CN106622150A - C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof - Google Patents

C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof Download PDF

Info

Publication number
CN106622150A
CN106622150A CN201710105025.1A CN201710105025A CN106622150A CN 106622150 A CN106622150 A CN 106622150A CN 201710105025 A CN201710105025 A CN 201710105025A CN 106622150 A CN106622150 A CN 106622150A
Authority
CN
China
Prior art keywords
ted
mtpa
ethane
preparation
preferential adsorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710105025.1A
Other languages
Chinese (zh)
Inventor
李忠
梁菀纹
夏启斌
周欣
肖静
李映伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201710105025.1A priority Critical patent/CN106622150A/en
Publication of CN106622150A publication Critical patent/CN106622150A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons

Abstract

The invention discloses a C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and a preparation method thereof. The preparation method comprises the steps of (1) reactant preparation: putting NiCl2*6H2O, 2-methyl-1,4-phthalic acid and triethylene diamine into a reaction kettle, adding N,N-dimethyl formamide, dropwise adding acetonitrile and performing ultrasonic treatment to obtain a uniformly mixed reaction mixture; and (2) material synthesis: performing reaction on the reaction mixture in the reaction kettle, performing centrifugal treatment, and performing purification, drying and vacuum activation on the obtained green solid to obtain the C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially. The C2H3N@Ni(2-MTPA)(TED)0.5 material prepared by the method has the characteristic of adsorbing ethane preferentially and has high adsorption capacity on ethane and ethylene.

