CN104326904A - Preparation method of metal organic framework materials for preferential adsorption of sulfide - Google Patents

Preparation method of metal organic framework materials for preferential adsorption of sulfide Download PDF

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Publication number
CN104326904A
CN104326904A CN201410483633.2A CN201410483633A CN104326904A CN 104326904 A CN104326904 A CN 104326904A CN 201410483633 A CN201410483633 A CN 201410483633A CN 104326904 A CN104326904 A CN 104326904A
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preparation
organic framework
metal organic
sulfide
framework materials
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林立刚
张潮
刘春雨
董美美
魏晨杰
邓盼珊
黄衡
张龙辉
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a preparation method of iron based metal organic frameworks, zinc based metal organic frameworks, copper based metal organic frameworks and chromium metal organic frameworks and application in the selective adsorption of sulfide. The method comprises the following steps: dissolving a metal ion compound and an organic ligand in a solvent, stirring to dissolve completely, heating to obtain a metal organic framework crystal, filtering, and drying to obtain a metal organic framework adsorption material, the metal organic framework adsorption material can be sued for preferential adsorption of sulfide in oil, and the adsorption capacity is greater than 10mgS / g.

Description

A kind of preparation method of the metal-organic framework materials for selective absorption sulphide
Technical field
The present invention relates to a kind of preparation technology of the metal-organic framework materials for selective absorption sulphide, the metallic organic framework sorbent material of preparation can be used for oil product deep desulfuration, belongs to field of chemical engineering.
Background technology
Along with the increase of vehicle guaranteeding organic quantity, the impact of motor vehicle emission pollutant on environment is on the rise, immense pressure is brought to city and regional air quality, according to analysis, the oil product key index relevant to motor vehicle emission comprises sulphur, manganese, benzene, lead, alkene etc., and the sulphur content most importantly in oil product, it almost determines all contaminants level of vehicular emission, no matter be PM2.5, oxynitride or hydrocarbon polymer, carbon monoxide, all can increase along with the increase of sulphur content.China's automobile oil standard still has certain gap compared with abroad, and the gasoline standard that current national most area uses is no more than 150ug/g for sulphur content, and diesel oil sulphur content must not more than 350ug/g; And the oil fuel standard of the developed countries such as America and Europe is for being no more than 10ug/g (Europe V standard).Meanwhile, China's processing high-sulfur crude oil amount just constantly increases, and Chinese Oil Refining Industry faces huge challenge, carry out the research of For Ultra-deep Desulfurization of Fuel Oils technology, develop more efficient process for cleanly preparing, become the task of top priority [Wang Jiming, petroleum and chemical industry is energy-conservation, 2011,4:42 ~ 46].
Hydrogen addition technology is the desulfurization technology of current industrial widespread use, and relative to other technology, hydrogenating desulfurization is comparatively proven technique.Catalytic desulfurhydrogenation technology (HDS) is a kind of sulfur method that conventional refinery enterprise generally adopts, at CATALYST Co-Mo-Al 2o 3or Ni-Mo-Al 2o 3effect under, the organosulfur in oil product can be changed into H by high temperature (300 ~ 350 DEG C) high pressure (5 ~ 10MPa) shortening 2s removes.But the method is when deep desulfuration, can reduce the content of alkene and aromatic hydrocarbon in fuel oil, cause the reduction of octane number of fuel oil, hydrogen consumption increases, and reactor volume increases, and facility investment and process cost sharply increase.Dynamics research shows: by current HDS technology, the massfraction of sulphur in diesel oil is dropped to 15ug/g from 500, and the volume of reactor and the consumption of catalyzer at least will increase by 2 times.Therefore, current HDS technology is difficult to the massfraction of sulphur in oil product to be reduced to below 10ug/g [Cheng Xiaoming, Wang Zhihong, Zhu Lin, refining and chemical industry, 2009,20:1 ~ 4].Therefore in the urgent need to the oil fuel deep desulfuration technology of other low cost.
