CN102241405A - Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method - Google Patents
Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method Download PDFInfo
- Publication number
- CN102241405A CN102241405A CN2010101781096A CN201010178109A CN102241405A CN 102241405 A CN102241405 A CN 102241405A CN 2010101781096 A CN2010101781096 A CN 2010101781096A CN 201010178109 A CN201010178109 A CN 201010178109A CN 102241405 A CN102241405 A CN 102241405A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- transition metal
- mesoporous
- aluminoshilicate
- reduced form
- 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
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of molecular sieves, and particularly relates to a reduced mesoporous aluminosilicate molecular sieve, a preparation method and an application thereof, and a diesel oil desulfurization method. The molecular sieve is prepared by the following steps: 1) preparing a mesoporous aluminosilicate molecular sieve; 2) modifying the molecular sieve with transition metals; and 3) reducing the transition-metal-ion-modified mesoporous aluminosilicate molecular sieve with a reduction gas at the reduction temperature of 200-700 DEG C. In the invention, a mesoporous aluminosilicate (MAS) adsorbent is a microporous and mesoporous composite molecular sieve, contains the primary and secondary structural elements of a microporous Y-shaped molecular sieve, not only maintains the high acid density and acid intensity of microporous molecular sieves, but also has larger pore size as well as good thermal stability and hydrothermal stability of mesoporous molecular sieves, thereby further improving the adsorption capacity and adsorption selectivity to sulfides. The optimal adsorption desulfurization effects are acquired through adjusting and controlling the reduction temperature and changing the shape and properties of the multi-valence transition metals on the adsorbent.
Description
Technical field
The present invention relates to the molecular sieve field, particularly, the present invention relates to a kind of reduced form mesoporous aluminoshilicate molecular sieve and preparation method thereof, application, diesel fuel desulfurization method.
Background technology
Sorbent material is sulfocompound such as dibenzothiophene and four or six dimethyl Dibenzothiophene etc. in the hydrorefined diesel oil of adsorbing and removing, the gasoline at normal temperatures and pressures, reach the purpose of ultra-deep desulfurization.
The sorbent material of existing adsorption desulfurize can be metal oxide (USP6,184,176,2001-2-6; USP6,338,794,2002-2-15), molecular sieve (USP5,935,422,1999-8-10; USP5454933,1995-10-3; ), gac (USP6,565,741,2003-5-20) and metal alloy (6,558,533,2003-5-6).On these sorbent materials carrying alkali metal or alkaline-earth metal can improve sorbent material the sulfide adsorption selectivity (USP5,935,422,1999-8-10); The carrying transition metal oxide compound can improve the adsorptive capacity of sulfide, improve sorbent material absorption property (4,085,195,1978-4-18); Carried noble metal ion or oxide compound can improve regenerability (USP5,843,300 of sorbent material; 1998-12-1).But these sorbent materials all are the micro-porous adsorption agent, and its duct is stopped up by macromolecular substance in the diesel oil easily, cause the absorption property loss.
The research that the MCM-41 of mesopore molecular sieve such as modification and SBA-15 carry out adsorption desulfurize also obtains paying attention to.Compare with micro porous molecular sieve, in the hydrogenated diesel oil system, mesopore molecular sieve adsorption desulfurize better performances (Chem Eng Sci, 2008,63:356-365; Energy Fuels, 2007,21,250-255).But mesoporous wall is an amorphous structure, and this can cause mesopore molecular sieve heat and hydrothermal stability poor, and the sorbent material pore passage structure is destroyed easily; Compare with micro porous molecular sieve (as Y zeolite), ion-exchange performance is poor, sorbent material modification poor performance, and surface acid density is lower, and is little to the sulfide saturated extent of adsorption.The main path that improves the sorbent material saturated extent of adsorption is to increase the surface acidity bit density, and it is transition metal modified etc. that concrete grammar has.The method of the modification of transition metal ion mainly is an ion exchange method, comprises gaseous ion exchange process (VPIE), ionic liquid phase exchange process (LPIE) and solid phase ion exchange method (SSIE).Compare with the ionic liquid phase exchange process, gaseous ion exchange process and the ion-exchange of solid phase ion exchange method are more complete, and the adsorptive capacity of sorbent material is bigger.But the ionic liquid phase exchange process but has advantage simple to operate.
