METHOD AND PLANT FOR OBTAINING A MAIN PRODUCT STREAM FOR THE PRODUCTION OF TRANSPORT FUEL

Abstract

The invention relates to a method and plant for obtaining a main product stream with hydrocarbons from a reactant comprising at least one substance of the group of alcohols and the group of ethers, for the production of transport fuel The reactant is fed to a prereactor stage, which is at least partially catalytically converted into an intermediate product stream, wherein the molar proportion of C2 to C5 hydrocarbon among all hydrocarbon of the inter-mediate product stream is at least 55 percent. The intermediate product stream is fed to a main reactor stage, in which the hydrocarbons of the intermediate product stream are oligomerized by means of a main reactor stage catalyst. The weight proportion of C10 to C16 hydrocarbons among all hydrocarbons of the main product stream is at least 15 percent. The catalyst is a metal organic framework

Claims

1. Method for obtaining a main product stream with hydrocarbons from a reactant, which reactant comprises at least one substance of the group of alcohols and the group of ethers, for the production of transport fuel, wherein the reactant is fed to a prereactor stage, in which prereactor stage the reactant is at least partially catalytically converted into an intermediate product stream, wherein the molar proportion of C2 to C5 hydrocarbon among all hydrocarbon of the intermediate product stream is at least 55 percent, wherein the intermediate product stream is fed to a main reactor stage, in which main reactor stage the hydrocarbons of the intermediate product stream are oligomerized by means of a main reactor stage catalyst for obtaining the main product stream, wherein the weight proportion of C10 to C16 hydrocarbons among all hydrocarbons of the main product stream is at least 15 percent, and the main reactor stage catalyst is a metal organic framework (MOF) catalyst.

2. Method according to claim 1, wherein the molar proportion of olefinic hydrocarbons among all hydrocarbons of the intermediate product stream is at least 50 percent.

3. Method according to claim 1, wherein, from the main product stream at least one transport fuel stream is obtained, preferably, that the main product stream is at least partially fed to a fractionator stage to obtain the at least one transport fuel stream, that the weight proportion of the C10 to C16 hydrocarbons among all hydrocarbons of the at least one transport fuel stream is at least 35 percent, in particular at least 50 percent.

4. Method according to claim 3, wherein the at least one transport fuel stream comprises a jet fuel stream and/or a jet fuel precursor stream and/or a diesel stream and/or a gasoline stream.

5. Method according to claim 4, wherein the jet fuel stream and/or a hydrogenated jet fuel stream primarily comprises jet fuel, in particular, that the jet fuel stream and/or the hydrogenated jet fuel stream substantially consists of jet fuel.

6. Method according to claim 3, wherein at least one recycle stream is obtained from the fractionator stage (13) and recycled to the main reactor stage, and the at least one recycle stream comprises a liquid recycle stream recycled to the main reactor stage with a pressure drop from the fractionator stage to the main reactor stage.

7. Method according to claim 3, wherein the fractionator stage comprises a depropanizer distillation column for separating the main product stream at least into a liquid main product stream and a gaseous stream and that the gaseous stream is at least partially recycled to the main reactor stage, preferably, that the recycled gaseous stream is compressed by a recycle gas blower.

8. Method according to claim 3, wherein, the molar proportion of olefinic C10 to C16 hydrocarbons among all C10 to C16 hydrocarbons of at least one of the at least one transport fuel streams, preferably the jet fuel precursor stream, is at least 60 percent.

9. Method according to claim 3, wherein one of the transport fuel streams, preferably the jet fuel precursor stream, is at least partially fed to a hydrogenation stage from which a hydrogenated transport fuel stream is obtained, and that a molar proportion of paraffinic C10 to C16 hydrocarbons among all C10 to C16 hydrocarbons of the hydrogenated jet fuel stream is at least 70 percent, and that a molar proportion of olefinic C10 to C16 hydrocarbons among all C10 to C16 hydrocarbons of the hydrogenated jet fuel stream is at most 20 percent.

10. Method according to claim 1, wherein the reactant is methanol or dimethyl ether, preferably that the dimethyl ether is derived from methanol.

11. Method according to claim 10, wherein the methanol is obtained by synthesis from a synthesis gas comprising hydrogen and at least one of carbon monoxide and carbon dioxide, and the carbon dioxide is obtained from ambient atmosphere by a direct air capture (DAC) device and/or or from the combustion of biomass, and the hydrogen is obtained from water by electrolysis, and the electrolysis is powered by electricity from renewable energy.