Description

The C of Preferential adsorption ethane2H3N@Ni(2-MTPA)(TED)0.5Material and preparation method thereof
Technical field
The present invention relates to the preparing technical field of the MOFs materials of Preferential adsorption ethane, and in particular to a kind of Preferential adsorption second The C of alkane2H3N@Ni(2-MTPA)(TED)0.5Material and preparation method thereof.
Background technology
Ethene is one of the most important product of petrochemical industry and important raw materials for production, in petrochemical industry, is with ethene A series of derivative compounds obtained by main production raw material occupy more than the 75% of whole industry product, people's daily life In the plastics, the terylene that most often touch etc. chemical products production, all be unable to do without ethene, it also referred to as " petrochemical industry it It is female ".
The main path that industrially obtain high-purity ethylene is mostly come from the alkene and alkane separation in cracking gas Out.It is industrial at present to separate with similar structure and physical property because ethene and ethane are two carbon hydrocarbon compounds Ethene and ethane typically separated using high pressure (7-28bar), low temperature (183-258K) rectifying column (Tao R, Patel M, Blok K.Olefins from conventional and heavy feedstocks:Energy use in steam cracking and alternative processes.Energy.2006；31(4):425-451.).Will be in such harshness Separation condition, will expend substantial amounts of energy, and this causes the running cost of ethylene/ethane mixed gas separation to occupy 75-85%'s Production cost of ethylene.For this purpose, people are being devoted to exploring new more energy efficient, ethene/second that operating condition is more gentle always Alkane separation method.The method reported over nearly 10 years mainly has reversible chemical complexometry, membrane separation process, absorption method.And absorption method because Gentle with operating condition, cost is relatively low, it is considered to be the most new method of the Olefin/Paraffin Separation of prospects for commercial application. In adsorption method of separation, adsorbent is that it is crucial, and its performance will determine the efficiency and energy consumption of this separation process.Report in recent years Can be applicable to C2H4/C2H6Detached adsorbent mainly has molecular sieve, activated carbon and metal-organic framework materials (MOFs) etc.. Way commonplace at present is by the way that Cu (I) and Ag (I) are supported on the carrier of high-ratio surface, by π key complexings Ethene in Preferential adsorption ethylene-ethane gaseous mixture, realizes the separation of ethylene-ethane.For example, Joel P et al. are by AgNO3Load In SiO2On, under the conditions of 70 DEG C and 1atm, AgNO3/SiO20.91mmol/g is reached to the adsorbance of ethene, to ethene/second Alkane adsorptive selectivity is 4.5 (Joel P., Ralph T.Y.New sorbents for olefin/paraffin separations by adsorption viaπ-complexation:synthesis and effects of substrates.Chemical Engineering Science,2000,55:2607-2616.).Li etc. has synthesized Ag+Function Porous aromatic skeleton material after change, this material reaches 4.1mmol/g to the adsorption capacity of ethene, while selective reach 125 (Li B,Zhang Y,Krishna R,Yao K,Han Y,Wu Z,et al.Introduction of pi- complexation into porous aromatic framework for highly selective adsorption of ethylene over ethane.J Am Chem Soc.2014；136(24):8654-8660.).Although these π complexings Adsorbent has the adsorptive selectivity of the characteristic of ethylene adsorption and high ethylene/ethane, but using the π key networks of Preferential adsorption ethene Closing adsorbent has obvious deficiency：First, π key is a kind of weak chemical bond, therefore compared to physisorption, ethene will be from π keys Being desorbed on the adsorbent of effect needs more power consumptions；Second, cracking gas is the mixed gas rich in ethene, for example, is being split The ratio of middle ethylene/ethane of venting one's spleen is up to 9：1, if carrying out adsorbing separation ethene and ethane using π keys adsorbent, it is meant that at this To adsorb the ethene of high-load in gaseous mixture in individual separation process, this must produce following two problems：(1) more absorption are needed Agent and higher volume of bed go ethylene adsorption；(2) highly purified ethene can only be obtained in desorption process, this must increase additionally Desorption flow process, and this desorption process need to consume more energy consumptions (because π key Absorptive complex waves belong to weak chemisorbed, absorption Force ratio is stronger).
To avoid problem above, this is accomplished by a kind of high-performance adsorbent with Preferential adsorption ethane of research and development, because this Planting adsorbent will make separation process become simple, and it only can be obtained by highly purified ethene in adsorption process absorption ethane, And because ethane is poor component, therefore adsorbent amount is relatively fewer, while needed for desorption process (ethane desorption) Energy consumption relatively low (due to there is no π key Absorptive complex waves).Therefore high-performance adsorbent of the research and development with Preferential adsorption ethane into For the problem of a great challenge.