Summary of the invention
The purpose of this invention is to provide the reduced form mesoporous aluminoshilicate molecular sieve that a kind of absorption property significantly improves.
A further object of the present invention provides a kind of method for preparing above-mentioned reduced form mesoporous aluminoshilicate molecular sieve.
Another object of the present invention provides the application of above-mentioned reduced form mesoporous aluminoshilicate molecular sieve.
Another object of the present invention provides a kind ofly uses above-mentioned reduced form mesoporous aluminoshilicate molecular sieve to carry out the method for diesel fuel desulfurization.
The present inventor is different from existing research angle, finds can improve the loading capacity and the selectivity of sorbent material with the transition metal modified mesoporous aluminoshilicate molecular sieve of hydrogen reducing.
According to reduced form mesoporous aluminoshilicate molecular sieve of the present invention, wherein, the method preparation of described molecular sieve by may further comprise the steps:
1) preparation mesoporous aluminoshilicate molecular sieve;
2) transition metal modified;
3) reduce the mesoporous aluminoshilicate molecular sieve that above-mentioned transition metal ion-modified crosses with reducing gas, needed temperature when transition metal fully reduces among the hydrogen-TPR result of the mesoporous aluminoshilicate molecular sieve of described transition metal modified mistake, preferably the mesoporous aluminoshilicate molecular sieve of crossing with the above-mentioned transition metal ion-modified of hydrogen reducing.Multivalence attitude metal ion is in different valence states with the reduction temperature difference, and the present inventor finds that after deliberation all fully the adsorption desulfurize effect of reductive transition metal is best.
According to reduced form mesoporous aluminoshilicate molecular sieve of the present invention, sorbent material is transition metal modified, can be ion-exchange techniques, also can be dipping method, also can be that the sorbent material preparation process directly adds transition metal salt.Transition metal salt can be vitriol, nitrate, muriate, acetate or the carbonate of iron, cobalt, nickel, zinc, copper, silver, lanthanum.
According to reduced form mesoporous aluminoshilicate molecular sieve of the present invention, wherein, in step 2) in, described load in the molecular sieve of transition metal ion the content of transition metal be 3～30wt%.
According to reduced form mesoporous aluminoshilicate mesopore molecular sieve of the present invention, wherein, the mesoporous aperture of described mesoporous aluminoshilicate molecular sieve is 2～4nm.
Therefore, the method for preparing reduced form mesoporous aluminoshilicate molecular sieve according to the present invention may further comprise the steps:
1) preparation mesoporous aluminoshilicate molecular sieve;
2) transition metal modified;
3) reduce the mesoporous aluminoshilicate molecular sieve that above-mentioned transition metal ion-modified crosses with reducing gas.
The present invention also provides the application of above-mentioned reduced form mesoporous aluminoshilicate molecular sieve, as adsorb the sulfocompound in the diesel oil as desulfuration adsorbent.
Therefore, diesel fuel desulfurization method according to the present invention comprises the step that sulfur-containing diesel is contacted with above-mentioned reduced form mesoporous aluminoshilicate molecular sieve.Preferably, in sulfur method of the present invention, the sulphur content of diesel oil is 50～500mL/g; The ratio of diesel oil and described reduced form mesoporous aluminoshilicate molecular sieve is 10～60mL/g, and the temperature of diesel oil is room temperature～150 ℃ during absorption.
Mesoporous Si-Al acid of the present invention (MAS) salt sorbent material is a kind of micropore and composite mesoporous molecular sieve, the primary and secondary structural unit that contains the micropore Y zeolite in its mesoporous wall, both keep micropore molecule higher sour density and strength of acid, had the larger aperture of mesopore molecular sieve and good thermostability and hydrothermal stability again.The reduced form sorbent material that the modification by transition metal ion and the processing of hydrogen reducing obtain can further improve loading capacity and the adsorption selectivity of sorbent material to sulfide.By regulation and control to reduction temperature, change form and the character of multivalence attitude transition metal on sorbent material, obtain the suitableeest adsorption desulfurize effect.
Description of drawings
Fig. 1 is the adsorption penetration curve of Ni (II)-MAS and Zn (II)-MAS.