12. Method according to claim 11, wherein the synthesis gas is obtained from the gasification of biomass.

13. Method according to claim 1, wherein for the catalytic conversion in the prereactor stage a silico-alumino-phosphate molecular sieve catalyst, particularly a SAPO-34-catalyst, or a zeolite catalyst, in particular a zeolite catalyst of the ZSM-5 type, is used.

14. Method according to claim 1, wherein the prereactor stage comprises a prereactor device for catalytic conversion of the reactant and a quench column, from which quench column the intermediate product stream is obtained as gas fraction, and a liquid fraction with carbon hydrates is obtained from the quench column, and the liquid fraction is fed to the main reactor stage and/or to the fractionator.

15. Method according to claim 1, wherein the metal organic framework (MOF) catalyst comprises a MOF lattice and a catalytically active site hosted in the MOF lattice, wherein the MOF lattice comprises a number of nodes and a number of linkers interconnecting the nodes, wherein the catalytically active site comprises a structure of formula: ##STR00034## wherein the catalytically active site according to the structure of formula comprises: M.sup.1, which is a transition metal, in particular Ni; L.sup.1 and/or L.sup.2, which are independently selected from: H, an alkyl group, an aryl group, an olefin, an organic group comprising a hetero-atom such as oxygen or nitrogen, CO, NO, NO.sub.2, CO.sub.2, a halogen atom, or wherein formula does not comprise L.sup.1 and/or L.sup.2, wherein preferably L.sup.1 and/or L.sup.2 are each aceto groups, wherein more preferably L.sup.1 and L.sup.2 together form an acetylacetonate group; E, which is selected from P, N, As, O, S, Bi; R.sup.1, which is selected from H, P, an alkyl group, an aryl group, in particular a phenyl group, or wherein formula does not comprise R.sup.1; R.sup.2, which is selected from R.sup.1; A, which is selected from O, N, S, a carboxylate group, an alcoholate group, a sulfide group, a sulfonate group, a phosphate group, an ester group, an amine group, an imine group, a pyridine group, ER.sup.1R.sup.2, or L.sup.1; D, which is an aliphatic group or an aryl group, in particular a phenyl group, wherein in case D is an aryl group, in particular a phenyl group, the aryl group, in particular the phenyl group, interconnects either A or C.sub.N with E via ortho, meta or para bonding of said A or C.sub.N and E to the aryl group, in particular to the phenyl group; X.sup.1, which is selected from a carboxylic acid group, sulfonic acid group, a carboxylate group, a sulfonate group, a carbonyl group, a hydroxyl group, a hydroxylate group, an amino group, an ammonium group, a phosphino group, a phosphonium group, a pyridine group, a pyridine derivative, an imidazole group, an imidazole derivative, an imidazolate group, a phosphonate group, a phosphonate derivative, a nitrile group, a boronic acid group, a boronic acid ester group, a triazole group, a triazolate group, atetrazole group, a tetrazolate group or wherein formula does not comprise X.sup.1; wherein the catalytically active site according to the structure of formula optionally comprises C.sub.n, which relates to a carbon chain with a number of n carbon atoms, wherein n=1-5 and wherein the carbon chain is linear or branched, wherein the catalytically active site is bound or coordinated to the MOF lattice, wherein the catalytically active site is bound or coordinated to the MOF lattice via X.sup.1 or in case that the catalytically active site according to the structure of formula does not comprise X.sup.1, the catalytically active site interacts with the MOF lattice by non-covalent interactions such as van der Waals interactions, dipole-dipole interactions, ion-dipole interactions or H-bridges.

