiiatoms M in the Oxidafcionsstu ε e + λ, M: ", H " i: j, such as Agg Ο o, '% Fe *' ", Ό 'iii i', > > ' . ·. . ·. f. ≪ v.'i " · " > >

Fti f * 11. ≫ NOT A WORD

In 1 ": gor I, the preparation of compound A by Rondensation reaction of -fine mel melamine with three moles of aldehydes is rare formation of a 2, 4, S-crisimino-1,3, S-triatine nucleus in only solution of malamine and Alcohol suitable solvent o. as Benko1, water, toluene, CS -'- Ci5 alcohols, ketones or Fther dargsstellt. Aldehydes R can be aromatic aldehydes and non-aromatic aldehydes and a mixture thereof, which together with the amino groups of the melamine, at least one Tu, r.-t; containing at least one functional carboxylic acid group or imine group, Dia Aldehyd® may comprise one or two hydroxy-methyl or amino groups,

The components of the binding compound A of the MOF according to the invention are pure by reaction with. Melamine the following aromatic aldehydes are suitable for use in a Carfoons plant: ··! - formylbenzoic acid, 2-formyl-benzoic acid, 4-formyl-1-hydrory-bonooesacetic acid, 1-fluoro-2-yl-β-hydroxyacetic acid bsnzoic acid, 4 ~ FoFkyi ~ 4 ^ hyoroyoic acid, 4 '' - Formyi ~ 5 ~ amino-benzoic acid i-FrirKiyl-F-affinino-benzosable, 1-fdrayl-4 "hyuroxy ~ hed: u> esaurs, 2-zormyi-S ~ hydroxy ~ banzoesäura, 4-formyl - 2f S-dlamino-benveic acid, 2 ~ fomyl-4 ~ amix} © - ~ bonr. ··, <:: ί ·: Η; : *:: &Gt;. F-Forrrayl - b -hydroxy-bssnzogaäarai S ~ Formyi ~ 3 ~ cs: Eboxy-benzoic acid, 2 {x-formvipheyl} acetic acid, 4- (4 '· forssyl 3'-metl5.oxyphoxy} -butyric acid , 4-formyl-benzamide, 8-Formyi Mapthoureure, 4-Formyl-Staphtoesäara, £ ~ Formyi -Faphoese,

Furthermore, for the VarbixKitingssiementa Ά, arfixxhmgsgsmSßexs MOB, the aldehydes can be used for reaction since mela- nin, with dinograms such as 4αχγγγγγΙνΙδΖΖ, 2-pormylpyrrole 1, F-pyridioa 1 dehyd, 5α pyrimidincarbaldehyde, and as nonaromatic aldehydes may be used 4-oxo-butyric acid, 5-ferric-2-butronitrile 1 or fomaldehyde,

Particularly preferred boron is the preparation of the compound; "- Kiolskül" ä of the erf gungsgeitsSen MOB are the aldehydes 4 ~ rormyl-benzoic acid, 2 ~ ForMyi ™ banzoesäerat 4-Förmyl-2 * S-dibydrozy -'bsrizoesänre, 4 ~ FörmyI-2 hydroxybenzoic acid, 4-ForayX ~ 2-sr; i: no ~ bsriKoessur: e, F-Forraylpyrtai, i ~ Forrsyl ~ ioidazol and i-Oxebutansdure. For the. The invention relates in particular to the following compositions: 2, 4, 6, -Triö 14-cerboxybentimino) -1, 3, 5-triazine, 2, 2, 4, 6, -Irisi2- ca tbo: · ybenz irono '-1, 3, 5-triezin, Fig. 3, 2,4,3, -tris (3,5-dicarboxybenzine kd.nos.i, 3,5-triazine, 4,4,6,6-tris {3-hydroxym-4 ~ ca.rbo &amp; yb & ruri: fenc $ - 'i% 3y5 ^ trcisKin., Fig. 5, 2, 4, 6, -Tris (3, 5 -dicarboxybenimino) ~ l, 3, 5 ~ t riasrn, .Fig, 6, 2 , 4,6, -Tris (3 amih.o-4 carboeybehrimino; -1, 3, sialiasin, Fig. 7, 2,4,6, -7.5: 16 (3, 6, &quot; Uamino &quot; carbo-benzoic acid} -1, 3, 5'-fiazine, Big, 8, 2, 4, 6, -Tris (4-esrhoxy-enyne-5-l, 3, 5-trzacin, Fig. 3 The use of these diffusibility A gives the result iadangsga :: iiäiie metal-organic framework by reaction pit: isheseas a® metal b-aselcate fc from the group consisting of Fe, Ay, Ce, dg, Cr, Cr, Ho, Do, Pt and Pd.