Fig. 2 is the H2-TPR collection of illustrative plates of Ni-MAS.
Fig. 3 is Ni-MAS adsorption desulfurize break-through curve to DBT under different reduction temperatures.
Fig. 4 is that the absorption saturated capacity of Ni (II)-MAS under different adsorption temps measured.
Fig. 5 is the comparison to the adsorption curve of DBT and toluene in the reduction front and back of Ni-MAS sorbent material, Fig. 5 A: reduction; Fig. 5 B:450 ℃ reduction.
Embodiment
The preparation of embodiment 1Ni (II)-MCM-41 and Ni (II)-Y
1, the preparation of mesopore molecular sieve MCM-41: selecting water glass is the silicon source, and sodium aluminate is the aluminium source, prepares in 100mL tetrafluoroethylene reactor.Surfactant concentration CTAB/SiO
2Mol ratio is 0.15, and the Si/Al ratio is 40, regulates pH to 10.0,120 ℃ of crystallization 24 hours.Product deionized water wash drying obtains MCM-41 after 400 ℃ of roastings.
2, transition metal modified mesopore molecular sieve (Ni (II)-MCM-41)
Adopt the method for ion-exchange, above-mentioned mesopore molecular sieve MCM-41 is joined the Ni (NO of 0.5mol/L
3)
2The aqueous solution, stirring at room 24h uses the deionized water wash suction filtration again, drying, 400 ℃ of roastings 4 hours obtain Ni (II)-MCM-41.
3, transition metal modified Y zeolite (Ni (II)-Y)
Adopt the method for ion-exchange, Y zeolite (buying from Qilu Petrochemical company catalyst plant) is joined the Ni (NO of 0.5mol/L
3)
2The aqueous solution, stirring at room 24h uses the deionized water wash suction filtration again, drying, 400 ℃ of roastings 4 hours obtain Ni (II)-Y.
Embodiment 2 preparation reduced form mesoporous aluminoshilicate molecular sieves
1, preparation mesoporous aluminoshilicate molecular sieve
Synthesizing of Y zeolite presoma: with 0.446g NaAlO
2, 1.619g NaOH and 4.0mL H
2The O heated and stirred adds the 7.1mL water glass solution and is stirred to the solution clarification to dissolving, and solution is transferred to room temperature ageing 24h in the plastic containers, obtains the y-type zeolite presoma.
Mesoporous aluminoshilicate MAS's is synthetic: the CTAB heated and stirred of various dose is dissolved in the 50mL water, in CTAB solution, add 12mL ammoniacal liquor, add the aged y-type zeolite precursor solution of 5mL then, regulate pH to 9-10 with 10% sulphuric acid soln, stir in the reactor of packing into behind the 3h crystallization 24h, 48h, 72h in 100 ℃, product obtains MAS through suction filtration, dry roasting, and its aperture is 3nm.
2, transition metal modified mesoporous aluminoshilicate molecular sieve (Ni (II)-MAS and Zn (II)-MAS)
Adopt the method for ion-exchange, above-mentioned mesoporous aluminoshilicate MAS is joined the Ni (NO of 0.5mol/L
3)
2And Zn (NO
3)
2The aqueous solution, stirring at room 24h uses the deionized water wash suction filtration again, and drying gets Ni (II)-MAS and Zn (II)-MAS, and wherein the content Ni of transition metal is 4.2wt%, and Zn is 5.6wt%.Repeatedly ion-exchange can improve the content of appendix metal, and after the exchange of 3 secondary ions, the Ni content among Ni (II)-MAS can bring up to 11.6%.
3, the transition metal modified mesoporous aluminoshilicate molecular sieve of reduction
Above-mentioned transition metal modified mesoporous aluminoshilicate molecular sieve Ni (II)-MAS or Zn (II)-MAS are placed nitrogen protection; be warming up to 450 ℃ of activation 2h; then with feeding hydrogen, high temperature reduction 2h promptly obtains reducing sorbent material Ni (II)-MAS or Zn (II)-MAS.