16. Method according to claim 15, wherein M.sup.1 is selected from Ni, Pd, Pt, Co, Fe, Ru, Rh, Ir, Os, W.

17. Method according to claim 15, wherein C.sub.n, is C.sub.1 or C.sub.2.

18. Method according to claim 15, wherein a) the nodes of the MOF are independently defined by a structure of M.sup.2.sub.wL.sup.3.sub.z, wherein M.sup.2 refers to one or more atoms of an element, wherein the element preferably is a metal, a semi-metal, an alkali metal, or an earth alkali metal, w=1-24, L.sup.3 refers to a ligand binding or coordinating to M.sup.2 via O, N, S, P, C, Cl, Br, I, z=0-24; and/or b) the linkers of the MOF are independently defined by a structure of R.sup.3.sub.xX.sup.2.sub.y, wherein R.sup.3 refers to a structure comprising a number of m=2-50 C atoms, wherein the structure comprises one or more functional groups selected from an amino group, an imido group, an amido group, a cyano group, a nitro group, an aldehyde group, an urea group, a thiourea group, an ester group, a carbonate group, an alcohol group, an ether group, a halogen, a phosphine derivative, a phosphine oxide derivative, an imidazolium group, a pyridino group, a triazole group, an imidazole group, a phosphate group, a sulfonic acid group, a sulfonate group, an enolate group, an imine group, a phenantroline group or combinations thereof, or wherein the structure does not comprise any of said functional groups, X.sup.2 is selected from a carboxylic acid group, a sulfonic acid group, a carboxylate group, a sulfonate group, a carbonyl group, a hydroxyl group, a hydroxylate group, an amino group, an ammonium group, a phosphino group, a phosphonium group, a pyridine group, a pyridine derivative, an imidazole group, an imidazole derivative, an imidazolate group, a phosphonate group, a phosphonate derivative, a nitrile group, a boronic acid group, an ester group, a triazole group, a triazolate group, a tetrazole group, a tetrazolate group, $x=1-8;$ $y=1-8.$

19. Plant for obtaining a main product stream with hydrocarbons from a reactant, which reactant comprises at least one substance of the group of alcohols and the group of ethers, for the production of transport fuel, wherein the plant comprises a prereactor stage to which prereactor stage the reactant is fed and in which prereactor stage the reactant is at least partially catalytically converted into an intermediate product stream, wherein the molar proportion of C2 to C5 hydrocarbon among all hydrocarbon of the intermediate product stream is at least 55 percent, wherein the plant comprises a main reactor stage to which the intermediate product stream is fed, which main reactor stage comprises a main reactor stage catalyst for oligomerizing the hydrocarbons of the intermediate product stream for obtaining a main product stream, wherein the weight proportion of C10 to C16 hydrocarbons among all hydrocarbons of the main product stream is at least 15 percent, characterized in that the main reactor stage catalyst is a metal organic framework catalyst.

Description

[0156] Further details, features, aims and advantages of the present invention are shown in the following with reference to figures describing embodiments. It is shown in

[0157] FIG. 1 a schematic representation of an embodiment of the plant according to the invention for executing an embodiment of the method according to the invention;

[0158] FIG. 2a-c schematic representations regarding a flow of hydrocarbons through a channel comprising a) a Ni zeolite catalyst, b) a Ni amorphous silica alumina catalyst and c) a Ni MOF that may be used as MOF catalyst according to the invention;

[0159] FIG. 3 a) PXRD of NU-1000 (curve 1) and of PO-TA-NU-1000 (curve 2); b) PXRD of Mg.sub.2(olz); c) Nitrogen physisorption isotherm for NU-1000, wherein both the adsorption curve (ads) and desorption curve (des) are illustrated; d) Nitrogen physisorption isotherm for PO-TA-NU-1000, wherein both the adsorption curve (ads) and desorption curve (des) are illustrated; e) Nitrogen physisorption isotherm for Mg.sub.2(olz), wherein the adsorption curve (ads) is illustrated.

[0160] The method according to the invention may be executed by the plant according to the invention shown in FIG. 1. In the plant shown, a main product stream 1 is obtained from methanol 2 as reactant 3. That methanol 2 is green methanol that has been obtained from a methanol synthesis reactor 32 fed a synthesis gas 35 substantially consisting of carbon dioxide and hydrogen. The hydrogen is provided by an electrolysis plant 33 powered with electricity from renewable energy and the carbon dioxide is obtained from ambient atmosphere by a direct air capture device 34. From the main product stream 1, a jet fuel precursor stream 4, a diesel stream 5, a gasoline stream 6, a liquified petroleum gas stream 7 and a fuel gas stream 36 are obtained. With the exception of the fuel gas stream 36, the mentioned streams present transport fuel streams 8 comprising a respective transport fuel.