Preparation of the metal-organic frameworks

The preparation of erfmägemäiien Ktstall organiscbea scaffolds by. Reaction of at least one MetelI compound B furfaced from the group consisting of Fe, Ag, Go, Hg, 2ή, Gr, Mo, Wb, Ft have been Pd since at least awsi of the diffracting Ä a metal di-carhoxylate, or metali-giimin or metal tricarboxylic acid, or metal trihydrate or compound of di-metal-oi-earfooxylate or di-metal diisdn or di-methyl tricarboxylate, or B: L ~ MetalI-triimine Ciusterearbindong, for example bevortogt. 2, 4,6, -Tris {4-estaroxybehaiminc J-i, 3,5-triazine, Fiepe, 2,4, 6, -Tris (e-earboxybenxis and} -I, 3, 5 ~ fcriaxin, Fig. 2, 4, 6, -Tris {3, S-diocarboxyentimino) -1,3,5-triasi.ri, Fig. 4, 2,4,6, -Tris (3-hydroxy-4-carboxybenxiMinoi -1, 3, S -triaxin, Fig. 6, 2, 4, 6, -Tris (3, S ~ di irarfooxYbeati-rioo: -1,3, S-tr iasine, Fig. 6, 2, 4, 6, -T. :: is {3 .δίίί1ηο "4 carboxybenzimine) -1,3, 5-t riaxir, Fig. 7, 2,4,6, -

Tri s (3, -. 6 disiainO "i ~ csrböxyraa; zidiho} -1, 3, .5 ^ -triazi", Fig. 8, 2,4,6 # -Tris (4-ca £ böxyiffiino) -X, 3.5 ~ taiazXn, Fig. 9,

The Metelivex Binding Method of Preparation of the Efferent MOF as Metal Nitrate, Metal Aroxycate, Matalioxalate, Metal Chloride, or .in the Form of More Important Mets 11 Compounds. vorliegsn. Suitable strings may include CuCl, 2nC12, hgCl, FeCis, WC16, KoCIS, Cr2013Co803) 2, 2n (H03) 2, EqWOS, Fe (S303) 2, WCin, MOC16, Cr2C13,

Cu {C2H302}; and others are used, the use * of the Mefalrverbinduogen is not limited to the gerannte.

Suitable solvents for preparing MOF according to the invention are methanol, ethanol, tetrahydrofuran, dioxane, water, dimethylformamide,

Methyltorstasnid and mixtures thereof. Preference is given to 1; 1 mixtures of methanol and. Ethylmethoxide, water and dimethylformamide, water and dimethylformamide,

Methanoi and methylfotmamide, diethylformamide and tetrahydrofuran, and 1: 1: 1 mixtures of methanol and diethylformamide and tetrahydrofuran, methanol and DietHylfomasdd and water, water and Diethylford & nuä and tetrahydrofuran, methanol and Diimrthyliioroamid and tetrahydrofuran, ethanol and propylformamid and tetrahydrofuran Methanol and diethylfoarardd and dioxane used,

To make more efficient production of he ifaihuigsgerä & o MOF bxw. the precursors are made of metal, soft copper compounds &quot; di carboxylst, di -Metel i'dfrtuodE-ccayita't? Mets i i -diimine metal dicarboxylate brw. Metal tricarboxylate, or mefc, all-triimine, or "tricarboxylic base," such as MaHCOI TCM003, KQH, NaOS rarer · deprotonation, the acid groups at the compound of the invention; and faster treatment with. at least one metal B selected from the group consisting of Fs, Ag, Cu, Mg, In, Cr, Mo, So, Pt and Pd.

The temperature only preparation of the organometallic scaffolds is between 20 4C - 250 1> C preferably 20 :: C ·· 80 Preferably, cur synthesis of the · MOF microsolest: Payment is used for heating.