Adsorption desulfurize is the Desulfurization Technology grown up in recent years, ultimate principle exactly by fuel with sulfide is had to special optionally sorbent material and fully contacts, sulfide or sulphur atom are adsorbed onto on sorbent material and remove, sorbent material uses through regeneration Posterior circle.Adsorption desulfurize have investment and process cost is low, desulfuration efficiency is high, can under mitigation condition production sulphur content in the feature of the low-sulfur oil fuel of below 50ug/g.Therefore, be expected to become the most promising low sulphur fuel oil production technology [Hao Haosheng, Li Ruoyan, Gu Binbin, application chemical industry, 2013,42:156 ~ 160].
Metallic organic framework (MOF) material is a kind of new function material that development in recent years is got up, it is a kind of material with supramolecule microporous network structure utilizing the metal-ligand generation complexing action between organic ligand and metal ion and formed, because it has special topological framework, the internal arrangement of rule and the duct of specific dimensions and shape, specific surface area is large, synthesis is convenient, the advantages such as skeleton scale is variable, therefore in gas adsorption, application prospect is more widely had, also huge application potential is had at the separation field of organic mixture, selective adsorption metal-organic framework materials being used for sulfide there is not yet patent report.
Summary of the invention
For solving the problems of the technologies described above, the object of the invention is to the metallic organic framework preparing different metal ion coordination, it is made not only to possess the pore passage structure of three-dimensional orthogonal, and there is unique string bag structure, be connected with the cavity in main aperture road, and select specific metal ion, can with sulphur atom generation complexing action in representative chalcogenide thiophene molecule, thus improve the desulfurization performance of metallic organic framework, reach the object of deep desulfuration.
For reaching as above object, the present invention from the different metal ion of metallic organic framework and this body structure, prepared different metal ion coordination metallic organic framework and for desulfurization.Adopt analog gasoline (normal heptane/thiophene mixture) to be separate object, with WK-2D Microcoulomb comprehensive analysis instrument, the feed liquid sulphur content before and after absorption is measured.
Technical solution of the present invention is: metal ion inorganic salt and organic ligand are dissolved in solvent, makes solution mix under mechanical stirring, adopts the method for heating to form crystalline material, after filtration, drying and processing, obtains metal-organic framework materials.
Described metal ion inorganic salt are the one of iron trichloride, zinc nitrate, cupric nitrate, chromium nitrate.
Described organic ligand is terephthalic acid and trimesic acid, preferred terephthalic acid.
Described solvent is DMF or DMF and alcohol mixture or water.
In the present invention, both metal ion inorganic salt and organic ligand mol ratio is 1: 1.
The heating high temperature that the present invention takes is 100 DEG C ~ 190 DEG C, chooses differing temps according to different metal inorganic salts.
In the present invention, heat-up time is 8 ~ 10 hours.
In the present invention, the temperature of drying and processing is 85 DEG C.
Microcoulomb comprehensive analysis instrument analysis condition is as follows:
Sample size: 4uL, standard specimen concentration: 500ng/uL, transformation efficiency: 80 ~ 120%,
Bias voltage: 75 ~ 140, magnification: 160, integrating resistor: 0.6
Stable section temperature: 700 DEG C, burning zone temperature: 800 DEG C, vaporization section temperature: 600 DEG C.
Metallic organic framework sweetening material prepared by the present invention has special topological framework, the internal arrangement of rule and the duct of specific dimensions and shape, select metal ion and thiophene molecule in sulphur atom have certain complexing action, adsorption effect and the sweetening power of metallic organic framework can be promoted.
The manufacture method of metal-organic framework materials of the present invention has the features such as process is simple, raw material sources are wide.
Accompanying drawing explanation
Fig. 1 is the microsctructural photograph of the Ferrious material organic backbone that the embodiment of the present invention 1 is synthesized.
Fig. 2 is the microsctructural photograph of the zinc system metallic organic framework of the 2-in-1 one-tenth of the embodiment of the present invention.