[0161] The reactant 3 passes a heat exchanger 9 and is fed to a prereactor stage 10 with a prereactor 10a for converting the methanol into light olefins with a SAPO-34 type catalyst. The hot gas product of the conversion in the prereactor 10a is fed to the lower section of a quench column 23 comprised by the prereactor stage 10. In the quench column 23, the higher boiling hydrocarbon components in the reactor effluent are condensed by passing a part of the bottom product from the quench column 23 via an external cooler of the prereactor stage 10 and recycling it back to the quench column 23.

[0162] Both hydrocarbon-rich liquids from the bottom section of the quench column 23 and the water-rich liquids from the top section of the quench column 23both presenting a respective liquid fraction 36are cooled further before being sent to a water/liquid extractor 24 of the prereactor stage 10 from which a water stream 27 and a hydrocarbon stream 28 is obtained.

[0163] The intermediate product stream 11 is obtained from the prereactor stage 10 by having a light olefin compressor 25 of the prereactor stage 10 compress the gaseous light olefin fraction leaving the quench column 23 at the toppresenting a gas fraction 37and having it dried in a standard zeolite drying unit 26 of the prereactor stage 10. This intermediate product stream 11 then is fed to main reactor stage 12 with a main reactor 12a from which the main product stream 1 is obtained.

[0164] That main product stream 1 is fed to a fractionator stage 13 with a depropanizer distillation column 14 operated at elevated pressure in which the main product stream 1 is separated into a liquid main product stream 15 and a gaseous product stream 16. That gaseous stream is split into a first sub-stream, which first substream is fed to a single stage recycle gas blower 17, thereby forming a recycled gaseous stream 18, and then recycled to the main reactor stage 12 by being fed to the intermediate product stream 11. The second sub-stream is fed to a stabilizer 22 to be described in more detail below.

[0165] The liquid main product stream 15 is successively passed through a depentanizer 19 and a main fractionator 20, both comprised by the fractionator stage 13, and from which a respective liquid olefin stream 21a, 21b is obtained. Each of these liquid olefin streams 21a, b is separated into two sub-streams, of which one is recycled to the main reactor 12a as a liquid stream and the other fed to the aforementioned stabilizer 22. The aforementioned hydrocarbon stream 28 is also fed to the stabilizer 22. From the stabilizer 22, the gasoline stream 6 and the liquified petroleum gas stream 7 are obtained.

[0166] The stabilizer 22 is a distillation column which separates lighter, volatile hydrocarbons and any potentially present inert gases (as for example, hydrogen, CO.sub.2, CO, nitrogen) from the mixture of hydrocarbon streams fed to the stablilizer 22, such that the gasoline stream 6 leaving the stabilizer 22 as the bottom product is stable at ambient conditions and fulfils the stability specifications applicable to gasoline transport fuel. Stable and stability refer to a composition which ensures that no relevant amount of hydrocarbon vapor is emitted during the later storage of the gasoline at ambient conditions.

[0167] The light hydrocarbons and inert compounds separated in the stabilizer 22 may leave the upper section of the stabilizer 22 as the liquified petroleum gas stream 7, which may be here understood as a green LPG stream and the fuel gas stream 36, which is also green in the sense of being climate-friendly. The liquified petroleum gas stream 7 preferably contains more than 80% by weight of the C3 to C5 hydrocarbons separated from the gasoline stream 6 in the stabilizer 22. The fuel gas stream 36 contains the balance of the light hydrocarbons separated from the gasoline stream 6 in the stabilizer 22 and additionally all gaseous hydrocarbon compounds and inerts contained in the feed streams to the stabilizer 22. The fuel gas stream 36 may be used to cover the fuel demand of process streams of the plant, for example in the steam-superheater of the steam and condensate system of the plant.