Production of the HOF coating aut polymers

The polymer buffers a polysulfide, polycarbonate,

Polyarylst, Bolyarylbereu, Poiya r yiather, polyimide, polyetherimide, fluorinated polyimide, polymethyl methacrylate ,. Polyamide, Geiluiose and polystyrene exist, bs can also co-polymers with the mentioned; Furthermore, phenolic resin phenolic structures as well as phenolic melamine resins, epoxy resins or melamine resins can also be used for the coating. The coating of porous polymers by disorganized metal organic motives is carried out by means of alternating and / or joint extrusion. warm dissolved Ve.rbindungsEnolekule «a and Hetaiii.ösuog B. The coating can be on flat, curled

Po.1 yroergawefeen and ac: * Hohbiae?: .. * ·· * aratt.finden.

Preference is given to porous "Folymerhoh.l fibers which. a Porsnveite of 10-5000 nm gewieen, Particularly suitable are unilaterally closed Bohlfaserr for Oltrei.il occurred ion or Mi kroi.il tratios ·; aas polysnon,

Folyetarsulfon, polyimide, polyether, etc., pol yamid ,,

The preparation of the coating with the metal-organic chemical according to the invention: Retcwerke.n besthexsd from 2, ^, B-Trlsimino-l, '3, S ~ triarine linker &amp; and at least one Metsilkömponer te 8 aasgewählt. consisting of the group consisting of Fe, & g, Ca, Pia, Sn, Cr, Mo, Io, Pt and Pd, includes the following steps: &) functionalizes the polymer surface, B} Raaks ion of the formed Hydfoky amine Groups with. .the acid groups dos betowerk Linkers &amp; C) Synthesis of the MOF Coating on the Polymerobaric Table. followed by the metal sols B, D) Activate the membrane by removing the L0sas55.it:i: ice. Ä) Funktioneji lyieran of Polym.eru with. Hydrq.s.y, & min: o or C & rboxy groups. If the surface does not contain any functional hydroxy-amiro- or carboxylic acid groups, they are generated by the chemical reaction. The functionalization with: acid and Bydroaygruppex: the surface fixsdeu preferred in aromatic polymers without functional group · -, instead. Varwenduxsg Finder · predicts Rolysulfone

Folyecheraulfone, Pglyamde,, Polysmide.

Di «Ecreugnng de ?; Hydroxy-amino or Cs-rboxyro groups on the polymer surface can be made by any means known to those skilled in the art. So kaxin the Fuhttionaiisierung ml ·: plasma of bdelgasen {argon, helium, oxygen, carbon dioxide) take place. Wide ϊ: the functionalization can be carried out by photooxidation followed by polymerization with acrylic acid or by Blanc reaction, iFormäidehyd, Saixsäurs and Sinkchlorid}, the reaction with Aryldiaroniumsalxan or the oxidation by peroxides such as R202 with iron sulfate or R2S208. B) reaction of the formed hydroxy-amine moieties; with the acid groups of the beteeer linker A consisting particularly preferably of a coke selected from the group consisting of 2, 4, 6, -Tr is cT-c & rboxybenriminoä -i, 3,5 ~ triasin, 2, 2,4, 6, -Tris {i-ocarboxybenzimino; -1,3,5 ~ triaxin, Fig. 3, 2,4,6, -Trls (3, S-dicarboxy-tenthimino) -I, 3,5-fcriasin, Fig. 4, 2,1,6, -Tris; 3- r.hydroxy-4 ·· carboxybanximlo} -I, 3,5-triaxin, Fig. 5, 2,4,6, -TrisP, 3-dicarboxybenzimino) -1,3,5-triaxin, Fig. 6, 2,4,6, -Tris {3 atsino-d earboxybensi kiinopi, 3, S-triacin, Fig., 2,4,6, -Tris; 3, 6 diam: ino "'4 ~ carboxybentiiv.io. o5 ~ i, 3, S-tri.axin, Fig. 3, 2, 4,6, -Tris i 4 ~ carhoxy: hmi.no} ~ -l, 3, S-triaxin, Fig, 9 or Reaction of the Uarboxy Groups with the Metal Solution B -nit: at least one metal B selected from the group consisting of Fe, Ag, Cu, Hg, in, Cr, Mo, Mo, Pt: and Pd, C5 The synthesis is HOF coating in the forums of the polymer and. on the polymar surface which this

