WO2021144813A1

WO2021144813A1 - Process for purification of hydrocarbons

Info

Publication number: WO2021144813A1
Application number: PCT/IN2021/050040
Authority: WO
Inventors: Tapas Kumar MAJI; Subhajit LAHA; Ritesh HALDAR
Original assignee: Jawaharlal Nehru Centre For Advanced Scientific Research
Priority date: 2020-01-15
Filing date: 2021-01-15
Publication date: 2021-07-22

Abstract

The present disclosure provides a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, {[ZnL₁L₂]L₃} wherein L1 is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II. The present disclosure also provides a process for obtaining the coordination polymer porous material of framework I and a process for separation of aliphatic compound from a mixed feed stream.

Description

PROCESS FOR PURIFICATION OF HYDROCARBONS

FIELD OF INVENTION

[0001] The present subject matter relates to the field of hydrocarbons, in particular relates to a process of purification of hydrocarbons.

BACKGROUND OF THE INVENTION

[0002] Purification of crude oil into its components has been of wide significance, because of its importance in chemical and petrochemical industries. The separation of hydrocarbons and small organic compounds in crude oil has been a challenge as these hydrocarbons have similar physical properties such as molecular weights, boiling points, dielectric constants. Industrially, the distillation process based on difference in boiling points has been the key method in compound separation. It is a difficult assignment for industries to separate those organic compounds having very minute boiling point difference. Porous coordination polymers (PCPs) or Metal-organic frameworks (MOFs) are widely recognized materials used in such separation and purification process because of their various structural and functional aspects. And the MOFs are far more promising for adsorption based separation or purification of a specific molecule from the mixture of hydrocarbons. (S. Kitagawa, R. Kitaura and S.- I. Noro, Angew. Chem. Int. Ed., 2004, 43, 2334; J. R. Li, R. J. Kuppler and H.-C. Zhou, Chem. Soc. Rev., 2009, 38, 1477). Of all the crude oil components, the class of volatile organic compounds such as benzene, toluene, xylene, the C8 aromatic isomers, and other aromatic isomers are industrially important because of their wide range of applications in preparing solvents, polymers, glues, paint products, pesticides, pharmaceuticals, agrochemicals and other organic intermediates. Separation of these mixtures into individual component by conventional methods is difficult since they have very similar physical properties. Hence separation using MOFs are preferred wherein the hydrocarbons are selectively adsorbed and the method found to be effective. There have been various investigations reported to separate and purify the hydrocarbon compounds.

[0003] US3558732A discloses an adsorptive separation process for the purification of hydrocarbons using crystalline aluminosilicate adsorbents and further desorption using toluene. EP1114808B1 reveals an apparatus for separation of hydrocarbon which employs cooling the gaseous hydrocarbon stream and separating after liquefaction using fractionation column. There is still a need in the state of art for obtaining a simple and an efficient process for purification of the hydrocarbons. SUMMARY OF THE INVENTION [0004] In an aspect of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, F₂ is 2,6-naphthalenedicarboxylate, F₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II.

[0005] In another aspect of the present disclosure, there is provided a complex of framework II obtained by the process, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Fi is o-phenanthroline, F₂ is 2,6-naphthalenedicarboxylate, F₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II.

[0006] In yet another aspect of the present disclosure, there is provided a process for purification of an aromatic feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, {[ZnLiL₂]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with an aromatic feed stream to obtain an output stream and a complex of framework II, wherein the aromatic feed stream comprises m-xylene and a mixture of o-xylene, p-xylene, and ethyl benzene, and the process of purification provides 100 % selectivity for m-xylene.

[0007] In one another aspect of the present disclosure, there is provided a process for separation of aliphatic compound from a mixed feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and L₃ is absent or dimethylformamide; b) contacting the framework I with a mixed feed stream to obtain an aliphatic -rich stream and an aromatic-rich complex of framework II, wherein the mixed feed stream comprises a mixture of one aromatic and one aliphatic compound, and the process of purification provides 100 % selectivity for m-xylene. [0008] These and other features, aspects, and advantages of the present subject matter will be better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. BRIEF DESCRIPTION OF DRAWINGS

[0009] The following drawings form a part of the present specification and are included to further illustrate aspects of the present disclosure. The disclosure may be better understood by reference to the drawings in combination with the detailed description of the specific embodiments presented herein.

[0010] Figure 1(a) and (b) illustrate the crystal structure and packing diagram of the framework compound 1, in accordance with an implementation of the present disclosure.

[0011] Figure 2 depicts the ¹ H -NMR spectrum for p-xylene (0.86) encapsulated compound la from the mixture of p-xylene and o-xylene, in accordance with an implementation of the present disclosure.

[0012] Figure 3 depicts the ¹ H -NMR spectrum for m-xylene (0.91) encapsulated compound la from the mixture of m-xylene and o-xylene, in accordance with an implementation of the present disclosure.

[0013] Figure 4 depicts the ¹ H -NMR spectrum for m-xylene (0.90) encapsulated compound la from the mixture of m-xylene and p-xylene, in accordance with an implementation of the present disclosure. [0014] Figure 5 depicts the ¹ H-NMR spectrum for m-xylene (0.905) encapsulated compound la from the 1 : 1 : 1 : 1 mixture of o- xylene, m- xylene, p-xylene and ethyl benzene (EB), in accordance with an implementation of the present disclosure.

[0015] Figure 6 depicts the ¹ H -NMR spectrum for styrene (0.65) encapsulated compound la from the mixture of styrene and ethyl benzene (EB), in accordance with an implementation of the present disclosure

[0016] Figure 7 depicts the ¹ H -NMR spectrum for benzene (0.64) encapsulated compound la from the mixture of benzene and cyclohexane, in accordance with an implementation of the present disclosure.

[0017] Figure 8 depicts the ¹ H -NMR spectrum for benzene (0.61) encapsulated compound la from the mixture of benzene and toluene, in accordance with an implementation of the present disclosure. [0018] Figure 9 depicts the ¹ H -NMR spectrum for benzene encapsulated compound la from the mixture of benzene (0.61) and mesitylene, in accordance with an implementation of the present disclosure.

[0019] Figure 10 depicts the ¹ H -NMR spectrum for benzene encapsulated compound la from the mixture of benzene (0.61 ) and 1,2,4-trimethylbenzene, in accordance with an implementation of the present disclosure.

[0020] Figure 11 depicts the ¹ H -NMR spectrum for p-dichlorobenzene encapsulated compound la from the mixture of p-dichlorobenzene and m-dichlorobenzene in accordance with an implementation of the present disclosure [0021] Figure 12 depicts the ¹ H -NMR spectrum for p-dichlorobenzene encapsulated compound la from the mixture of p-dichlorobenzene and o-dichlorobenzene, in accordance with an implementation of the present disclosure.