In recent years, the report such as Bergh etc. and Gucuyener ZIF-7 realizes Preferential adsorption ethane by " cell breath ", and Under the conditions of 100kPa, 25 DEG C, ZIF-7 is about 2mmol/g (adsorption capacity is less than normal) (van den Bergh to ethane adsorbance J.,Gucuyener C.,Pidko E.A.,et al.Understanding the anomalous alkane selectivity of ZIF-7in the separation of light alkane/alkene mixtures[J] .Chemistry,2011,17(32):8832-8840.)(Canan Guyener J.v.d.B.Ethane/Ethene Separation Turned on Its Head:Selective Ethane Adsorption on the Metal- Organic Framework ZIF-7through a Gate-Opening Mechanism[J].2010,132:17704- 17706.).Pires and Pillai etc. reports that IRMOF-8 has the characteristic of Preferential adsorption ethane, and in 100kPa, 25 DEG C of bars Under part, the ethane adsorption capacity of IRMOF-8 is 4.0mmol/g, but the selectivity factor of ethylene/ethane less than 2 (Pires J, Pinto ML,Saini VK.Ethane selective IRMOF-8 and its significance in ethane- ethylene separation by adsorption.ACS applied materials&interfaces.2014；6 (15):12093-12099.)(Pillai RS,Pinto ML,Pires J,Jorge M,Gomes JR.Understanding Gas adsorption selectivity in IRMOF-8using molecular simulation.ACS applied materials&interfaces.2015；7(1):624-637.).Recently, Liang etc. has synthesized a kind of pair of part MOF material Ni(BDC)(TED)0.5, the adsorbance of ethane of the material under the conditions of 100kPa, 298K is up to 5.0mmol/g, ethylene absorption amount For 3.4mmol/g (Liang W., Xu F., Zhou X., et al.Ethane selective adsorbent Ni (bdc) (ted)0.5with high uptake and its significance in adsorption separation of ethane and ethylene[J].Chemical Engineering Science,2016,148:275-281.).Although this A little MOFs adsorbents have the feature of Preferential adsorption ethane, but, separation selectivity still relatively low to ethylene-ethane adsorption capacity is not Height, for these problems, this project by invention one kind can not only Preferential adsorption ethane, while there is higher absorption to ethane and ethylene The new MOFs sorbing materials C of capacity2H3N@Ni(2-MTPA)(TED)0.5Preparation method.
The content of the invention
It is an object of the invention to provide one kind is than existing Ni (BDC) (TED)0.5Inhale with more excellent ethane, ethene The new MOFs sorbing materials C of attached performance2H3N@Ni(2-MTPA)(TED)0.5And preparation method thereof.The MOFs sorbing materials C2H3N@Ni(2-MTPA)(TED)0.5All there is very high-adsorption-capacity to ethane and ethene, and there is Preferential adsorption to ethane.
The object of the invention is achieved through the following technical solutions.
The C of Preferential adsorption ethane2H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, comprises the steps：
(1) reactant is prepared：By NiCl2·6H2O, 2- methyl isophthalic acid, 4 phthalic acids (2-MTPA) and triethylene diamine (TED) it is placed in reactor, adds DMF (DMF), then acetonitrile (C2H3N) is added dropwise, it is ultrasonically treated, mixed Close uniform reactant mixture；
(2) synthesis of material：Reactant mixture is reacted in a kettle., and reaction terminates rear centrifugal treating, obtains green Color solid；The green solid for obtaining is purified, is dried, vacuum activating, obtain the C of the Preferential adsorption ethane2H3N@Ni (2-MTPA)(TED)0.5Material.
Further, in step (1), the NiCl2·6H2O, 2- methyl isophthalic acid, 4 phthalic acids, triethylene diamine, N, N- The mass ratio of dimethylformamide and acetonitrile is 1:0.6:0.3:140:0.05～1:0.7:0.4:280:0.3.
Further, in step (1), the ultrasonically treated time is 5～20min.
Further, in step (2), the reaction is 18～36h of reaction at 100～130 DEG C.
Further, in step (2), the rotating speed of the centrifugal treating is 7000～8000r/min, the time of centrifugal treating For 2～4min.
Further, in step (2), the purifying is to soak 48～72h at room temperature using DMF, And the N,N-dimethylformamide more renewed per 12h.
Further, in step (2), the drying is in 120～150 DEG C of 4～8h of drying.
Further, in step (2), the vacuum activating be under vacuum 120～150 DEG C of heat-activateds 8～ 16h。
The C of Preferential adsorption ethane obtained in preparation method by described in any of the above-described2H3N@Ni(2-MTPA)(TED)0.5 Material.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) C prepared by the present invention2H3N@Ni(2-MTPA)(TED)0.5Adsorbent, with existing Ni (BDC) (TED)0.5Inhale Attached dose is compared, and with the feature for becoming apparent from Preferential adsorption ethane, and higher adsorption capacity is respectively provided with to ethane and ethene, potential The application prospect of good adsorbing separation ethane and ethylene；
(2) preparation method process operation of the invention is simple, easily realizes, reproducible.
Description of the drawings
Fig. 1 is C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The N of sorbing material2Adsorption isotherm line chart (77K)；
Fig. 2 is C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The XRD diffraction patterns of sorbing material；
Fig. 3 a are 1#C prepared by embodiment 12H3N@Ni(2-MTPA)(TED)0.5Absorption of the sorbing material to ethane and ethene Isollaothermic chart (298K)；
Fig. 3 b are 2#C prepared by embodiment 22H3N@Ni(2-MTPA)(TED)0.5Absorption of the sorbing material to ethane and ethene Isollaothermic chart (298K)；
Fig. 3 c are 3#C prepared by embodiment 32H3N@Ni(2-MTPA)(TED)0.5Absorption of the sorbing material to ethane and ethene Isollaothermic chart (298K)；
Fig. 3 d be Ni (BDC) (TED)0.5To ethane and the adsorption isotherm line chart (298K) of ethene.
Specific embodiment
With reference to the accompanying drawings and detailed description the invention will be further described, and the present invention is not limited to this.
Embodiment 1
(1) NiCl is weighed2·6H2O(n1=0.214g), 2- methyl isophthalic acids, 4 phthalic acid (n2=0.130g), triethylene two Amine (n3=0.066g) in reactor, add DMF (n5=30g), acetonitrile (n is then added dropwise4= 0.012g), ultrasonically treated 20min, the reactant mixture being uniformly mixed, wherein the consumption mass ratio of various materials is n1: n2:n3:n4:n5=1:0.61:0.31:0.056:140；
(2) reactor equipped with reaction-ure mixture is put in 120 DEG C of baking ovens, after reaction 24h, with 7000r/min's Rotating speed centrifugal treating 4min, obtains greenish solid product；
(3) greenish solid product is carried out into immersion 48h using DMF, the DMF more renewed per 12h is purified；Will purifying Solid material afterwards is placed in 120 DEG C and is dried 8h, then 150 DEG C of activation 12h of vacuum, obtains C2H3N@Ni(2-MTPA)(TED)0.5Absorption Agent, is designated as 1#C2H3N@Ni(2-MTPA)(TED)0.5。
Embodiment 2
(1) NiCl is weighed2·6H2O(n1=0.214g), 2- methyl isophthalic acids, 4 phthalic acid (n2=0.130g), triethylene two Amine (n3=0.066g) in reactor, add DMF (n5=30g), acetonitrile (n is then added dropwise4= 0.024g), ultrasonically treated 10min, the reactant mixture being uniformly mixed, wherein the consumption mass ratio of various materials is n1: n2:n3:n4:n5=1:0.61:0.31:0.112:140；
(2) reactor equipped with reaction-ure mixture is put in 130 DEG C of baking ovens, after reaction 18h, with 8000r/min's Rotating speed centrifugal treating 2min, obtains greenish solid product；