Geometries of: carbon lasers, '' 'honeycomb structure by alternating indices of solutions and afowech'seld reaction of the ssuregrasppexi of the linker which particularly preferably consists of at least one compound soft; is selected from the group 2, 4,6, &quot; Tr.is {&quot; • -carboxyhe.aoisriino) -1,3., 5--1: r iasi n, Fig. 2, 2,4, 6, -Tris {.2-carbo% yt> enzimino} "1,3,5-fc-riazine, Fig. 3, 2.4.6, -Tris x 3, S -di c & r boxybeis si istino) -1, 3, a-irrine, Fig. 4, 2.4.6, -Tris (3 "hydroxy ~ 4" carboxybenzimino; -1,3, 5 ~ t r iasi a, Fig. 5, 2, 4, 6, -Tris {3, S-dicfarooxybeonimixso) -I, 3, o-triarine, Fig. 6, 2,4,6, -tris (3-amino-4-carfooxybenzylamino) -1,3, S-trisin, Fig. # 2,4, 6, -Tris &lt; 3, 6 diaKi: in O &quot; 4 &quot; : rboxybensi®inc) "1,3, S-triazine, Fig. 8, 2,4, 6, -Tris {4 ~ c and rboiscyixaiao) -1, 3, S-triarine, Fig. 9, and by alternately pumping through of solutions and reaction with the Meta 1 i component 8 with at least one metal B susgewdhlt from the group consisting of Fe, .Hg, Gu, Mg, Zn, Cr, Mo, Wo, Ft and Fd, particularly preferred are solutions of the chlorides CuCX2 , FeCX2, AgCl, and MC 16. The stepwise construction of the meta-1 organic network: consisting of dexa 1, 3, 5-tris ~, in-2, 4,6-trisagin linker L and the metal coronene B xait at least "Inexa metal B susgewähic from the group to the Fe, hg, Cu, Hg, 3a, Cr, Mo, So, Fl: and Pd provided by stepwise1 reaction whereby alternately the solution which the linker Ά xait the 2,4,6 Trisimino ~ I, 3,6-triasine contains nucleus and the solution contains the meticomponent B through the di p Through the Durohpumpan under a pressure between 0.5 --- 25 bar is: ensures that MOP crystal © also know in the pores of hollow fibers Djlntbetrldie ^ t: * darden know. Ewiseken the Esschichtuageschritten can a Waschschriti; with methanol, ethanol, isopropanol, water or Auatcn egg ngafüge. Matal 1 Compound B and 2, 4, S-Trisiminp-1, 3, 6-Triaein -10.0.000 &amp; washed out. D) The activity of the membrane can be determined by Aafheieeo. and stand for the abs orb 1 e r t. en sol s anga m i 11 e bsele ko i e es, follow or by uplifting and evacuation. The membrane is stored under nitrogen or argon to avoid reactions with oxygen and water.

Use of the olefinic Metai 1-organic Ges: Os bmetribr anen

The use of the erfindurgsgamäBee Poiymermembranen with Baschiqhtühg to MOE consisting of at least one Verbindungeelement A softer selected from a group consisting of 2,4, 6, -Tris (4 ~ carboxybenzim.ino} -1, 3, S-kriasin, Fig.2 , 2,4, S, -Tris (T-earboxybeneiniino) -1,3,3-triatin, Fig. 3, 2,4,6, -Tris (3, S-dicarboxybenzairmire) ~ 1,3, S- triagir, Fig. 4, 2,4,6, -Tris C3-hydroxy-4'-carboxybenzimino; ~ 1,3,5-trimer in, Eid. 5, 2,4,6, -Tris {3,5-dicarboxybenaimino ) -1, 3, B-triarine, Fig. 6, 2, 4, 6, - Tris {3 affiiGC "4 carboxybenaitinoi ··· !, 3, S'-triaine, Fig. 7, 2, 4, 6, -Tris {3, 6 dlami.no-4-carboxybenrimino; -1, 3, S-trissin, Fig. 3, 2,4, 6, -Tr is ii-csrboxyimino; -1,3, S -triatin, Fig. 3. with the metal component Xe with at least one metal.! B selected from the group consisting of Fe, Ag, Cu, Mg, Oo, Cr, Mo, so, Pt and fki'A &amp; rfn ttrrr ^ FS & sfcringming, gas storage of hydrogen, methane, as well as catalysts for reactions cur alkane isomer ization, metbatbeese, oxidation of phenol and Benroi and further reactions for the sine temperatures; Under 300 'hl is sufficient to be used. The applications of the invention MOF are not limited to this enumeration. In Figure 10, the uses of only gas separation of ethane and propene from a mixed gas stream is described in more detail:

Figure 10 schematically shows the use of the MOP / polymer membrane of the present invention in a two-step process for the separation of the ether: ether and propene at which a H2, CH4, C2H6, C2.H4, C3H8, C3H4 and C4H8 contains d & rgesteXitv

In the first writing Ά is a Gsasfcrom Ά consisting of a mixture of C2BS and C3H8 or C2B6 and C4810 or C3B8 and C4H10 via a catalyst as described in $ 02013/133330 cur maximization of C3H6 between 6SÖ ~ 700 "0 im. Reactor A ambled. Sur gas separation is after compression to teerst the hydrogen by Foiymermembran A for separation of gases and then with the invention MöF / Poiymermehsan Ά the olefins C2R4 and G3H6 from the gas stream of CR4, C2K6, C3H8 and C4H18 contains burned, As Polymsrmembrsr, A can each The Polyssetmemhran known to those skilled in the art serve only selective separation of hydrogen from an aik & nhaifcrgen gas stream as on !!

Beispi "! a polyimide · - *; Pol ysirl: ftJrf-; Polyamide-Polypropylene-Polyethylene Medbran as well as polymer membranes from Co-Polytssrex? or fui'kiiopalisierte polymers of said polymerite membranes, susceptiichich may be contained in the membranes metal atoms or Seoüihe. As a novelty MöFe MöF / Polymer Mehran & know metal-organic frameworks: consisting of at least one: yarbißdaogselement h which is selected from a group consisting of 2,4, - 6, -Tris (4-carboxybensimino) -1 # 3 ». 5-tratin, Fig. 2, 2, 4, 6, -Tr in (2-cs.rbi> aybenaimioo} -1, -3, 5-fcriasin, Fig. 3, 2, 4, 6, - &quot; Tris (3,5-dicarboxybenrirrdno) -1, 3,5-t Kl3.2in, Fig. 4, 2, i, 6, "Tr is i3 - bydroxy-4-carfeoxyfee" zimlno} -1,3, 5-txiazirs, Fig, 5, 2, 4, 6, - &quot; tris {3,5-dicarhoxybexesixairxo) -1,3, S-triasin, Fig, - 6, 2, 4,6, -Tris (3-amino -4 carhoxybensistino} -1,3, S-triasin, Fig. 7, 2,4,6, -Tris (3, δ diamino-4-csrboxybeasamino) -X, 3, S-triaain, Fig, 3, 2, 4,6, -Tris (4 ~ earboxyirdno) -1,3, S "triaxin, Fig. 9, with the metal component" B with at least one metal B selected from the group consisting of .aas Fe, du, Cu, Mg, in, Mo, W can do Gaatnhnng be used.