[0022] Figure 13(a-d) depict the vapour adsorption profiles for compound la at 293 K (a) xylene isomers, (b) styrene and ethyl benzene (EB) (c) benzene and cyclohexane, (d) benzene and toluene, in accordance with an implementation of the present disclosure.

[0023] Figure 14 (a-b) depict the vapor adsorption profiles for compound la at 298 K (a) fluorobenzene, chlorobenzene, bromobenzene, iodobenzene and (b) fluorobenzene and o-difluorobenzene, m-difluorobenzene, p-difluorobenzene (1,2-DFB 1,3-DFB, 1,4-DFB), in accordance with an implementation of the present disclosure.

[0024] Figure 15 (a), (b) and (c) illustrate the crystal structure and packing diagram of the framework compounds (a) lb, (b) lc and (c) Id, in accordance with an implementation of the present disclosure.

[0025] Figure 16 (a), (b) illustrate the crystal structure and packing diagram of the framework compounds (a) le, and (b) If, in accordance with an implementation of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION [0026] Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any or more of such steps or features.

Definitions:

[0027] For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.

[0028] The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

[0029] The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as “consists of only”.

[0030] Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or steps.

[0031] The term “including” is used to mean “including but not limited to”, “including” and “including but not limited to” are used interchangeably. [0032] The term “framework” refers to the group of compounds which contains metal atoms/ions coordinated to the organic ligands to form one, two or three dimensional structures. In the present disclosure, the framework also refers to the coordination polymer porous compound. [0033] The term “ID”, “2D”, “3D” refers to one -dimensional, two-dimensional and three dimensional structures of frameworks respectively.

[0034] The term “ coordination polymer porous material” refers to the framework compounds as defined above with 1D/2D/3D structures. In the present disclosure, the coordination porous polymer material is the framework I as disclosed herein. The terms “framework”, “framework compound”, “compound of framework”, “coordination polymer porous material of framework” can be used interchangeably. [0035] The term “adsorbent” refer to a compound that can adsorb other substances onto its surface. In the present disclosure, the term adsorbent refers to the framework compound (host) that adsorb other organic compounds (guest). The pores of the framework compound adsorb the guest compounds and is referred as physisorption. [0036] The term “purification” refers to extraction of a particular component from a mixture of components. In particular in the present disclosure purification of hydrocarbons represent the extraction of individual component present in the hydrocarbon input stream. In specific the purification of hydrocarbon refers to preferential and selective extraction of a hydrocarbon over other (i.e.) m-xylene over p-xylene, p-xylene over o-xylene and so on.

[0037] The term “C8 isomers” refer to hydrocarbons containing xylene isomers and ethyl benzene, in particular it refers to a mixture of m-xylene, p-xylene, o-xylene and ethyl benzene. In the present disclosure, the term C8 isomers can be interchangeably used with “C8 aromatic isomers”.

[0038] The term “hydrocarbon input feed stream” refers to a mixture of hydrocarbon that are subjected to purification/separation. The hydrocarbon input feed steam will contain two or more hydrocarbons selected from o-xylene, m-xylene, p- xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m-dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol. The hydrocarbons also refer to organic compounds that are aliphatic or aromatic may be saturated or unsaturated, or a mixture of all of these.

[0039] The term “complex of framework II” refers to a metal complex of framework II, which comprises zinc with ligands LI, L2 and a guest molecule X. When a hydrocarbon input feed stream is contacted with framework I, the hydrocarbon in the hydrocarbon input feed stream complexes with framework I to form framework II. In the present disclosure, the framework I acts as an adsorbent and the hydrocarbons act as a guest, thus forms a complex of framework II. The framework I selectively forms a complex of framework II with the hydrocarbons in the hydrocarbon input feed stream. The selective adsorption aids in the process of purification hydrocarbon input feed stream in the present disclosure.

[0040] The term “guest molecules” refer to hydrocarbons which gets incorporated in the coordination polymer porous material. In the present disclosure, the guest molecules complexes with framework I to form framework II comprising the guest molecule or ‘X’. The guest molecules of the present disclosure include but not limited to o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m-dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol and so on. [0041] Halogens include fluorine, chlorine, bromine and iodine. The term

“halobenzene” refers to benzene substituted with one halogen. Halobenzene includes fluorobenzene, chlorobenzene, bromobenzene and iodobenzene. Dihalobenzene (DHB) refers to benzene substituted with two halogens. Dihalobenzene can be ortho- dihalobenzene, meta-dihalobenzene or p-dihalobenzene. Dihalobenzene includes 1,2- difluorobenzene, 1,3-difluorobenzene, 1 ,4-difluorobenzene, 1,2-dichlorobenzene, 1,3- dichlorobenzene, 1,4-dichlorobenzene, 1 ,2-dibromobenzene, 1,3-dibromobenzene, 1 ,4-dibromobenzene, 1 ,2-diiodobenzene, 1,3-diiodobenzene, and 1 ,4-diiodobenzene. [0042] The term “purified stream” refers to a hydrocarbon containing stream purified or separated from the hydrocarbon input feed stream. For example, in a hydrocarbon input feed stream comprising ethyl benzene and styrene, the styrene complexes with framework I to form framework II and with enhanced purity of ethyl benzene.

[0043] The term “aromatic feed stream” refers to a mixture aromatic compounds that requires purification or separation into different aromatic compounds. In the present disclosure, the aromatic feed stream refers to a mixture comprising m-xylene and a mixture of o-xylene, p-xylene, and ethylbenzene. [0044] The term “output stream” refers to a mixture of aromatic compounds purified from the aromatic feed stream. In the present disclosure, the aromatic feed stream is contacted with framework I to form the output stream and a complex of framework II.

[0045] The term “mixed feed stream” refers to a mixture of organic compounds comprising aliphatic and aromatic compounds. For example, the mixed feed stream refers to a mixture comprising cyclohexane, o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, and benzene.

[0046] The term “selectivity” refers to the adsorption of the compound of framework I towards the hydrocarbon input feed stream. The framework I selectively able to adsorb a hydrocarbon from the hydrocarbon input feed stream. The selectivity ranges up to 100% for specific hydrocarbons. For example, in the present disclosure, the framework I exhibits 100% selectivity towards adsorption of m-xylene. Thus, the selectivity aids in the process of purification of the hydrocarbon and further to recover the selectively adsorbed hydrocarbons. [0047] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.