(3) greenish solid product is carried out into immersion 60h using DMF, the DMF more renewed per 12h is purified；Will purifying Solid material afterwards is placed in 130 DEG C and is dried 6h, then 120 DEG C of activation 16h of vacuum, obtains C2H3N@Ni(2-MTPA)(TED)0.5Absorption Agent, is designated as 2#C2H3N@Ni(2-MTPA)(TED)0.5。
Embodiment 3
(1) NiCl is weighed2·6H2O(n1=0.214g), 2- methyl isophthalic acids, 4 phthalic acid (n2=0.130g), triethylene two Amine (n3=0.066g) in reactor, add DMF (n5=30g), acetonitrile (n is then added dropwise4= 0.06g), ultrasonically treated 20min, the reactant mixture being uniformly mixed, wherein the consumption mass ratio of various materials is 1: 0.61:0.31:0.280:140；
(2) reactor equipped with reaction-ure mixture is put in 100 DEG C of baking ovens, after reaction 36h, with 8000r/min's Rotating speed centrifugal treating 3min, obtains greenish solid product；
(3) greenish solid product is carried out into immersion 72h using DMF, the DMF more renewed per 12h is purified；Will purifying Solid material afterwards is placed in 150 DEG C and is dried 4h, then 130 DEG C of activation 8h of vacuum, obtains C2H3N@Ni(2-MTPA)(TED)0.5Absorption Agent, is designated as 3#C2H3N@Ni(2-MTPA)(TED)0.5。
C2H3N@Ni(2-MTPA)(TED)0.5Adsorbent is characterized and performance measurement
C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The architectural feature and ethylene-ethane of sorbing material Absorption property, characterizes and the performance test results are as follows：
(1)C2H3N@Ni(2-MTPA)(TED)0.5The pore structure of adsorbent is characterized
Fig. 1 is C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The N of sorbing material2Adsorption isotherm line chart (77K) C that, as shown in Figure 1, prepared by each embodiment2H3N@Ni(2-MTPA)(TED)0.5The N of sorbing material2Adsorption isotherm is I Type thermoisopleth, as Langmuir thermoisopleths, illustrate C prepared by each embodiment2H3N@Ni(2-MTPA)(TED)0.5Sorbing material It is poromerics.
C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The BET specific surface area and pore structure of sorbing material Parameter is as shown in table 1.
C prepared by 1 embodiment of table 1～32H3N@Ni(2-MTPA)(TED)0.5The specific surface area and pore structure of sorbing material Parameter
As shown in Table 1, the 1#C that prepared by embodiment 12H3N@Ni(2-MTPA)(TED)0.5The BET specific surface area of sorbing material Maximum, has reached 1554m2/ g, pore volume has reached 0.66cm3/g；With C2H3The increase of N content, C2H3N@Ni(2-MTPA) (TED)0.5The specific surface area of sorbing material and pore volume decline；The C that each embodiment is prepared2H3N@Ni(2-MTPA)(TED)0.5 The average pore size of sorbing material is C prepared by each embodiment2H3N@Ni(2-MTPA)(TED)0.5Sorbing material There is good loose structure.
Fig. 2 is C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The XRD diffraction patterns of sorbing material, from figure As can be seen that there is stronger characteristic peak in 2 θ=8.18 °, 9.39 °, 12.49 ° and the positions such as 16.49 °, show C2H3N@Ni (2-MTPA)(TED)0.5Sorbing material has good crystal structure.
(2)C2H3N@Ni(2-MTPA)(TED)0.5Absorption of the adsorbent to ethane and ethylene
Fig. 3 a, Fig. 3 b and Fig. 3 c are respectively the C of the preparation of embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5Sorbing material exists Ethane, ethylene absorption isollaothermic chart under the conditions of 298K, Fig. 3 d be Ni (BDC) (TED)0.5Sorbing material is under the conditions of 298K Ethane, ethylene absorption isollaothermic chart；It can be seen that C prepared by each embodiment2H3N@Ni(2-MTPA)(TED)0.5Absorption The ethane adsorption isotherm of material is above its corresponding ethylene absorption thermoisopleth, shows that these sorbing materials have Preferential adsorption Ethane feature；And adsorption capacity is all higher, wherein the adsorbance of ethane is 5.3～6.4mmol/g, and the adsorbance of ethene is 4.0～4.9mmol/g, is above Ni (BDC) (TED)0.5Sorbing material is to ethane and the adsorbance of ethene.
C prepared by embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5The ethane and ethylene adsorbance of sorbing material, it is and existing Adsorbent Ni (BDC) prepared by technology is (TED)0.5, adsorbent ZIF-7 (document van den Bergh J., Gucuyener C., Pidko E.A.,et al.Understanding the anomalous alkane selectivity of ZIF-7in the separation of light alkane/alkene mixtures[J].Chemistry,2011,17(32):8832- 8840. or document Canan Guyener J.v.d.B.Ethane/Ethene Separation Turned on Its Head: Selective Ethane Adsorption on the Metal-Organic Framework ZIF-7 through a Gate-Opening Mechanism[J].2010,132:17704-17706.), adsorbent ZIF-8 (document U.Bohme, B.Barth,C.Paula,A.Kuhnt,W.Schwieger,A.Mundstock,J.Caro,M.Hartmann,Ethene/ ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27and ZIF-8,Langmuir:the ACS journal Of surfaces and colloids, 29 (2013) 8592-8600.), adsorbent IRMOF-8 (document Pires J, Pinto ML,Saini VK.Ethane selective IRMOF-8and its significance in ethane-ethylene separation by adsorption.ACS applied materials&interfaces.2014；6(15):12093- 12099. or document Pillai RS, Pinto ML, Pires J, Jorge M, Gomes JR.Understanding Gas adsorption selectivity in IRMOF-8using molecular simulation.ACS applied materials&interfaces.2015；7(1):The comparing result of ethane and ethylene adsorbance 624-637.) is as shown in table 2.
C prepared by 2 embodiment of table 1～32H3N@Ni(2-MTPA)(TED)0.5The ethane second of sorbing material and other adsorbents The comparing result of alkene adsorbance
As shown in Table 2, C obtained in embodiment 1～32H3N@Ni(2-MTPA)(TED)0.5Sorbing material is inhaled to ethane, ethene Attached performance is superior to ethane, the ethylene absorption performance of adsorbent prepared by most of prior art；Wherein, 2#C2H3N@Ni(2- MTPA)(TED)0.5Ethane adsorbance under the conditions of 298K, 1bar is 6.4mmol/g, and ethylene absorption amount is 4.9mmol/g, bright Show higher than existing Ni (BDC) (TED)0.5To ethane, the adsorbance (ethane of ethylene gas：5.0mmol/, ethene：3.4mmol/ g).Understand, C prepared by the present invention2H3N@Ni(2-MTPA)(TED)0.5Material is potential fine in terms of adsorbing separation ethene, ethane Application prospect.