Fig. 3 is the microsctructural photograph of the copper system metallic organic framework that the embodiment of the present invention 3 is synthesized.
Fig. 4 is the microsctructural photograph of the chromium system metallic organic framework that the embodiment of the present invention 4 is synthesized.
Embodiment
Below provide specific embodiments of the invention, but the present invention is not by the restriction of embodiment:
Embodiment 1:
The preparation of Ferrious material organic backbone: weigh 1.8528g iron trichloride with meticulous balance, 1.328g terephthalic acid, graduated cylinder measures 40mlN, dinethylformamide, they are all poured in beaker and mixes, after they all dissolve, solution is all poured in the hydrothermal reaction kettle of tetrafluoroethylene inwall.Heat 10 hours in vacuum drying oven at 150 DEG C, use funnel vacuum filtration afterwards, by the vacuum-drying more than 5 hours at 85 DEG C of the filtrate of gained, the yellow crystals of gained is Ferrious material organic backbone.It is basically identical that this material is rectangular bulk and form, and size is even, and its microtexture is shown in Fig. 1.
Implementation result: adopt analog gasoline (normal heptane, thiophene) to be separate object, initial sulphur content is 310ug/g, and service temperature is 25 DEG C, and the loading capacity of obtained Ferrious material organic backbone is 11.2mg S/g.
Embodiment 2:
The preparation of zinc system metallic organic framework: weigh 0.334g terephthalic acid with meticulous balance, 1.2g zinc nitrate, graduated cylinder measures the DMF of 40ml, pours in beaker and stirs with rotor, make it to dissolve rapidly.Measure 2.2ml triethylamine afterwards, with glue head dropper, it is dropwise instilled in beaker slowly, constantly stir simultaneously, then use the hydrogen peroxide that 3 ~ 4 30% got by glue head dropper instead, stir in instillation beaker, obtain white precipitate.Wash with DMF with after funnel vacuum filtration, finally white depositions is put into crucible at 85 DEG C at dry 8 hours of vacuum drying oven.Prepare zinc system metallic organic framework, its microtexture is shown in Fig. 2.
Implementation result: adopt analog gasoline (normal heptane, thiophene) to be separate object, initial sulphur content is 310ug/g, and service temperature is 25 DEG C, and the loading capacity of obtained zinc system metallic organic framework is 12.3mg S/g.
Embodiment 3:
The preparation of copper system metallic organic framework: weigh 3g Trimesic acid with meticulous balance, 6g nitrate trihydrate copper, the N of 30ml is measured respectively with graduated cylinder, dinethylformamide, the ethanol of 30ml, the water of 30ml, then pour in beaker, magnetic agitation 10 minutes, it is made to dissolve completely, then above-mentioned solution is poured into Erlenmeyer flask, be placed on the upper asbestos gauge of pad in loft drier, heat 8 hours at 100 DEG C, solution colour becomes blue-greenish colour gradually by blueness, become blackish green by blue-greenish colour again, now at the bottom of Erlenmeyer flask, adhere to blue layer crystal, this blue colored crystal funnel vacuum filtration is got off.Be poured among crucible by the blue colored crystal of gained, vacuum-drying 10 hours at 85 DEG C, namely gained crystal is copper system metallic organic framework, and the sample shape of synthesis is octahedral structure, and crystalline structure is complete, even particle size, and its microtexture is shown in Fig. 3.
Implementation result: adopt analog gasoline (normal heptane, thiophene) to be separate object, initial sulphur content is 310ug/g, and service temperature is 25 DEG C, and the loading capacity of obtained copper system metallic organic framework is 16.4mg S/g.
Embodiment 4:
The preparation of chromium system metallic organic framework: claim 4g nine water chromium nitrate with meticulous balance, 1.64g terephthalic acid, 0.205g sodium acetate, measures the water of 50ml with graduated cylinder, in beaker, mix and blend makes it all dissolve in 30 minutes, then to pour in hydrothermal reaction kettle 190 DEG C of reactions 10 hours into.After reaction, vacuum filtration obtains crystal settling, after washing, and 85 DEG C of dryings 5 hours in vacuum drying oven, obtain green crystal, be chromium system metallic organic framework, its crystal morphology is regular grain pattern, smooth surface, crystal grain size is even, and its microtexture is shown in Fig. 4.
Implementation result: adopt analog gasoline (normal heptane, thiophene) to be separate object, initial sulphur content is 310ug/g, and service temperature is 25 DEG C, and the loading capacity of obtained copper system metallic organic framework is 10.3mg S/g.