[0048] Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a temperature range of 100 °C to 140°C should be interpreted to include not only the explicitly recited limits of about 100 °C to 140 °C, but also to include sub-ranges, such as 100 °C to 135 °C, 105 °C to 140 °C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 100.5 °C, 120.0 °C and 134.9 °C, for example.

[0049] The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally equivalent products, compositions, and methods are clearly within the scope of the disclosure, as described herein.

[0050] From the above, it can be understood that there is a need for obtaining a process for purifying the hydrocarbons. Separation of industrially important solvents having similar chemical and physical properties has been one of the basic challenges faced by industries. The present disclosure in this regard provides a process for the purification of the hydrocarbon stream containing volatile organic compounds using a metal organic framework or coordination polymer porous framework. The significant aspect of a coordination polymer porous framework material is the design of molecular building block which directs the formation of targeted chemical and physical properties for various applications. The framework compound disclosed in the present disclosure can selectively adsorb specific isomers/compound from the mixture and this preferential selectivity was due to its shape, aromaticity and planarity. The present invention discloses a 3D porous supramolecular framework with aromatic-philic adaptive coordination spaces which shows selective uptake of the hydrocarbons. The porous supramolecular framework formed by the non-covalent interaction between ID coordination polymers molded by continuous linkage of 2,6- naphthalenedicarboxylate, o-phenanthroline and Zn(II) addresses the purification challenges of the industrially imperative hydrocarbon solvents. The porous coordination polymer exhibits a dynamic framework structure to host the hydrocarbon selectively. Further, the framework structure reveals structural flexibility which allows crystal formation inclusive of the guest molecules. [0051] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II.

[0052] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃]

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II{[ZnLiL₂]X), and the X is selected from m-xylene, styrene, p-xylene, o-xylene, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m-dihalobenzene, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole or quinoline. [0053] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream to obtain a purified stream and a complex of framework II, wherein the hydrocarbon input feed stream comprises at least two molecules selected from o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m- dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol and m-cresol. [0054] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream comprising o-xylene, m-xylene, or p-xylene to form a complex of framework II with m-xylene. [0055] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream comprising ethylbenzene and styrene to form a complex of framework II with styrene. [0056] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream comprising cyclohexane and benzene to form a complex of framework II with benzene. [0057] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises halobenzene, o-dihalobenzene, p- dihalobenzene and m-dihalobenzene. [0058] In another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises chlorobenzene, o-dichlorobenzene, p- dichlorobenzene and m- dichlorobenzene. In yet another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises fluorobenzene, o-difluorobenzene, p-difluorobenzene and m-difluorobenzene. In one another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises bromobenzene, o-dibromobenzene, p- dibromobenzene and m-dibromobenzene. In second another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises iodobenzene, bromobenzene, o-dibromobenzene, and p-dibromobenzene. In further another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises iodobenzene, bromobenzene, chlorobenzene, and fluorobenzene.

[0059] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the framework I selectively forms the complex of framework II with halobenzene, wherein the halobenzene is fluorobenzene, chlorobenzene, bromobenzene and iodobenzene. In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream comprising halobenzene, o- dihalobenzene, p-dihalobenzene and m-dihalobenzene to form a complex of framework II with halobenzene. [0060] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the hydrocarbon input feed stream comprises phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole and quinoline. In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I; b) contacting the framework I with a hydrocarbon input feed stream comprising o-cresol, p-cresol, m-cresol to form a complex of framework II with m-cresol.

[0061] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprises at least two molecules selected from o-xylene, m-xylene, p-xylene or ethyl benzene and the framework I has selectivity in order m-xylene>p-xylene>o- xylene>ethyl benzene.

[0062] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃]

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprising ethylbenzene and styrene and the framework I has selectivity in order styrene >ethylbenzene.

[0063] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprising cyclohexane and benzene, and the framework I has selectivity in order benzene>cyclohexane.

[0064] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃]

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprising fluorobenzene, o-difluorobenzene, m-difluorobenzene and p- difluorobenzene, and the framework I has selectivity in order of fluorobenzene > o- difluorobenzene > m-difluorobenzene > p-difluorobenzene.

[0065] In another embodiment of the present disclosure there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the framework I has selectivity in order of p-difluorobenzene > o-difluorobenzene; p- difluorobenzene > m-difluorobenzene; or p-difluorobenzene >fluorobenzene. [0066] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, wherein Li is o- phenanthroline, L2 is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprising chlorobenzene, o-dichlorobenzene, m-dichlorobenzene and p- dichlorobenzene, and the framework I has selectivity in order of chlorobenzene > p- dichlorobenzene > m-dichlorobenzene > o-dichlorobenzene. [0067] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, wherein Li is o- phenanthroline, L2 is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the hydrocarbon input feed stream comprising fluorobenzene, chlorobenzene, bromobenzene and iodobenzene, and the compound of framework I has selectivity in order of chlorobenzene > bromobenzene > iodobenzene > fluorobenzene. This selectivity has been considered by batch reaction where the affinity of equimolar concentration of isomer is used and the selectivity is further analyzed by SCXRD and NMR.

[0068] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, wherein obtaining the coordination polymer porous material of framework I comprises the steps of: a) contacting 2,6- naphthalenedicarboxylic acid and o-phenanthroline in the presence of a solvent to obtain a first solution; and b) contacting the first solution with at least one zinc precursor to obtain the framework I and wherein the 2,6-naphthalenedicarboxylic acid to the o-phenanthroline to the at least one zinc precursor mole ratio is 1:1:1. [0069] In an embodiment of the present disclosure, there is provided a process for obtaining the coordination polymer porous material of framework I, wherein said process comprises a) contacting 2,6-naphthalenedicarboxylic acid and o- phenanthroline in the presence of a solvent to obtain a first solution; and b) contacting the first solution with at least one zinc precursor to obtain the framework I, and the contacting 2, 6-naphthalenedicarboxylic acid and o-phenanthroline is carried out at a temperature in the range of 20 - 30 °C for a period of 3 - 10 minutes in the presence of dimethyl formamide as the solvent.