[0168] From the main fractionator, the jet fuel precursor stream 4 and the diesel stream 5 are obtained. The jet fuel stream precursor 4 is fed to a hydrogenation stage 30 in order to meet jet fuel specifications and a hydrogenated jet fuel stream 31 is obtained. Wherein the results given in FIG. 3 a)-e) are self-explaining, it is now referred to FIGS. 2 a)-c), illustrating a schematic flow of hydrocarbons through a channel 100 (representing a reactor) comprising a) a Ni zeolite catalyst, b) a Ni amorphous silica alumina catalyst and c) a Ni MOF that may be used as MOF catalyst according to the invention. Educt feed stream E of a first hydrocarbon composition enters the respective channel 100, the hydrocarbons flow along diffusion paths 111, 112, 113 and exit the channel 100 as product stream P. The Ni zeolite catalyst illustrated in FIG. 2a provides a well-defined pore structure, see the building blocks 115 of the catalyst. The building blocks 115 (and also the building blocks 116, 117) comprise catalytically active Ni centers 120. The relatively small pore size (e. g. 12 Angstrm) restricts the length of the hydrocarbon conversion. The diffusion of molecules flowing through the channel 100 is restricted by the structure (building blocks 115) of the catalyst, which may also cause trapping of longer molecules. The Ni amorphous silica alumina catalyst illustrated in FIG. 2b provides an ill-defined pore-structure (caused by building blocks 116) with a large range of pore sizes (e.g. 15-100 Angstrm). Such catalysts generally do not provide sufficient yield in the preferred range of hydrocarbons with a carbon count of 9-18, preferably 10-16 carbon atoms. Ni MOFs (which may be a MOF catalyst according to the invention) provide a well-defined pore structure with pore sizes of e.g. 30Angstrm. Molecules may easily penetrate (diffuse) through the building blocks 117 of the catalyst. Such a catalyst has shown to be efficient for forming hydrocarbons with a carbon count of 9-18, preferably 10-16 carbon atoms.

Experiments

[0169] The following examples are used to describe the invention. Based on the examples, the person skilled in the art can easily conclude that and how to vary certain parameters or structures as given in the above description.

Synthesis of of Basic MOFS NU-1000 and Mg.SUB.2.(olz)

NU-1000

[0170] ZrOCl.sub.2.Math.8 H.sub.2O (2.47 g, 7.51 mmol, 1.0 eq.) and benzoic acid (49.34 g, 400.00 mmol, 53.3 eq.) were mixed in 150 mL DMF in a 250 mL screw-capped bottle, sonicated until clear dissolution and then incubated in an oven at 100 C. for 1 h. Parallel to this, H.sub.4TBAPy (1.02 g, 1.49 mmol) was dissolved in 50 mL DMF in another 250 ml bottle, incubated in the oven at 100 C. for 30 min. and sonicated while cooling down for 20 min. The H.sub.4TBAPy solution was then added together with TFA (1 mL, 12.95 mmol) to the premade Zr-node-containing solution. The yellow suspension was briefly shaken and placed in a pre-heated oven at 120 C. for 17 h.

[0171] After cooling down to room temperature, the precipitate was isolated by filtration through a Sartorius filter and washed three times with 75 ml of DMF, with 1 h soaking between washes. The solid was then further washed four times with 75 mL of DMSO, again with soaking for 1 h between washes. Afterwards, the material was dispersed in a solution of 450 mL DMSO and 18 mL of a 8 M aqueous HCl solution and kept at room temperature for 21 h. The solid was then isolated via filtration through a Sartorius filter, washed thrice with 75 mL of DMSO and soaked in 300 mL EtOH overnight. The solid was filtrated again, soaked twice with 300 ml EtOH over the course of 7 h and then kept in 300 mL EtOH. To this suspension, triethylamine (0.2 mL, 1.43 mmol) was added and kept for 22 h at room temperature. This process was repeated once more. The yellow solid was isolated via filtration, washed five times with 300 mL EtOH and dried in a vacuum oven at 80 C. for 1 h. The MOF was activated under vacuum for 18 h at 120 C. to yield fully desolvated NU-1000.

Mg.SUB.2.(olz)

[0172] Mg(NO.sub.3).sub.2.Math.6 H.sub.2O (2.26 g, 8.81 mmol, 2.1 eq.) was dissolved in 112 mL EtOH, and Na.sub.2(olz) (1.50 g, 4.20 mmol, 1.0 eq.) was dissolved separately in 198 mL DMF. The olsalazine solution was additionally sonicated for 15 min. Both solutions were combined in a 500 mL screw-capped borosilicate glass bottle and sonicated again for 10 min. The bottle was sealed, put in a sand bath, and heated in an oven at 120 C. for 24 h.

[0173] The reaction mixture containing a yellow precipitate was slowly cooled down to room temperature, filtered through a Sartorius filter and was washed with successive aliquots of DMF (3100 mL) at 80 C., followed by aliquots of MeOH (3100 mL) at 60 C. The solid was subjected to a solvent exchange by suspending it twice in 300 mL of fresh MeOH and heating to 60 C. for a minimum of 24 h in the oven. The methanol-solvated material was isolated in the rotatory evaporator and activated under vacuum for 24 h at 250 C. to yield fully desolvated Mg.sub.2(olz).