The desulfurization performance of embodiment 3 differing moleculars sieve carrier relatively
Adopt reduced form Ni (the II)-Y of embodiment 1-2 preparation, Ni (II)-MAS, Ni (II)-MCM-41 sorbent material removes the sulfocompound in the diesel oil, and diesel oil is 30mL/g with the ratio of sorbent material.The performance of diesel oil, as shown in table 1, carry out the comparison of adsorption desulfurize effect for three kinds of diesel oil of different nature (being labeled as A, B, C respectively).Table 1 is the performance of three kinds of hydrogenated diesel oils.
The physico-chemical property of three kinds of hydrogenated diesel oils of table 1
Annotate: nd20 is the refractive index of diesel samples
Result after the desulfurization is as shown in table 2:
Table 2 diesel oil adsorption desulfurizing result, μ g/g (finish ratio: 30mL/g)
Change diesel oil is 10mL/g and 60mL/g with the ratio of sorbent material, uses Ni (the II)-Y of embodiment 1-2 preparation, and Ni (II)-MAS, Ni (II)-MCM-41 sorbent material remove the sulfocompound in the diesel oil (A, B, C), and the result after the desulfurization is shown in table 3,4:
Table 3 diesel oil adsorption desulfurizing result, μ g/g (finish ratio: 10mL/g)
Table 4 diesel oil adsorption desulfurizing result, μ g/g (finish ratio: 60mL/g)
By above table 2-4 as can be seen, adsorptive power size to diesel oil is followed successively by Ni (II)-MAS＞Ni (II)-MCM-41＞Ni (II)-Y, under the identical condition of appendix transition metal, the mesoporous aluminoshilicate sorbent material (MAS) that contains the micro porous molecular sieve structural unit in the hole wall has bigger loading capacity than micro porous molecular sieve (Y zeolite) and mesopore molecular sieve (MCM-41).
Embodiment 4 different metal ionic desulfurization performances relatively
Two kinds of reduced form mesoporous aluminoshilicate sorbent material Ni (II)-MAS or Zn (II)-MAS have been carried out the comparison of adsorption desulfurize effect to the simulated oil system on fixed bed.The reduction temperature of sorbent material is 450 ℃.Simulated oil is the octane solution of 2mmol/LDBT, and adsorption temp is 50 ℃, and flow velocity is 0.2mL/min during absorption.As shown in Figure 1.The modified effect of Ni metal is better than Zn metal, and under the same condition, the saturated extent of adsorption of Ni-MAS sorbent material is bigger than Zn-MAS sorbent material.
Reduced form mesoporous aluminoshilicate Ni (the II)-selection of MAS reduction temperature and the comparison of sweetening effectiveness.According to hydrogen-TPR characterization result of Ni (II)-MAS, as shown in Figure 2, the selective reduction temperature is respectively does not reduce, and 400 ℃ of reduction and 450 ℃ of reduction make the Ni element in the sorbent material be in three kinds of different forms.Compare its adsorption desulfurize effect again, as shown in Figure 3,450 ℃ of sorbent materials that reduction obtains, its sweetening effectiveness is best.And 390 ℃ of sorbent materials that reduction obtains, its absorption property can improve the loading capacity of sorbent material on the contrary not as unreduced sorbent material though the reduction processing be described, and the selection of reduction temperature but is a critical step very, if can not fully reduce, can suppress the sweetening effectiveness of sorbent material on the contrary.
Embodiment 6
The ADSORPTION IN A FIXED BED desulfurization performance of the hydrogenated diesel oil of reduced form mesoporous aluminoshilicate Ni (II)-MAS, hydrogenated diesel oil with 90ppm is a raw material, investigated the influence of adsorption temp at 30,70 and 110 ℃ to desulfurization performance, flow velocity is 0.2mL/min, as shown in Figure 4, the adsorption penetration point of sorbent material is respectively 7,12 and the 18mL/g sorbent material.As can be seen, along with the rising of temperature, sorbent material increases the sulphur loading capacity of diesel oil, and sweetening effectiveness strengthens.