[0070] In an embodiment of the present disclosure, there is provided a process for obtaining the coordination polymer porous material of framework I as disclosed herein, wherein the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 5 - 15 minutes and then heated to a temperature in the range of 100 - 140 °C for a period in the range of 30 - 50 hours. In another embodiment of the present disclosure, there is provided a process for obtaining the framework I as disclosed herein, wherein the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 7 - 12 minutes and then heated to a temperature in the range of 110 - 130 °C for a period in the range of 32 - 45 hours. In yet another embodiment of the present disclosure, there is provided a process for obtaining the framework I as disclosed herein, wherein the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 9 - 11 minutes and then heated to a temperature in the range of 115 - 125 °C for a period in the range of 34 - 40 hours. In one another embodiment of the present disclosure, there is provided a process for obtaining the framework I as disclosed herein, wherein the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 10 minutes and then heated to a temperature of 120 °C for a period of 36 hours. [0071] In an embodiment of the present disclosure, there is provided a process for obtaining the coordination polymer porous material of framework I, wherein said process comprises a) contacting 2,6-naphthalenedicarboxylic acid and o- phenanthroline in the presence of the solvent to obtain a first solution; and b) contacting the first solution with at least one zinc precursor to obtain the framework I, wherein the contacting 2, 6-naphthalenedicarboxylic acid and o-phenanthroline is carried out at a temperature in the range of 20 - 30 °C for a period of 3 - 10 minutes and the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 5 - 15 minutes and then heated to a temperature in the range of 100 - 140 °C for a period in the range of 30 - 50 hours and the 2,6-naphthalenedicarboxylic acid to the o-phenanthroline to the at least one zinc precursor mole ratio is 1:1:1.

[0072] In an embodiment of the present disclosure, there is provided a process for obtaining the coordination polymer porous material of framework I, wherein said process comprises a) contacting 2,6-naphthalenedicarboxylic acid and o- phenanthroline in the presence of a solvent to obtain a first solution; and b) contacting the first solution with at least one zinc precursor to obtain the coordination polymer porous material of framework I, wherein the zinc precursor is zinc nitrate and the solvent is dimethyl formamide. [0073] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, Ls is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein obtaining a coordination polymer porous material of framework I comprises the steps of: i) contacting 2,6- naphthalenedicarboxylic acid and o-phenanthroline at a temperature in the range of 20 - 30 °C for a period of 3 - 10 minutes in the presence of dimethyl form amide to obtain a first solution; and ii) contacting the first solution with zinc nitrate under ultrasonic agitation for a period of 5 - 15 minutes and then heated to a temperature in the range of 100 - 140 °C for a period in the range of 30 - 50 hours to obtain the coordination polymer porous material of framework I; and the 2,6- naphthalenedicarboxylic acid to the o-phenanthroline to zinc nitrate is in the mole ratio of 1 : 1 : 1.

[0074] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the compound of framework I with a hydrocarbon input feed stream to form a purified stream and a complex of framework II, wherein the process is a batch reaction and wherein in the batch reaction is carried out by contacting the framework I with a hydrocarbon input feed stream at a temperature in the range of 25-35 °C for a period in the range of 30 - 50 hours. In another embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, wherein in the batch reaction is carried out by contacting the framework I with a hydrocarbon input feed stream at a temperature in the range of 25-35°C for a period in the range of 35 - 49 hours.

[0075] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃] Framework I wherein Li is o-phenanthroline, L2 is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the process is a batch reaction carried out by contacting the framework I with a hydrocarbon input feed stream at a temperature in the range of 25-35 °C for a period in the range of 30 - 50 hours under stirring in the range of 200 - 500 rpm.

[0076] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the compound of framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the process is a batch reaction is carried out by contacting the coordination polymer porous material of framework I with a hydrocarbon input feed stream comprising at least two molecules selected from o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m-dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p- cresol, or m-cresol at temperature in the range of 25-35 °C for a period in the range of 30 - 50 hours under stirring in the range of 200 - 500 rpm.

[0077] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the process is a flow through reaction.

[0078] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, wherein the process is a flow through reaction and wherein the framework I is packed into a column and contacting the framework I with a hydrocarbon input feed stream is carried out with residence time in the range of 100 - 150 minutes.

[0079] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, wherein the process is a flow through reaction and wherein the framework I is packed into a column and contacting the framework I with a hydrocarbon input feed stream is carried out with residence time in the range of 100 - 150 minutes and the column had a length of 4cm and a diameter of 0.5 cm.

[0080] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II, wherein the process is a flow through reaction; the framework I is packed into a column and contacting the framework I with a hydrocarbon input feed stream is carried out with residence time in the range of 100 - 150 minutes and wherein the column had a length of 4cm and a diameter of 0.5 cm.

[0081] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, {[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L3 is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream to form a complex of framework II { [ZnLiL₂]X], wherein the process is a flow through reaction and the framework I is packed into a column and contacting the compound of framework I with a hydrocarbon input feed stream comprising at least two molecules selected from o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m- dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, or m-cresol is carried out with residence time in the range of 100 - 150 minutes.

[0082] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with the hydrocarbon input feed stream to form a complex of framework II

{[ZnLiL₂]X]

Framework II wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and X is selected from m-xylene, styrene, p-xylene, o-xylene, benzene, halobenzene, o- dihalobenzene, p-dihalobenzene, m-dihalobenzene, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole or quinoline.

[0083] In an embodiment of the present disclosure, there is provided a process for purification of a hydrocarbon input feed stream as disclosed herein, wherein the X is recovered from the framework II by heating the framework II to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa.

[0084] In an embodiment of the present disclosure, there is provided a process for obtaining a complex having framework II {[ZnLiL₂]X}

Framework II wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and X is selected from m-xylene, styrene, p-xylene, o-xylene, benzene, halobenzene, dihalobenzene, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole or quinoline wherein said process comprising a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with a hydrocarbon input feed stream comprising at least two molecules selected from o-xylene, m-xylene, p- xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p-dihalobenzene, m-dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, or m-cresol to form a complex of framework II { [ZnLiL₂]X .

[0085] In an embodiment of the present disclosure there is provided a process for purification of an aromatic feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃] Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with an aromatic feed stream to obtain an output stream and a m-xylene-rich complex, wherein the aromatic feed stream comprises m-xylene and a mixture of o-xylene, p-xylene, and ethylbenzene, and the process of purification provides 100 % selectivity for m-xylene.

[0086] In an embodiment of the present disclosure there is provided a process for purification of an aromatic feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with an aromatic feed stream to obtain an output stream and a m-xylene-rich complex, wherein the aromatic feed stream comprises m-xylene and a mixture of o-xylene, p-xylene, and ethylbenzene, and the process of purification provides 100 % selectivity for m-xylene, wherein the m-xylene is recovered from the complex by heating the complex to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa. [0087] In an embodiment of the present disclosure there is provided a process for separation of aliphatic compound from a mixed feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃]

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and L₃ is absent or dimethylformamide; b) contacting the framework I with a mixed feed stream to obtain an aliphatic-rich stream and an aromatic -rich complex, the mixed feed stream comprises a mixture of one aromatic and one aliphatic compound, and the process of purification provides 100 % selectivity for m-xylene. [0088] In an embodiment of the present disclosure there is provided a process for separation of aliphatic compound from a mixed feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃] Framework I, wherein Li is o-phenanthroline, L2 is 2,6-naphthalenedicarboxylate, and L3 is absent or dimethylformamide; b) contacting the framework I with a mixed feed stream to obtain an aliphatic-rich stream and an aromatic-rich complex, wherein the mixed feed stream comprises a mixture of one aromatic compound selected from the group consisting o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, benzene and cyclohexane, and the process provides 100 % selectivity for m-xylene.

