MOFs method used for deep removing of dibenzothiophene sulfides in automobile diesel oil

A dibenzothiophene and sulfide technology, applied in chemical instruments and methods, copper organic compounds, zinc organic compounds, etc., can solve the problems of Cu-BTC pore blockage and poor mass transfer performance, and achieve enhanced adsorption and mass transfer The effects of rate, pore structure order, and large adsorption capacity

Active Publication Date: 2016-06-08
SINOPEC YANGZI PETROCHEM +1
View PDF4 Cites 13 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

South Korea SungHwaJhung [NazmulAbedinKhan, SungHwaJhung. Adsorptive removal of benzothiophene using porous copper-benzonetricarboxylate loaded with phosphotungsticacid [J]. Fuel Processing Technology, 2012, 100: 49-54] added PWA to the aqueous solution of Cu-BTC to modify Cu-benzothiophene-BTC. When the initial sulfur capacity of benzothiophene is 1000ppm, the equilibrium sulfur capacity of modified Cu-BTC to benzothiophene is 35.58mgS / g ads , which is 1.27 times the adsorption sulfur capacity of Cu-BTC to benzothiophene, but the mass transfer performance of Cu-BTC after modification is poor; South Korea LeviT. 2011,103:261-265] will Mo (CO 3 ) 6 The adsorption of dibenzothiophene on MOF-5 is studied. When the initial sulfur capacity of dibenzothiophene is 1000ppm, the adsorption breakthrough sulfur capacity of MOF-5 loaded with Mo for dibenzothiophene is 14.21mgS / g ads , while the adsorption breakthrough sulfur capacity of MOF-5 for dibenzothiophene is only 11.10mgS / g ads , the adsorption sulfur capacity of modified MOF-5 to dibenzothiophene is 1.28 times that of MOF-5, and the Cu-BTC channel is prone to be blocked during the modification process; it can be seen that the modified metal organic framework can Improve the adsorption sulfur capacity of sulfide, but the modified adsorbents in the above literature are all tested for raw materials with a sulfur content of 1000ppm, and have not been studied for samples with low sulfur content (about 50ppm, which mainly affects the adsorption driving force)
At the same time, there are still problems in mass transfer of modified MOFs materials

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • MOFs method used for deep removing of dibenzothiophene sulfides in automobile diesel oil
  • MOFs method used for deep removing of dibenzothiophene sulfides in automobile diesel oil

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Cr(NO 3 ) 3 9H 2 O. Terephthalic acid, hydrofluoric acid and water are stirred at a molar ratio of 1:1:1:280 for 30 minutes and then coated on a copper plate with a thickness of 1 mm. The copper plate is placed in a stainless steel adsorption column and heated at 250 ° C Reacted for 12 hours, when the initial sulfur concentration was 350ppm, the saturated sulfur capacity of the modified organic framework p-dibenzothiophene in Case 1 was 150.08mg-DBT / g ads , the saturated sulfur capacity of metal-organic framework p-dibenzothiophene before modification is 96.2mg-DBT / g ads .

Embodiment 2

[0025] 0.22mmol of Cu(NO 3 ) 2 2.5H 2 O and 0.076mmol of 3,3,5,5-biphenyltetracarboxylic acid were dissolved in N,N-dimethylformamide / ethanol / water (volume ratio 3:2:2), at 30°C Stir for 45 minutes, and then apply it on an aluminum plate with a thickness of 1.5 mm. Keep the reaction temperature at 50° C. for 48 hours to synthesize a three-dimensional metal-organic framework by hydrothermal synthesis. The metal-organic framework and unit cell structure synthesized in Case 2 are as follows figure 1 shown. The adsorption sulfur capacity of the modified metal-organic framework for 4-methyldibenzothiophene is 8.9 mg / gads, which is 210% of the adsorption sulfur capacity of the unmodified metal-organic framework.

Embodiment 3

[0027] Zn(NO 3 ) 2 ·6H 2 O and 4,4,4-tris(N,N-bis(4-carboxyphenyl)-amino)triphenylamine dissolved in N,N-dimethylacetamide and water, Zn(NO 3 ) 2 ·6H 2 O, 4,4,4-tris(N,N-bis(4-carboxyphenyl)-amino)triphenylamine, N,N-dimethylacetamide and water in a molar ratio of 1:20:10: 10. Mix evenly. After stirring, apply it on an iron plate with a thickness of 0.5 mm. Under nitrogen atmosphere, heat up to 220°C and react for 24 hours to obtain a three-dimensional network topology. The unit cell structure of the synthesized MOFs is as follows: figure 2 shown. In Case 3, the adsorption capacity of 4,6-dimethyldibenzothiophene in diesel reached 20.0mg / g ads , has almost no adsorption capacity for alkanes and aromatics.

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention discloses a MOFs method used for deep removing of dibenzothiophene sulfides in automobile diesel oil, and belongs to the field of application of novel porous adsorption materials in chemical engineering. The MOFs method comprises following steps: an organic ligand and a metal salt are dissolved in deionized water, a solvent is added, and a metal plate is coated with a prepared reaction liquid until the thickness of an obtained coating layer ranges from 0.1 to 2mm; the metal plate is delivered into an adsorption column, reaction is carried out for 8 to 24h at 30 to 220 DEG C; diesel oil is added via a bottom end, and a modified doublemetal organic framework synthesized in the metal adsorption column is used for absorption removal of sulfides. The MOFs method possesses relatively large adsorption capacity and excellent selectivity; reaction can be carried out at normal temperature under normal pressure; energy consumption is reduced; and adsorbent desulphurization efficiency is increased.

Description

technical field [0001] The invention belongs to the application of novel porous adsorption materials in the field of chemical industry, and in particular relates to a method for deeply removing MOFs of dibenzothiophene sulfides from vehicle diesel oil. Background technique [0002] The principle of adsorption desulfurization technology is to use an adsorbent with selective adsorption capacity to directly separate dibenzothiophene sulfides in diesel oil, so as to realize desulfurization of diesel oil, without the participation of hydrogen, at low temperature and normal pressure, with mild operating conditions . The adsorption methods of dibenzothiophene sulfides in diesel can be divided into physical adsorption and chemical adsorption. Chemisorption methods include π-complex adsorption mechanism (based on the formation of π-complex bond between adsorbate and adsorbent) and S-M coordination adsorption mechanism (based on the force formed between metal and sulfide). In adsorp...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): B01J20/22C10G25/00C07F3/08C07F1/08C07F3/06C07F15/02
Inventor 崔群贺春尧王海燕汤磊卞杨燕姚虎卿
Owner SINOPEC YANGZI PETROCHEM
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products