Embodiment 7
Reduced form mesoporous aluminoshilicate Ni (II)-MAS is to the adsorption selectivity measure of merit of DBT.Exist competitive adsorption between aromatic hydroxy compound and the sulfide in the diesel oil, thus can be to influencing the adsorption effect of sorbent material to sulfide.With toluene is model compound, has investigated the adsorption selectivity of reduced form sorbent material Ni (II)-MAS to DBT.Octane solution with 3mmol/LDBT+20mmol/L toluene is raw material, and 450 ℃ of reductive sorbent materials and reductive sorbent material are not contrasted, and adsorption temp is 50 ℃, and flow velocity is 0.2mL/min.As shown in Figure 5, sorbent material is not respectively 8.2mL/g and 7.4mL/g to the saturated extent of adsorption of DBT and toluene when reducing, relatively absorption is than 0.17, and the sorbent material after the reduction is respectively 12.6mL/g and 8.9mL/g to the adsorptive capacity of DBT and toluene, and absorption is than being 0.21 relatively.As can be seen, reduction is handled and can be improved the adsorption selectivity of sorbent material to sulfide.
Claims (10)
1. a reduced form mesoporous aluminoshilicate molecular sieve is characterized in that, the method preparation of described molecular sieve by may further comprise the steps:
1) preparation mesoporous aluminoshilicate molecular sieve;
2) transition metal modified;
3) reduce the mesoporous aluminoshilicate molecular sieve of above-mentioned transition metal modified mistake with reducing gas, reduction temperature is needed temperature when transition metal fully reduces among the hydrogen-TPR result of mesoporous aluminoshilicate molecular sieve of described transition metal modified mistake.
2. reduced form mesoporous aluminoshilicate molecular sieve according to claim 1 is characterized in that, in step 2) in, the content of transition metal is 3～30wt% in the transition metal modified molecular sieve.
3. reduced form mesoporous aluminoshilicate molecular sieve according to claim 1 is characterized in that described transition metal is iron, cobalt, nickel, zinc, copper, lanthanum.
4. reduced form mesoporous aluminoshilicate molecular sieve according to claim 1 is characterized in that the mesoporous aperture of described mesoporous aluminoshilicate molecular sieve is 2～4nm.
5. reduced form mesoporous aluminoshilicate molecular sieve according to claim 1 is characterized in that, in step 3), with the above-mentioned transition metal modified mesoporous aluminoshilicate molecular sieve of hydrogen reducing.
6. method for preparing reduced form mesoporous aluminoshilicate molecular sieve said method comprising the steps of:
1) preparation mesoporous aluminoshilicate molecular sieve;
2) transition metal modified;
3) reduce above-mentioned transition metal modified mesoporous aluminoshilicate molecular sieve with reducing gas, needed temperature when transition metal fully reduces among the hydrogen-TPR result of the mesoporous aluminoshilicate molecular sieve of described transition metal modified mistake.
7. the application of the described reduced form mesoporous aluminoshilicate of claim 1 molecular sieve.
8. the described reduced form mesoporous aluminoshilicate of claim 1 molecular sieve is as the application of desulfuration adsorbent.
9. a diesel fuel desulfurization method is characterized in that, described method comprises the step that the described reduced form mesoporous aluminoshilicate of sulfur-containing diesel and claim 1 molecular sieve is contacted.
10. sulfur method according to claim 9 is characterized in that, the sulphur content of diesel oil is 50～500mL/g; The ratio of diesel oil and described reduced form mesoporous aluminoshilicate molecular sieve is 10～60mL/g, and the temperature of diesel oil is room temperature～150 ℃ during absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101781096A CN102241405A (en) | 2010-05-14 | 2010-05-14 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101781096A CN102241405A (en) | 2010-05-14 | 2010-05-14 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102241405A true CN102241405A (en) | 2011-11-16 |
Family
ID=44959690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101781096A Pending CN102241405A (en) | 2010-05-14 | 2010-05-14 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102241405A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2573838C2 (en) * | 2014-05-08 | 2016-01-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Астраханский государственный технический университет" | Catalyst production method for demerptanisation of hydrocarbon mixtures |
| CN109485060A (en) * | 2017-09-13 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of SBA-16 molecular sieve and the preparation method and application thereof of Nanoscale Iron modification |