[0089] In an embodiment of the present disclosure there is provided a process for separation of aliphatic compound from a mixed feed stream, said process comprising: a)obtaining a coordination polymer porous material of framework I,

{[ZnLiL ]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and L3 is absent or dimethylformamide; b) contacting the framework I with a mixed feed stream to obtain an aliphatic-rich stream and an aromatic-rich complex, wherein the mixed feed stream comprises a mixture of one aromatic and one aliphatic compound, and the process of purification provides 100 % selectivity for m-xylene, the aromatic compound is selected from the group consisting o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, and benzene and the aliphatic compound is cyclohexane and the aromatic compound is recovered from the complex by heating the complex of framework II by heating the framework II to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa.

[0090] Although the subject matter has been described in considerable detail with reference to certain preferred embodiments thereof, other embodiments are possible. EXAMPLES

[0091] The disclosure will now be illustrated with working examples, which is intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods, devices, and materials are described herein. It is to be understood that this disclosure is not limited to particular methods, and experimental conditions described, as such methods and conditions may apply.

[0092] The present disclosure provides a flexible, dynamic porous framework containing zinc metal coordinated with the organic ligands 2,6- naphthalenedicarboxylate and o-phenanthroline. The framework has a 3D supramolecular structure with specific pore volumes. This feature of the framework along with its aromaticity was advantageous in the adherence of the organic molecules into its cavity which facilitated the purification of the hydrocarbons by selective adsorption. The hydrocarbons of the present disclosure are xylene isomers (o-xylene, p-xylene, m-xylene), styrene, ethyl benzene, benzene and cyclohexane. The coordination polymer porous framework showed selective adsorption over m- xylene in a mixture of xylene isomers, styrene over a mixture of styrene and ethyl benzene and benzene over mixture of cyclohexane and benzene. A convenient process for the purification involved contacting the hydrocarbon mixture with the coordination polymer porous framework under moderate conditions. The process of the present disclosure can be industrially scaled as well.

Example 1

Synthesis of coordination polymer porous Framework I{[ZnLiL2]L3}

[0093] The process of purification of the hydrocarbon input feed stream was carried out using the coordination polymer porous framework I {[ZnLiL2]L3 , wherein Li is o-phenanthroline (o-phen), L2 is 2,6-naphthalenedicarboxylate(ndc), L3 is absent or dimethylformamide (DMF). In the present disclosure, the framework compound l{[Zn(ndc)(o-phen)]-DMF)} and framework compound la [Zn(ndc)(o-phen)] was synthesized according to the methodology provided herein. Ligand solution (First solution) was obtained by dissolving 2,6-naphthalenedicarboxylic acid (0.022 g, 0.1 mmol) and o-phenanthroline (0.020 g, 0.1 mmol) in 5 mL of dimethylformamide (DMF) at a temperature in the range of 20 - 30 °C for a period of 3 - 10 minutes. 0.030 g (0.1 mmol) of Zn(N0₃)₂-6FL0 was added to the ligand solution, ultra- sonicated for a period of 10 minutes and then transferred to the sealed glass vial. This sealed glass vial was kept in an oven at 120 °C for 36 hours. Crystals of framework compound 1 were isolated and washed with fresh DMF and was subjected to powder X-ray diffraction measurement to check the phase purity. Framework compound la ([Zn(ndc)(o-phen)]) was prepared by heating the framework compound 1 at 160°C for 12 hours under reduced pressure of 1 xlO ¹ Pa. Figure 1(a) depicts the framework compound 1 wherein supramolecular pores in framework compound 1 occupied by DMF and figure 1(b) illustrates supramolecular pocket between o-phenanthroline rings from neighboring ID polymers. Example 2

Process of purification of hydrocarbon input stream

[0094] The process for purification of the hydrocarbon input stream was performed via batch reaction and flow through reaction.

Batch reaction: [0095] In an example of the batch reaction, the framework compound la (~ 100 mg) was immersed in feed stream 1 which 1:1: 1:1 mixture of the C8 isomers (i.e.,) mixture of m-xylene, p-xylene, o-xylene and ethyl benzene (0.1 mL each) in 3 mL hexane and stirred at RT condition. Several fractions of solvent mixtures were collected at different time intervals (5 min, 15 min, 45 min and 2 h) and gas chromatography experiments were carried out to find out the relative ratios of the isomers. This experiment was carried out twice and the reproducibility was validated. Table 1 showed the percentages of each C8 aromatic isomers found at different time intervals from two set of batch experiments performed. Table 1

0096] It can be observed from Table 1 that with increasing time, m-xylene isomer decreased in the mixture; while the other three isomer ratio did not change much. Within 2 hours m-xylene uptake saturated, which indicated very fast diffusion of m- xylene into the supramolecular pores of the framework compound la.

[0097] This experiment indicated that even in presence of other xylene isomers and ethyl benzene, the framework compound la was selective towards m-xylene and thus having 100% selectivity towards m-xylene.

[0098] In the similar manner explained as above, the purification was performed for the other hydrocarbon input feed streams. The other input feed streams were purified and the other feed stream comprised ethyl benzene and styrene and the framework compound la showed selectivity towards styrene. Another feed stream comprised benzene and cyclohexane, and the framework compound la showed selectivity towards styrene. [0099] In a hydrocarbon input feed stream comprising halobenzene, o-dihalobenzene, p-dihalobenzene and m-dihalobenzene, the order of selectivity was found to be chlorobenzene > p-dichlorobenzene > m-dichlorobenzene > o-dichlorobenzene or p- difluorobenzene > o-difluorobenzene or p-difluorobenzene > m-difluorobenzene and chlorobenzene > bromobenzene> iodobenzene> fluorobenzene. In another example, the hydrocarbon input feed stream comprised o-cresol, p-cresol, and m-cresol. The order of selectivity for cresol series was found to be m-cresol> p-cresol; m-cresol> o- cresol.