Claims (6)

1. the preparation method for the metal-organic framework materials of selective absorption sulphide, its technical scheme is: be dissolved in solvent by the metal ion inorganic salt of mol ratio 1: 1 and organic ligand, solution is made to mix under mechanical stirring, reacting by heating certain hour forms crystalline material at a certain temperature, after filtration, drying and processing, obtain metal-organic framework materials.
2. preparation method according to claim 1, is characterized in that described metal ion inorganic salt are at least one in iron trichloride, zinc nitrate, cupric nitrate or chromium nitrate.
3. preparation method according to claim 1, is characterized in that described organic ligand is terephthalic acid and trimesic acid, preferred terephthalic acid.
4. preparation method according to claim 1, is characterized in that described solvent is at least one in DMF, DMF and alcohol mixture, water.
5. preparation method according to claim 1, is characterized in that described Heating temperature is 100 DEG C ~ 190 DEG C.
6. preparation method according to claim 1, is characterized in that the described reaction times is 8 ~ 10 hours.
CN201410483633.2A 2014-09-17 2014-09-17 Preparation method of metal organic framework materials for preferential adsorption of sulfide Pending CN104326904A (en)

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Cited By (9)

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CN105418938A (en) * 2015-12-08 2016-03-23 华南理工大学 Hierarchical pore HKUST-1 material, preparation method and appliance
CN105597823A (en) * 2016-01-06 2016-05-25 南昌航空大学 Preparation method of PPy-PANI/TiO2 NTs composite photocatalyst
CN106064101A (en) * 2016-06-20 2016-11-02 广东工业大学 A kind of iron-based MOFs catalysis material and preparation and application thereof
CN106861640A (en) * 2017-04-11 2017-06-20 中国石油大学(华东) The preparation method of organic sulfur compound adsorption desulfurizing agent in a kind of natural gas
CN107179302A (en) * 2017-04-24 2017-09-19 西北师范大学 Applications of the Zn MOFs in 4 nitrophenols are detected
CN108097015A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of amine liquid desulfurization absorbent and its preparation method and application
CN109575306A (en) * 2018-12-20 2019-04-05 华东理工大学 A kind of modified Cu-BTC material and its preparation method and application
CN109627648A (en) * 2018-12-14 2019-04-16 天津工业大学 A kind of light sensitivity perforated membrane and preparation method thereof and a kind of light-operated membrane contactor
CN114920948A (en) * 2022-05-30 2022-08-19 北京科技大学 Preparation method and application of copper metal organic framework material

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418938A (en) * 2015-12-08 2016-03-23 华南理工大学 Hierarchical pore HKUST-1 material, preparation method and appliance
CN105418938B (en) * 2015-12-08 2017-12-01 华南理工大学 A kind of materials of multi-stage porous HKUST 1 and preparation method and application
CN105597823A (en) * 2016-01-06 2016-05-25 南昌航空大学 Preparation method of PPy-PANI/TiO2 NTs composite photocatalyst
CN106064101A (en) * 2016-06-20 2016-11-02 广东工业大学 A kind of iron-based MOFs catalysis material and preparation and application thereof
CN108097015A (en) * 2016-11-25 2018-06-01 中国石油化工股份有限公司 A kind of amine liquid desulfurization absorbent and its preparation method and application
CN108097015B (en) * 2016-11-25 2021-03-05 中国石油化工股份有限公司 Amine liquid desulfurization absorbent, preparation method and application thereof
CN106861640A (en) * 2017-04-11 2017-06-20 中国石油大学(华东) The preparation method of organic sulfur compound adsorption desulfurizing agent in a kind of natural gas
CN107179302A (en) * 2017-04-24 2017-09-19 西北师范大学 Applications of the Zn MOFs in 4 nitrophenols are detected
CN109627648A (en) * 2018-12-14 2019-04-16 天津工业大学 A kind of light sensitivity perforated membrane and preparation method thereof and a kind of light-operated membrane contactor
CN109575306A (en) * 2018-12-20 2019-04-05 华东理工大学 A kind of modified Cu-BTC material and its preparation method and application
CN109575306B (en) * 2018-12-20 2022-03-25 华东理工大学 Modified Cu-BTC material and preparation method and application thereof
CN114920948A (en) * 2022-05-30 2022-08-19 北京科技大学 Preparation method and application of copper metal organic framework material

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Application publication date: 20150204