| CN115869903A (en) * | 2022-09-26 | 2023-03-31 | 南京工业大学 | Copper-based zeolite molecular sieve hybrid material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980862A (en) * | 2004-04-23 | 2007-06-13 | 麻省理工学院 | Mesostructured zeolitic materials, and methods of making and using the same |
| CN101381280A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院大连化学物理研究所 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
-
2010
- 2010-05-14 CN CN2010101781096A patent/CN102241405A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980862A (en) * | 2004-04-23 | 2007-06-13 | 麻省理工学院 | Mesostructured zeolitic materials, and methods of making and using the same |
| CN101381280A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院大连化学物理研究所 | Application of Ni base supported catalyst in hydrogenolysis process of glycyl alcohol |
Non-Patent Citations (1)
| Title |
|---|
| 唐煌等: "介孔硅铝酸盐吸附剂的柴油吸附脱硫研究", 《中国科学B辑:化学》, vol. 39, no. 2, 31 December 2009 (2009-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2573838C2 (en) * | 2014-05-08 | 2016-01-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Астраханский государственный технический университет" | Catalyst production method for demerptanisation of hydrocarbon mixtures |
| CN109485060A (en) * | 2017-09-13 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of SBA-16 molecular sieve and the preparation method and application thereof of Nanoscale Iron modification |
| CN109485060B (en) * | 2017-09-13 | 2020-12-18 | 中国石油化工股份有限公司 | SBA-16 molecular sieve modified by nano iron and preparation method and application thereof |
| CN115869903A (en) * | 2022-09-26 | 2023-03-31 | 南京工业大学 | Copper-based zeolite molecular sieve hybrid material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tian et al. | Enhanced adsorption desulfurization performance over hierarchically structured zeolite Y | |
| Subhan et al. | Highly dispersive lanthanum oxide fabricated in confined space of SBA-15 for adsorptive desulfurization | |
| CN100548487C (en) | A kind of aromatized eutectic superfine zeolite grain catalyst and its production and application | |
| CN103252211B (en) | Molecular sieve desulfurizer and preparation method thereof | |
| Nuntang et al. | Comparative study on adsorptive removal of thiophenic sulfurs over Y and USY zeolites | |
| CN101481627A (en) | Hydrocarbon oil desulphurization adsorbing agent and use method thereof | |
| CN106102901A (en) | For removing the reproducible of sulphur compound from air-flow | |
| TWI264464B (en) | Process for removal of nitrogen containing contaminants from gas oil feedstreams | |
| Subhan et al. | Highly dispersive Cu species constructed in mesoporous silica derived from ZSM-5 for batch and continuous adsorptive desulfurization of thiophene | |
| Ullah et al. | Cation–anion double hydrolysis derived mesoporous mixed oxides for reactive adsorption desulfurization | |
| Li et al. | Ultra‐deep desulfurization adsorbents for hydrotreated diesel with magnetic mesoporous aluminosilicates | |
| CN103381353B (en) | Preparation method of clay base gasoline desulfurization adsorbent | |
| CN102895948A (en) | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof | |
| Liu et al. | New Cu2O-SiO2 composite aerogel-like desulfurization adsorbents with different molar ratio of Si/Cu based on π-complexation | |
| CN104667861B (en) | A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline | |
| Guo et al. | Synthesis and adsorption desulfurization performance of modified mesoporous silica materials M-MCM-41 (M= Fe, Co, Zn) | |
| Li et al. | Preparation of CuNaY zeolites with microwave irradiation and their application for removing thiophene from model fuel | |
| Huang et al. | Facile synthesis of mesoporous kaolin catalyst carrier and its application in deep oxidative desulfurization | |
| Ahmadian et al. | Sulfur dioxide removal from flue gas by supported CuO nanoparticle adsorbents | |
| CN102241405A (en) | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method | |
| Zhang et al. | Deep desulfurization of model oil by photocatalytic air oxidation and adsorption using Ti (1− x) M x O 2 (M= Zr, Ce) | |
| Zu et al. | Deep removal of thiophene and benzothiophene in low-sulfur fuels over the efficient CeAlSBA-15 adsorbent synthesized by sequential alumination and cerium incorporation | |
| Maghsoudi et al. | Enhanced adsorption desulfurization performance over modified zeolite clinoptilolite for a model fuel in a competitive process | |
| Bi et al. | Titanium dioxide-modified nanosized TS-1 zeolite-supported phosphotungstic acid as a catalyst for deep catalytic oxidative desulfurization of fuel oil | |
| RU2448771C1 (en) | Adsorbent desulphuriser for liquid phases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111116 |