Batch reaction and analysis using¹H-NMR: [0100] In another process of batch reaction, lOOmg of framework compound la was suspended in 3ml hexane solution with 0.5 ml of hydrocarbon input feed streams. The suspension was stirred for 2 days (i.e.) between 30-50 hours and washed with hexane. 5 mg of the washed powder sample was digested in d⁶-Dimethylsulphoxide (DMSO) with cone. HC1. Further, to understand the selective adsorption of framework compound la over the mixture of input stream ¹ H-NMR study was performed.

[0101] Similar to the process explained above in this example, the batch experiment was performed on the mixtures of o-xylene / p-xylene, o-xylene / m-xylene, m-xylene / p-xylene, o- xylene/ m- xylene/ p-xylene/ ethyl benzene (EB), styrene / ethyl benzene, benzene / cyclohexane, benzene / toluene, benzene / mesitylene and benzene / 1, 2, 4- trimethylbenzene.

[0102] The batch experiment characterized by ¹ H-NMR defined the number of molecules present per unit cell of the corresponding crystal framework. Figure 2 represent the ¹ H -NMR spectrum for p-xylene encapsulated compound la from the mixture of p-xylene and o-xylene. It can be observed that the presence of p-xylene isomer inside the cavity of supramolecular pocket over o-xylene isomer. Figures 3 and 4, validated the exclusive presence of m-xylene and the absence of o-xylene and p-xylene in the framework, respectively. The study also suggested that 0.43 molecules of p-xylene from the mixture of p-xylene and o-xylene, 0.67 molecules of m-xylene from the mixture of m-xylene and o-xylene, and 0.61 molecules of m- xylene from the mixture of m-xylene and p-xylene, respectively, were encapsulated within the framework. Figure 5 depict the ¹ H-NMR spectrum for m-xylene (0.905) encapsulated compound la from the 1 : 1 : 1 : 1 mixture of o- xylene, m- xylene, p- xylene and ethyl benzene (EB)

[0103] Figure 6 depict the ¹ H -NMR spectrum for styrene encapsulated compound la from the mixture of styrene and ethyl benzene (EB). It can be seen that the preferential encapsulation of styrene over ethyl benzene and 0.62 molecules of styrene got encapsulated in the framework in the mixture styrene/ ethyl benzene. Similarly Figures 7, 8, 9 and 10 represented the benzene encapsulation in the framework over the mixtures of benzene/cyclohexane (0.64 benzene), benzene/toluene (0.61 benzene), benzene/mesitylene (0.61 benzene), and benzene/ 1,2,4-trimethylbenzene (0.61 benzene).

[0104] ¹ H-NMR analysis also proved the preferential adsorption of the framework compound la as m-xylene over p-xylene over o-xylene , styrene over ethyl benzene and benzene over toluene, cyclohexane, mesitylene and 1,2,4-trimethylbenzene.

[0105] Figures 11 and 12 illustrated the p-dichlorobenzene encapsulated compound of framework compound la in the mixtures of p-dichlorobenzene/m- dichorobenzene (Figure 11) and p-dichlorobenzene/o-dichorobenzene (Figure 12).

¹ H-NMR analysis further proved the preferential adsorption of the framework compound la with p-dichlorobenzene over m-dichorobenzene and o- dichorobenzene. Flow through reaction:

The process for purification of the hydrocarbon input stream was performed via a flow through reaction. For this process, a fixed bed column of framework compound la using a glass pipe was made. The diameter of the column was 0.5 cm and the length 4 cm. This column was prepared using framework compound la as adsorbent and held by cotton plug from both ends. Column was packed using hexane as eluent and the stability of the packed column was tested by continuous flow of hexane for several minutes. Hydrocarbon input feed stream was added from the top into the column and the fractions were collected at regular intervals. In an actual process of flow through reaction, the hydrocarbon input feed streaml the C8 isomers mixture of m-xylene, p-xylene, o-xylene and ethyl benzene (0.4ml each) in the ratio of 1: 1: 1: 1 in 0.5 mL hexane was added from the top and was held for 45 minutes for complete diffusion. 7 fractions at 5, 10, 15, 20, 25, 30 and 45 min were collected to check the percentages of the various components of the mixture. 25% of m-xylene was added along with other isomers to the hexane. After 20 minutes 3-4% of m-xylene was retained from eluting mixture. This experiment was carried out twice and the reproducibility was validated. Percentages of each C8 isomers found in the eluent at different time intervals from two set of experiments are tabulated as shown in Table 2.

Table 2

[0106] The gas chromatographic experiments clearly showed the absence of m- xylene till 10 min (breakthrough time), after that the fractions collected till 45th minutes, m-xylene concentration increased and finally saturated. Thus, it can be determined that till 10 min the column can separate the m-xylene efficiently from the feed stream (i.e.,) mixtures of C8 isomers.

Similarly, the flow through reaction was used for the purification of the other hydrocarbon input feed streams and was observed that the framework compound la was able to preferentially adsorb styrene over ethyl benzene, and benzene over cyclohexane. Example 3

Characterization of hydrocarbon encapsulated Frameworks [0107] In all the above examples explained, the hydrocarbons get adsorbed on to the pores of the framework compound 1. The hydrocarbons get encapsulated into the framework preferentially one over the other. In order to understand the preferential adsorption and the extent of adsorption and desorption, vapor adsorption isotherms were obtained for the various feed streams.

[0108] Furthermore, to understand the spatial arrangement of the hydrocarbons on to the pores of the framework compounds were studied. For instance, in an input feed stream containing m-xylene and p-xylene, m-xylene formed a complex with the framework compound la. The crystals of the m-xylene encapsulated framework compound lb was subjected to single crystal x-ray diffraction. Similarly, p-xylene, o- xylene, styrene and toluene encapsulated framework compounds lc, Id, le and If respectively, were analyzed using single crystal x-ray diffraction. Vapour Adsorption Profiles