The alkanes CB4, C £ H6, C38§ and € 46X0 which have been burned by the MOF / polymer membrane are then diluted in the second step with € 266 and thus the Gasström B hargestelIt. second step B, the gas stream B becomes softer than a mixture of reactors CF.4 and C2H6, from incompletely hydrogenated gases after the reaction &, C2K6, C3RP and C4H10 and. From eagesateteo C2H6 there is a catalyst, as described in WO20I3 / 13S3P0, for which MaximiMtnug »cefM'between 700-730 * C is implemented in the B occupant. The subsequent gas separation is after compression to 5-50 bar: first the hydrogen with CeIs Polymezmeffibran B separated and then .alt the erfindnngsgemaban MOF / Poymmermebran B the olefins C2H4 and C3H6 aas the gas stream of CK4, C2R6, C3H8 and C4H10 contains burned, As the polymer membrane 8, any of the polycondensation membranes known to those skilled in the art can only selectively remove hydrogen from an alkane-containing gas stream, such as a polyimide, polysorbate, polyamide, polypropylene, membrane membrane, or polymeric membranes of co-polymers or finely crystalline Polymers of the mentioned Polymsrmembranen, in addition, in the membranes. Metal atoms or oils may be included. Ms e r in du du g g.... E e e e MO MO MO MO MO MO MO MO MO MO y y y y y He He He He He He He anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan anorgan which is selected from a group consisting of 2,4,6-tris {i-carboxybenzimino; -I, 3,5-trichloroethane; fig. 2, '7, 4,' 6, tris M-carhörybenzimino} -1/3, S ~ triasin, Fig. 3, 2,4,6, -Tris (3,3-bicarbi> xybenximiro; ~ I, 3,5-triaain, Fig. 4, 2, i, 6, - Tris (3-hydroxy-4-carboxybenhiirino) -1,3 :, -S-friszine, Fig, 5, 2,4,6, -tris (3,5-dicarboxybenzimino) -1,3,5-triazine, Big , 6, 2,4,6, -Tris (3 amitio-4 carhosyhenxiMiroi -1,3, 5-trazin, Fig. 7, 2,4,6, -Tris (3,6 diamsne-I-esrboxybensimino) ~ 1, 3, S-trissin, Fig. 6, 2,4, e, -Tris. (I-narboxylmino5-1, 3, 5-triarine, Fig. 9. with the metal component B with at least one metal S selected from the Group consisting of Fe, Ag, Cu, Hg, En, Mo, w can be used for gas separation, the olefin is' Sel'cff'd ''? '& Xd: lx! &Lt; 5 \' 3gsgs83M & ed GOF / Polymeriaebran B, the resulting methane, which is scarce, is formed by the 'we i raaks in A.; Nb B into a remethaniser which is of the invention MOF / Belyesrans Hran B nschgesebaltet is separated Vierden. Am Demetharrlrei: is a compressor followed by. rapidly de-energizing the gas, which causes the gas to cool to -120 ° C and thereby present only CH4 gas, which can be burnt off as liquid C2HS, -C3B8 and C4H1Ü. The chased CHi in the burners of reactor A and Reactor B is assigned to the Aesrisa entrance.

Claims (8)