Synthesis of Functional NU-1000 MOFs

Example 1 (PO-TA-NU-1000)

[0174] A 0.1 M solution of 2-(diphenylphopshino) terephthalic acid in DMF (6.2 mL) was added to solid NU-1000 (502 mg) three-necked, round-bottomed flask under inert atmosphere. The suspension was stirred at 60 C. overnight. The solid was filtered off and washed with DMF and methanol and afterwards dried in high vacuum at 60 C. overnight to give PO-TA-NU-1000.

Example 2 (P-NU-1000)

[0175] A 0.1 M solution of 4-(diphenylphosphino) benzoic acid in MeCN (6.9 mL) was added to solid NU-1000 (503 mg) three-necked, round-bottomed flask under inert atmosphere. The suspension was stirred at 60 C. overnight. The solid was filtered off and washed with MeCN and methanol and afterwards dried in high vacuum at 60 C. overnight to give P-NU-1000.

Example 3 (PS-NU-1000)

[0176] A 0.1 M solution of sodium diphenylphosphinobenzene-3-sulfonate in H.sub.2O (6.9 mL) was added to solid NU-1000 (503 mg) three-necked, round-bottomed flask under inert atmosphere. The suspension was stirred at 60 C. overnight. The solid was filtered off and washed with H.sub.2O and methanol and afterwards dried in high vacuum at 60 C. overnight to give PS-NU-1000.

Synthesis of Nickel Functional MOFs

Example of Ni Catalyst Preparation from Functional MOF (PO-TA)-NU-1000

[0177] PO-TA-NU-1000 (120.3 mg) was activated by heating at 120 C. under vacuum for 4 h. A 0.1 M Ni solution was prepared dissolving Ni(acac).sub.2 (133.9 mg) in toluene (5 mL) yielding a green solution. The Ni solution (0.5 mL) was added through incipient wetness impregnation to PO-TA-NU-1000. The solid was dried in vacuum at room temperature to give Ni@ (PO-TA)-NU-1000.

Example of Ni Catalyst Preparation from Nickel Complex and Functional MOF (Ni(PO)@ NU-1000)

[0178] NU-1000 (120.3 mg) was activated by heating at 120 C. under vacuum for 4 h. A 0.1 M Ni solution was prepared dissolving 2-(diphenylphosphino) benzoic acid (307 mg) and Ni(acac).sub.2 (269 mg) in toluene (10 mL) yielding a green solution. The Ni solution (0.5 mL) was added through incipient wetness impregnation to PO-TA-NU-1000. The solid was dried in vacuum at room temperature to give Ni(PO)@ NU-1000.

Example of Ni Catalyst Preparation from Nickel Complex and Functional MOF (Ni(PO-TA)@ Mg.sub.2(olz))

[0179] Mg.sub.2(olz) (150 mg) was activated by heating at 250 C. under vacuum for 24 h. A 0.14 M Ni solution was prepared dissolving 2-(diphenylphopshino) terephthalic acid (151 mg) and Ni(acac).sub.2 (111 mg) in THF (3 mL) yielding a green solution. The Ni solution (0.3 mL) was added through incipient wetness impregnation to Mg.sub.2(olz). The solid was dried in vacuum at room temperature to give Ni(PO-TA)@Mg.sub.2(olz)).

Example of Ni Catalyst Preparation from Nickel Complex and Functional MOF (Ni(PO)@ Mg.sub.2(olz))

[0180] Mg.sub.2(olz) (150 mg) was activated by heating at 250 C. under vacuum for 24 h. A 0.14 M Ni solution was prepared dissolving 2-(diphenylphosphino) benzoic acid (132 mg) and Ni(acac).sub.2 (111 mg) in toluene (3 mL) yielding a green solution. The Ni solution (0.3 mL) was added through incipient wetness impregnation to Mg.sub.2(olz). The solid was dried in vacuum at room temperature to give Ni(PO)@Mg.sub.2(olz)).