Claims (9)

1. the C of Preferential adsorption ethane2H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, it is characterised in that including as follows Step：
（1）Reactant is prepared：By NiCl2•6H2O, 2- methyl isophthalic acid, 4 phthalic acids and triethylene diamine are placed in reactor, are added DMF, then acetonitrile is added dropwise, ultrasonically treated, the reactant mixture being uniformly mixed；
（2）The synthesis of material：Reactant mixture is reacted in a kettle., and reaction terminates rear centrifugal treating, obtains green solid Body；The green solid for obtaining is purified, is dried, vacuum activating, obtain the C of the Preferential adsorption ethane2H3N@Ni(2- MTPA)(TED)0.5Material.
2. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（1）In, the NiCl2•6H2O, 2- methyl isophthalic acid, 4 phthalic acids, triethylene diamine, N, N- dimethyl methyls The mass ratio of acid amides and acetonitrile is 1:0.6:0.3:140:0.05～1:0.7:0.4:280:0.3.
3. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（1）In, the ultrasonically treated time is 5 ~ 20min.
4. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（2）In, the reaction is 18 ~ 36h of reaction at 100 ~ 130 DEG C.
5. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（2）In, the rotating speed of the centrifugal treating is 7000 ~ 8000 r/min, and the time of centrifugal treating is 2 ~ 4 min。
6. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（2）In, the purifying is to soak 48 ~ 72h at room temperature using DMF, and per 12h The N,N-dimethylformamide for more renewing.
7. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（2）In, the drying is in 120 ~ 150 DEG C of h of drying 4 ~ 8.
8. the C of Preferential adsorption ethane according to claim 12H3N@Ni(2-MTPA)(TED)0.5The preparation method of material, Characterized in that, step（2）In, the vacuum activating is 120 ~ 150 DEG C of 8 ~ 16h of heat-activated under vacuum.
9. the C of Preferential adsorption ethane obtained in the preparation method described in any one of claim 1 ~ 82H3N@Ni(2-MTPA) (TED)0.5Material.
CN201710105025.1A 2017-02-25 2017-02-25 C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof Pending CN106622150A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710105025.1A CN106622150A (en) 2017-02-25 2017-02-25 C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710105025.1A CN106622150A (en) 2017-02-25 2017-02-25 C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof

Publications (1)

Publication Number Publication Date
CN106622150A true CN106622150A (en) 2017-05-10

Family

ID=58846760

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710105025.1A Pending CN106622150A (en) 2017-02-25 2017-02-25 C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106622150A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997383A (en) * 2018-07-18 2018-12-14 嘉兴学院 Metal organic framework compound and its preparation method and application
CN114452938A (en) * 2021-12-30 2022-05-10 浙江大学 Alkane preferential adsorption microporous material and preparation method and application thereof
CN114570369A (en) * 2022-01-07 2022-06-03 华南理工大学 MOFs derived nanosheet self-assembly grading double-layer hollow nanomaterial and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1689670A1 (en) * 2003-11-24 2006-08-16 Basf Aktiengesellschaft Method for the controlled storage and release of gases using an electrochemically produced crystalline, porous, organometallic skeleton material
CN101585856A (en) * 2008-05-23 2009-11-25 安徽大学 With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation
CN101816924A (en) * 2010-04-13 2010-09-01 东南大学 Metal organic framework material used for absorbing and separating CO2 and preparation method thereof
CN102617646A (en) * 2012-02-29 2012-08-01 中国科学院宁波材料技术与工程研究所 Preparation method of nanoscale metal organic framework materials
CN103058810A (en) * 2013-01-15 2013-04-24 中国石油大学(北京) Method for separating ethane and ethylene in mixed gas
CN103748064A (en) * 2011-08-17 2014-04-23 株式会社可乐丽 Metal complex and adsorbent material, storage material, and separating material comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1689670A1 (en) * 2003-11-24 2006-08-16 Basf Aktiengesellschaft Method for the controlled storage and release of gases using an electrochemically produced crystalline, porous, organometallic skeleton material
CN101585856A (en) * 2008-05-23 2009-11-25 安徽大学 With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation
CN101816924A (en) * 2010-04-13 2010-09-01 东南大学 Metal organic framework material used for absorbing and separating CO2 and preparation method thereof
CN103748064A (en) * 2011-08-17 2014-04-23 株式会社可乐丽 Metal complex and adsorbent material, storage material, and separating material comprising same
CN102617646A (en) * 2012-02-29 2012-08-01 中国科学院宁波材料技术与工程研究所 Preparation method of nanoscale metal organic framework materials
CN103058810A (en) * 2013-01-15 2013-04-24 中国石油大学(北京) Method for separating ethane and ethylene in mixed gas