The invention relates to MetaiX-organic scaffolds which are constructed of molecular berbinysis products A. at least two carboxy- and X-isftinograms and metallic nodal points B, characterized in that the linking elements are attached to one another "! 2,4, B-tri-ieino-1,3, S-triasl.: · Or 2, S-imixso-l, 3, S-triasine nucleus are soft due to the reaction of melamine with aldehydes, which are usually mirxkuw- en .: eixre Carbcxy- or Irringruppen have, and be obtained as k.oordiη Π io unsaturated »metailische nodal points 8 at least one metal from the group Mg, Cu, Sn, Aq, Fe, W, Mo, Cr, V Rt, Bd is chosen 2. The invention relates to metal-organic scaffolds wet claim 1, characterized in that as connecting elements: h at least one verbi.ndungsed emerd: is selected from a group consisting of 2,4, 6 &gt; -Triss (4-csrboKybentimiiio} -I , 3, 5 ~ triaxix, 2,4,6, -Tris, 2-carboavbenrimino; -1, 3, S-triasin, 2,4, 6, - Tris {3, S-dicarboxybenaimiro) -1,3 , S-triasin, 2.4, · S, --Tris (U'-hydroxysycarboxylic isynesino) -, 3, 5 triasin, 2,4,6, -Tris {3, S-dicarboyloximixso; ·· 1, 3, 8 ~ trius irr, 2,4, 6, -Tris 3 ami.no - 4 earboxybenrisuno>, 3,5 ~ t.riasin, 2,4,6, -Tris {3,3 &lt; Siamir! 0-4-carboxy-beta-3-tetrato) -3, 3,5-t.riaxin, 2, 4,6, -tris- {4- [l, 3, o-trissin, and as coordinatively unsaturated xylyloid knot-derived B rnirKiestens a metal from the Group Mg, Cu, in, Mg, Ag, it, w, Mo, Cr, Pt is chosen, 3. The invention relates to metal-organic frameworks according to claim 1 and 2, characterized gak ο η η s elohnefc that cluster compounds we 1 marriage before? coordially inactive unsaturated Metsllatöm "in the first, rweifeen or drifcteo Oxidationsstufe entha 1 th be gebied by the resection of the metal components B which at least one metal to the group consisting of Mg, Cu, Rn, Mg, An, Fe, Cr, Pt and at least one VsrhirKiongselement .6 from the group 2, 4,6, -Tris {4 ~ caxboxybe: nzimino) -1,3, 5 ~ tria.xin, 2,4,6, -Tris il-carbaxybensiiaino; ~ 1.3.5- tsia: siü, 2,4,6, -Tris i3, 5-dicarboxybenKiw.inoi -1,3, S-ttizzin, 3, 4, 6, -Tris (G-hydroxy-i-carfooxybenximioo -1,3,5-triazine, 2,4,6-tris ¢ 3, 5-di c & x'boxyben almino5-1,3,5-triasine, 2,4,6-tris-3-amino-4-carboxybentyl cinema } -1, 3, S'-fcriszine, 2,4,6 ', -tris (3,6 diaxsino-i-carboxybensirdno-1,3, S-triazine, 2, 4, 6, -tris (--- 00 rbc / yc; :: no; ~ I, 3,5-triazine, wherein each Ciusterverbindong of MOF contains at least two metal atoms and at least • two VerfoLadungsgieaxtote. 4, The invention "organizes" scaffolds according to claim. 1 ~ 3, thereby gekexmxeicxhn "t that Met: all-a'rgard.scben dissolved ® a regular porous structure exhibit" "for molecule rare absorption freely accessible coordinatively unsaturated metallic nodal points, which consist of metals M in the oxidation state M <J, Μ: ϊϊ, M '; Knv, and M * Vi, have geometries of at least 1 nm in diameter and porosity; at least 0.4 csh g "A or 0.5 ccr g" 1 or more. 5, The invention relates to the production of coatings of the Metäil "-öxmanische Gerüst according to claim 1-4 on the surface and in the pores of porous polymers, characterized gefcan» Keicb »et that as polymers hollow fibers or fabric consisting of polyimide, Polyamide, Paly.su 1 ton, Pbiyethex'su J.fo: n be used on the surface and in dynes pyns, first be chemically functionalized with hydrox- carboxy- or hmn-groups and the synthesis of MGE- The process is then carried out by alternately or by the usual means of duron pumping of solutions of the connections A and of the metallic nodes B, 6, The invention relates to the use of the polymex membrane coated with detailed organic scaffolds according to claim 1 only olefin pi raffi rs tre ο nu .hiy, * * dddufije kkeήn be without t, as the polymer / MTF membrane is in In the first stage, methane is densely separated, prior to each olefin dye separation by the Polymar / MOF membrane, a hydrogen separation of Krittele polymer methyl occurs, and before hydrogen separation, the C2H6, C3H8, and C4H10 educts contains in rustic reactor uriges et st. 7. The invention relates to the use of Pclytäer / MOP 'membrane coated with metal-organic frameworks according to claim 1-5 svr Ole.fln paraffin separation, thereby gak®noseich »et that a two-stage process is used, which consists of two In each gas separation step, hydrogen is first separated from polyimides or polyetharimides in a polarizer or polyethy- lide polysaccharide, and thereafter the Oiefin bars are separated in the downstream MOF / foliar membranes to separate the ovals Ether, and Bropen takes place from the alkanes methane, ethane, propane and butane. 8, Oie invention relates to the use of the coated: Pclyvaerrm-mibranen with the metal-organic frameworks according to claim 1-5, characterized gek? A "a" 3. c | ife "st; * d®s5 * 'sl ^' tSlä K &amp; tiuysafc'qren door Methaface reactions of olefins and alkanes; Oxygen ions, reductions, hydrofluoric acid, and alkylating acids may have been used prior to unsaturated carbonates. Thus, the invention relates to the use of the polymer / metal-organic frameworks. Claim X-S, thereby gekannse.icb.net. that the polymer / KOF membranes are used exu: gas storage of carbon dioxide, hydrogen or methane. Hk The invention relates to the use of the polymer / metal-organic frameworks according to claim X-5 as AbsorherraateriaXierw thereby gaksnnreichnatf that the Bolyxaer / MOF membranes in hex: Ütrveittechnik. by absorption of heavy metals by binding to the Itrdn-o groups L.i.dhförverbiodungen A., as well as drugs for the absorption of Eharmsseutika: or in; Gastrenxrong by absorption of Qie fineh by Fl "binding to the Rugängllohen metäiixsehen nodes is used.