Example of Ni Catalyst Preparation from Nickel Complex and Functional MOF (Ni(PCy2O-TA)@ NU-1000)

[0181] NU-1000 (150.6 mg) was activated by heating at 120 C. under vacuum for 4 h. A 0.1 M Ni solution was prepared dissolving 2-(dicyclohexylphosphino) terephthalic acid. HCl (420 mg), triethylamine (0.8 mL) and Ni(acac).sub.2 (267 mg) in methanol (10 mL) yielding a brown solution. The Ni solution (0.5 mL) was added through incipient wetness impregnation to NU-1000. The solid was dried in vacuum at room temperature to give Ni(PCy2O-TA)@NU-1000.

Example of Ni Catalyst Preparation from Nickel Complex and Functional MOF (Ni(PPh.sub.2O-TA)@ NU-1000)

[0182] NU-1000 (150.3 mg) was activated by heating at 120 C. under vacuum for 4 h. A 0.1 M Ni solution was prepared dissolving 2-(diphenylphopshino) terephthalic acid (370 mg) and NiCl.sub.2.glyme (224 mg) in methanol (10 mL) yielding a yellow solution. The Ni solution (0.5 mL) was added through incipient wetness impregnation to NU-1000. The solid was dried in vacuum at room temperature to give Ni(PPh2O-TA)@NU-1000.

Example of Pd Catalyst Preparation from Palladium Complex and Functional MOF (Pd(PPh.sub.2O-TA)@ NU-1000)

[0183] NU-1000 (150.2 mg) was activated by heating at 120 C. under vacuum for 4 h. A 0.05 M Pd solution was prepared dissolving 2-(diphenylphopshino) terephthalic acid (369 mg) and Pd(acac).sub.2 (307 mg) in methanol (20 mL) yielding an orange solution. The Pd solution (1 mL) was added through incipient wetness impregnation to NU-1000. The solid was dried in vacuum at room temperature to give Pd(PPh.sub.2O-TA)@NU-1000.

Catalysis

[0184] M@ type of MOF (M=Ni, Pd) (see table below for exact amounts) was placed in a 60 mL high pressure autoclave and flushed with Ar and then shortly with ethylene gas. The reactor was then pressurized with 10 bar ethylene at room temperature for 1 h. A 0.5 M solution of NaBH.sub.4 solution in anhydrous MeCN (0.5 mL) was added via syringe thereto. The reactor was closed, shortly flushed with ethylene gas, pressurized to 40 bar ethylene, and then heated to 80 C. for 2.5 h. The reactor was cooled down to room temperature and the pressure released. Toluene (1.3 mL) was added and the solution was transferred into a vial and analyzed by GC-FID.

TABLE-US-00001 C10-C16 M@ type of MOF MOF Amount (mg) Selectivity (%) Ni@(PPh.sub.2O-TA)-NU-1000 76 55 Ni@P-NU-1000 108 18 Ni(PPh.sub.2O-TA)@Mg.sub.2(olz) 100 45 Ni(PO)@Mg.sub.2(olz) 100 12 Ni(PCy.sup.2O-TA)@NU-1000 130 35 Ni(PPh.sup.2O-TA)@NU-1000 111 29 Pd(PPh.sup.2O-TA)@NU-1000 99 0

Characterization

[0185] Powder X-ray diffraction (PXRD) measurements were conducted on a Bruker D8 Advance diffractometer working in Bragg-Brentano geometry, with Cu K1 radiation wavelength of 1.541 . Diffraction was measured in the 20 range between 2 and 25.

[0186] Nitrogen sorption measurements were conducted on a Micromeritics 3Flex Physisorption instrument at 77 K, after activating at 120 C. under vacuum for 16-20 hours. The specific surface area was determined according to the Brunauer-Emmett-Teller (BET) method by fitting the isotherms in the 0.01 to 0.1 p/p.sub.0 range to meet the consistency criteria.

[0187] UPLC-MS experiments were performed on a Waters Acquity UPLC H-Class system equipped with a Waters BEH C18 (1.7 m) column, Acquity PDA UV/VIS and Acquity QDa ESI-MS detectors.

[0188] The MOFs were characterized by Powder X-ray diffraction and nitrogen physisorption. FIGS. 1a,b shows the PXRD and FIGS. 1c-e the nitrogen adsorption isotherms, respectively, of NU-1000, PO-TA-NU-1000 and Mg.sub.2(olz). The functional MOFs and Nickel functional MOFs were characterized and the function and nickel quantified by UPLC-UV and UPLC-MS after digestion of the MOF under basic conditions.