[0109] The selective adsorption of the framework over the mixture of hydrocarbon was further demonstrated by the vapor adsorption isotherms. Figure 13 depicts the vapour adsorption profiles for compound la at 293 K (a) xylene isomers, (b) styrene and ethyl benzene (EB) (c) benzene and cyclohexane, (d) benzene and toluene. The adsorption isotherm of compound la was measured by single component vapour adsorption experiments of the mixture of hydrocarbon at 293 K. Figure 13a showed the stepwise uptakes for all three xylene isomers whereas ethyl benzene did not show any uptake. As the figure 13a showed, after a relative pressure P/Po ~ 0.05, the o- xylene uptake increased sharply and reached to final uptake amount of 74.7 mmol per mol. For p-xylene a steep uptake occurred at P/Po ~ 0.03 and the final uptake amount was 86.3 mmol per mole. In case of m-xylene, the steep was observed at P/Po ~ 0.03 and after this pressure uptake was very steep compared to that of other hydrocarbons and the final uptake amount was 92.4 mmol per mol. In all the isotherms, it can be observed that the adsorbed molecules were not released even at very low pressure, suggested that all the hydrocarbons were strongly encapsulated in the framework compound la. The slightly higher and steeper uptake for m-xylene at low pressure region compared to o-xylene/p-xylene indicated that framework had higher affinity towards m-xylene. The higher uptake capacity of p-xylene over o-xylene in vapour phase explained the higher selectivity of p-xylene from 1:1 mixture of o-xylene/p- xylene in liquid phase. Figure 13b illustrated the adsorption isotherm of styrene and ethyl benzene. For styrene steep uptake occurred at P/Po ~ 0.012 and increased sharply and reached to final uptake amount of 12.2 ml/g whereas there was no uptake observed for ethyl benzene. Adsorption isotherm showed that styrene molecules were not released even at very low pressure suggested its strong encapsulation in the framework. Ethyl benzene cannot be encapsulated in the framework as realized from vapour adsorption isotherm. Figure 13c illustrated the adsorption isotherm of benzene and cyclohexane. A steep uptake occurred at pressure P/Po~ O.lwith benzene and hardly any uptake for cyclohexane. This proved benzene encapsulated strongly in the framework. Figure 13d explained the adsorption isotherm of toluene and benzene. The vapor phase adsorption isotherm with toluene was quite similar to benzene. Toluene uptake at threshold pressure (P/Po~ 0.1) was 27.3 ml was less than benzene (30.2 ml at P/Po~ 0.1). [0110] Figure 14 (a-b) depict the vapor adsorption profiles for compound la at 298 K

(a) fluorobenzene, chlorobenzene, bromobenzene, iodobenzene and (b) fluorobenzene and o-difluorobenzene, m-difluorobenzene, p-difluorobenzene (1,2-DFB 1,3-DFB, 1,4-DFB). Figure 14a shows the halobenzene vapor adsorption isotherm of framework I. The halobenzene got adsorbed on to the pores of the framework compound and encapsulated into the framework preferentially one over the other. In order to understand the preferential adsorption and the extent of adsorption and desorption vapor adsorption isotherms were obtained for the various feed streams and the framework I exhibited the selectivity in the order of fluorobenzene>chlorobenzene>bromobenzene>iodobenzene. From Figure 14b, it can be clearly understood that the compound of the framework I has the selectivity in the order fluorobenzene>o-difluorobenzene> m-difluorobenzene> p-difluorobenzene. [0111] Thus, it can be inferred from the vapour adsorption isotherms that the preferential adsorption of m-xylene over p-xylene over o-xylene. Further in a mixture of styrene and ethyl benzene, styrene was favored over ethyl benzene. Benzene gets adsorbed to the framework preferentially over toluene and cyclohexane. Halobenzene is preferentially adsorbed over the dihalobenzene. This preferential adsorption of the framework was found to be essential and crucial in the separation and purification of the mixture of hydrocarbon.

Single X-ray diffraction measurement

[0112] The hydrocarbon encapsulated framework compounds of lb, lc, Id, le and If obtained from the above examples were subjected to Single X-ray diffraction measurement. Table 3 shows the single X-ray diffraction data for the obtained lb, lc, Id, le and If.

Table3:

[0113] It can be observed from the Table 3 that the compounds lb, lc, Id, le and If crystallized in different space group. Figure 15 represent the orientation of the methyl groups of ortho, meta and para-xylene isomers in compounds (a) lb, (b) lc and (c) Id with xylene guests colored in pink, green and yellow, respectively and Figure 16 illustrated the spatial position of the styrene and toluene in compounds (a) le, and (b) If, respectively.

[0114] The single crystal X-ray diffraction revealed the position of the xylene isomers in the supramolecular pocket. Compound lb, the ortho xylene encapsulated framework crystallized in orthorhombic Pbca space group and the asymmetric unit contains one Zn²⁺, one ndc, one o-phen and one guest o-xylene. The structure (Figure 2a) resembled compound 1, only dissimilarity was instead of DMF molecule o- Xylene was sandwiched between the o-phen aromatic rings. The other two frameworks with meta and para isomers (lc and Id, respectively) crystallized in orthorhombic Pc and P2i/c space group, respectively (Figure 15b, 15c). The styrene encapsulated framework (le) crystallized in monoclinic P2i/c space group. It can be observed that the p· · p distances are almost same between xylene isomers and o-phen (3.649 (o-Xylene), 3.568 (m-Xylene) and 3.679 A (p-Xylene)), the methyl group directions were different. Also, it was observed from figure 16(a) that styrene was sandwiched between the two o-phen ligands by replacing the DMF guest molecule and the ID chains were stacked in such a fashion that two o-phen rings from neighbouring ID chains leave an optimal spacing (7.82 A) which was occupied by DMF molecules, although the p· · p distance between aromatic ring of styrene and o- phen was 3.92 A. Similarly, the toluene encapsulated framework compound If crystallized in monoclinic P2i/c space group (Figure 16b).

[0115] Tables 4 to 7 illustrate the single crystal XRD of the crystals of the framework la crystallized with respective guest molecules such as fluorobenzene, o- difluorobenzene(l,2-DFB), m- difluorobenzene(l,3-DFB), p-difluorobenzene(l,4- DFB), chlorobenzene, o-dichlorobenzene, m- dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, p- dibromobenzene, iodobenzene, phenol, m- cresol, carbazole and quinoline, in different space groups of the supramolecular pocket of the compound. Table 4:

Table 5:

Table 6

Table 7:

[0116] The study on single crystal XRD of the crystals of these framework compounds enabled to identify the spatial arrangement of these molecules within the framework and the structure revealed the flexibility of the framework, the binding sites, orientation of these X molecules (guest molecules) inside the supramolecular pocket of the framework and thus substantiated the preferential adsorption.