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIE YANG ET AL.: ""Methyl modified MOF-5: a water stable hydrogen storage material"", 《CHEMICAL COMMUNICATION》 *
WANWEN LIANG ET AL.: ""Ethane selective adsorbent Ni(bdc)(ted)0.5 with high uptake and its significance in adsorption separation of ethane and ethylene"", 《CHEMICAL ENGINEERING SCIENCE》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997383A (en) * 2018-07-18 2018-12-14 嘉兴学院 Metal organic framework compound and its preparation method and application
CN108997383B (en) * 2018-07-18 2020-12-01 嘉兴学院 Metal organic framework compound and preparation method and application thereof
CN114452938A (en) * 2021-12-30 2022-05-10 浙江大学 Alkane preferential adsorption microporous material and preparation method and application thereof
CN114570369A (en) * 2022-01-07 2022-06-03 华南理工大学 MOFs derived nanosheet self-assembly grading double-layer hollow nanomaterial and preparation method thereof

Similar Documents

Publication Publication Date Title
Chen et al. An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene
Ma et al. CO adsorption on activated carbon-supported Cu-based adsorbent prepared by a facile route
Chang et al. Immobilization of Ag (i) into a metal–organic framework with–SO 3 H sites for highly selective olefin–paraffin separation at room temperature
KR101728809B1 (en) Nanoporous inorganic-organic hybrid materials with nitrogen sorption selectivity and a method for selective separation of nitrogen-containing gas mixtures using the same
Li et al. Advances of metal‐organic frameworks in energy and environmental applications
WO2020156426A1 (en) Method for adsorbing and separating ethylene from ethane on the basis of super-microporous metal organic frame material
EP2868649B1 (en) Metal complex, and absorbent material, storage material and separation material comprising the metal complex
KR102100896B1 (en) Organic-inorganic porous hybrid material containing intramolecular anhydride groups, adsorbent composition comprising the same and usage thereof for the separation of gaseous hydrocarbon mixtures
CN108014752A (en) A kind of separation method for the metal-organic framework material and ethylene-ethane for being used to separate ethane and ethene
WO2021197211A1 (en) Method for separating c8 aromatic hydrocarbon isomer mixture
CN104492375B (en) A kind of adsorbent for reclaiming CO from industrial tail gas and its preparation method and application
He et al. Modification of the pore environment in UiO-type metal-organic framework toward boosting the separation of propane/propylene
CN108704609A (en) Monolayer CuCl/ acticarbon preparation methods for CO adsorbing separations
CN106622150A (en) C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof
CN107442084A (en) A kind of poly-dopamine pitch base composite porous carbon adsorbing material of Preferential adsorption ethane and preparation method and application
Wang et al. Exploiting the pore size and functionalization effects in UiO topology structures for the separation of light hydrocarbons
CN108440235B (en) Method for separating 1, 3-butadiene from four-carbon hydrocarbon mixed gas
Jiang et al. Constructing C2H2 anchoring traps within MOF interpenetration nets as C2H2/CO2 and C2H2/C2H4 bifunctional separator
Yu et al. A Robust Metal‐Organic Framework with Scalable Synthesis and Optimal Adsorption and Desorption for Energy‐Efficient Ethylene Purification
Guo et al. A pillared-layer metal–organic framework for efficient separation of C3H8/C2H6/CH4 in natural gas
WO2020156423A1 (en) Method for separating ethylene from ethane
Zhang et al. A new honeycomb MOF for C 2 H 4 purification and C 3 H 6 enrichment by separating methanol to olefin products
He et al. Ultramicroporous metal–organic framework Qc-5-Cu for highly selective adsorption of CO2 from C2H4 stream
KR20160045223A (en) Method for separating and/or purifying mixtures containing olefins and acetylenes using crystalline nano-porous hybrid adsorbent
Qasem et al. Enhancing CO 2 adsorption capacity and cycling stability of Mg-MOF-74

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170510

RJ01 Rejection of invention patent application after publication