Example 4

Separation / Recovery of the hydrocarbon from the Framework: [0117] In all the above examples explained, the adsorbed hydrocarbon compound was recovered from the framework compound by heating the framework compound to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa. For example, the recovery of m-xylene from the m-xylene encapsulated framework compound (lb) was done by heating the compound lb to a temperature of 170 °C under a pressure of 10 ¹ Pa for 18-20 hours. Similarly, the separation of the adsorbed p-xylene, o-xylene, styrene and toluene from the framework compounds lc, Id, le and If respectively was attained, by heating the corresponding framework compounds to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa. Advantages of the present disclosure

The present disclosure provides a process for purification of hydrocarbons using the flexible porous coordination polymer compound of framework I. The Framework I compound is a dynamic porous coordination porous polymer which is capable of selectively adsorb the hydrocarbon from a mixture of hydrocarbons. The framework I selectively adsorbs m-xylene over the xylene isomers and the C8 isomers. Additionally, the porous framework was efficient in preferential uptake of p-xylene over o-xylene, styrene over ethyl benzene, benzene over cyclohexane and halobenzene over dihalobenzene. The process provides 100% selectivity in the adsorption of m-xylene. The present disclosure also provides a process for purification of hydrocarbon stream comprising phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole and quinoline. Vapor adsorption profile and batch, flow through experiments substantiated the preferential adsorption of a specific hydrocarbon over the other hydrocarbons in the mixture. Single X-ray crystallography is used to determine the binding sites of the framework compounds with the adsorbed guest molecules. The present disclosure also provides a process to recover the guest molecules from the framework which enhances the purification process. The process of the present disclosure aids in the separation and purification of all the industrially important hydrocarbons. The volatile hydrocarbon mixtures having similar properties is efficiently purified using the process the explained herein. The process explained herein, is energy efficient, economically feasible, reproducible and industrially applicable.

Claims

/ We claim:

1. A process for purification of a hydrocarbon input feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

2. The process as claimed in claim 1, wherein the hydrocarbon input feed stream comprises at least two molecules selected from o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, cyclohexane, benzene, halobenzene, o-dihalobenzene, p- dihalobenzene, m-dihalobenzene, aniline, indole, carbazole, quinoline, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, or m-cresol.

3. The process for purification of a hydrocarbon input feed stream as claimed in claim 1 , wherein the process is a batch reaction and is carried out by contacting the framework I with the hydrocarbon input feed stream at a temperature in the range of 25 - 35 °C for a period in the range of 30 - 50 hours.

4. The process for purification of a hydrocarbon input feed stream as claimed in claim 1, wherein the process is a flow through reaction and is carried out by contacting the framework I packed into a column with the hydrocarbon input feed stream with residence time in the range of 100 - 150 minutes.

5. The process as claimed in any one of the claims 1 to 4, wherein the hydrocarbon input feed stream comprises at least two molecules selected from o-xylene, m- xylene, or p-xylene and the framework I selectively forms the complex of framework II with m-xylene.

6. The process as claimed in any one of the claims 1 to 4, wherein the hydrocarbon input feed stream comprises ethylbenzene and styrene and the framework I selectively forms the complex of framework II with styrene.

7. The process as claimed in any one of the claims 1 to 4, wherein the hydrocarbon input feed stream comprises cyclohexane and benzene and the framework I selectively forms the complex of framework II with benzene.

8. The process as claimed in any one of the claims 1 to 4, wherein the hydrocarbon input feed stream comprises halobenzene, o-dihalobenzene, p-dihalobenzene and m-dihalobenzene and the framework I selectively forms the complex of framework II with halobenzene.

9. The process as claimed in any one of the claims 1 to 4, wherein the hydrocarbon input feed stream comprises phenol, catechol, hydroquinone, resorcinol, o- cresol, p-cresol, m-cresol, carbazole and quinoline.

10. The process as claimed in claim 1, wherein obtaining the coordination polymer porous material of framework I comprises the steps of: a) contacting 2,6-naphthalenedicarboxylic acid and o-phenanthroline in the presence of a solvent to obtain a first solution; and b) contacting the first solution with at least one zinc precursor to obtain the coordination polymer porous material of framework I, wherein the 2,6-naphthalenedicarboxylic acid to the o-phenanthroline to the at least one zinc precursor mole ratio is 1:1:1.

11. The process as claimed in claim 10, wherein the contacting 2, 6- naphthalenedicarboxylic acid and o-phenanthroline is carried out at a temperature in the range of 20 - 30 °C for a period of 3 - 10 minutes.

12. The process as claimed in claim 10, wherein the contacting the first solution with at least one zinc precursor is carried out under ultrasonic agitation for a period of 5 - 15 minutes and then heated to a temperature in the range of 100 - 140 °C for a period in the range of 30 - 50 hours.

13. The process for purification of a hydrocarbon input feed stream as claimed in claim 1 , wherein the complex of framework II is

{[ZnLiL₂]X}

Framework II, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and X is selected from m-xylene, styrene, p-xylene, o-xylene, benzene, halobenzene, o- dihalobenzene, p-dihalobenzene, m-dihalobenzene, phenol, catechol, hydroquinone, resorcinol, o-cresol, p-cresol, m-cresol, carbazole or quinoline .

14. The process as claimed in claim 13, wherein the X is recovered from the framework II by heating the framework II to a temperature in the range of 150 -

180 °C under a pressure in the range of 10 ¹ - 10² Pa.

15. A complex of framework II obtained by the process as claimed in claim 1.

16. A process for purification of an aromatic feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I, {[ZnLiL₂]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, L₃ is absent or dimethylformamide; b) contacting the framework I with an aromatic feed stream to obtain an output stream and a complex of framework II, wherein the aromatic feed stream comprises m-xylene and a mixture of o-xylene, p-xylene, and ethylbenzene, and the process of purification provides 100 % selectivity for m-xylene.

17. The process as claimed in claim 16, wherein the m-xylene is recovered from the framework II by heating the framework II to a temperature in the range of 150 -

180 °C under a pressure in the range of 10 ¹ - 10² Pa.

18. A process for separation of aliphatic compound from a mixed feed stream, said process comprising: a) obtaining a coordination polymer porous material of framework I,

{[ZnLiL₂]L₃}

Framework I, wherein Li is o-phenanthroline, L₂ is 2,6-naphthalenedicarboxylate, and L₃ is absent or dimethylformamide; b) contacting the framework I with a mixed feed stream to obtain an aliphatic - rich stream and an aromatic-rich complex of framework II, wherein the mixed feed stream comprises a mixture of one aromatic and one aliphatic compound, and the process of purification provides 100 % selectivity for m-xylene.

19. The process as claimed in claim 18, wherein the aromatic compound is selected from the group consisting o-xylene, m-xylene, p-xylene, ethylbenzene, styrene, and benzene; and the aliphatic compound is cyclohexane.

20. The process for separation of aliphatic compound from a mixed feed stream as claimed in claim 18, wherein the aromatic compound is recovered from the framework II by heating the framework II to a temperature in the range of 150 - 180 °C under a pressure in the range of 10 ¹ - 10² Pa.