CN101381621A - Use of mesoporous aluminoshilicate - Google Patents
Use of mesoporous aluminoshilicate Download PDFInfo
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- CN101381621A CN101381621A CNA2007101212799A CN200710121279A CN101381621A CN 101381621 A CN101381621 A CN 101381621A CN A2007101212799 A CNA2007101212799 A CN A2007101212799A CN 200710121279 A CN200710121279 A CN 200710121279A CN 101381621 A CN101381621 A CN 101381621A
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Abstract
The invention belongs to the technical field of clean diesel oil production, which particularly relates to application of meso-porous aluminosilicate. The meso-porous aluminosilicate can be used as a deep desulfurization adsorbent of diesel oil. The diesel oil of which the sulfur content is between 50 and 500 ppm is contacted with the desulfurization adsorbent of a meso-porous aluminosilicate material for exchanging with transition metal, wherein the ratio of the diesel oil to the desulfurization adsorbent of the meso-porous aluminosilicate material is between 5 and 50mL/g; and during the adsorption, the temperature of the diesel oil is between the room temperature and 200 DEG C. The desulfurization adsorbent of the meso-porous aluminosilicate material provided by the invention comprises a meso-porous structure and micropore molecular sieve structure units according to the meso-porous ratio; the pore diameter of the adsorbent is larger, and the adsorbent has acidity and large quantity; the adsorption and the desulfurization effects on the diesel oil and petroleum are good; and when the diesel oil of which the sulfur content is between 50 and 500 ppm is contacted with the adsorbent, the sulfur content of the diesel oil can be lowered to 30 ppm, even 0 ppm.
Description
Technical field
The invention belongs to technical field of clean diesel oil production, particularly relate to application of meso-porous aluminosilicate.
Background technology
Using desulfuration adsorbent that oil product is carried out the catalysis adsorption desulfurize is the purpose that reaches deep desulfuration at normal temperatures and pressures with the sulfocompound in adsorbents adsorb diesel oil, the gasoline.Because the catalysis adsorption desulfurize influences the octane value of gasoline and yield hardly and can realize the super low sulfur production of oil product, thereby has caused great attention both domestic and external.The sorbent material that is used for adsorption desulfurize can be that (USP 6,184,176,2001-2-6 for metal oxide; USP 6,338,794,2002-2-15), (USP 5,935,422,1999-8-10 for molecular sieve; USP 5,454,933,1995-10-3), gac (USP 6,565,741,2003-5-20) and metal alloy (USP 6,558,533,2003-5-6).Carrying alkali metal or alkaline-earth metal can improve the sulfide adsorption selectivity of sorbent material (USP 5,935,422,1999-8-10) on these sorbent materials; The carrying transition metal oxide compound can improve the adsorptive capacity of sulfide, and (USP 4,085,195,1978-4-18) to improve the absorption property of sorbent material; Carried noble metal ion or oxide compound can improve sorbent material regenerability (USP5,843,300,1998-12-1).Bibliographical information π complexing adsorbent has good selectivity for adsorption desulfurize.Report Cu (I)/Y sorbent materials such as the Yang of University of Michigan have higher selectivity with respect to aromatic hydrocarbon to organic sulfide.(J.Am.Chem.Soc.2004，126，992.；AIChE?J.2004，50，791.；Science2003，301，79；J.Amer.Chem.Soc.，126，992(2004)；Ind.Eng.Chem.Res.，43，1081(2004).Ind.Eng.Chem.Res.，43，769(2004))。
The diesel desulfurization sorbents of bibliographical information has two kinds: the micropore NaY sorbent material of modification and the mesopore molecular sieve of modification, and as SBA-15, MCM-41 etc.For micro porous molecular sieve, though its acidic site number is less, ion-exchange performance good, microvoid structure is blocked easily, mass-transfer performance is poor, and therefore, the adsorption desulfurize performance is bad in the diesel oil system; Though the mesopore molecular sieve mass-transfer performance is good, its acidic site number is less, and is little to the sulfide saturated extent of adsorption.Wherein adopt in the preparation document of mesoporous aluminoshilicate Y zeolite is ground, join in the surfactant soln, obtain mesoporous-micropore composite material through hydrothermal crystallizing, can cause micro porous molecular sieve crystal grain at the inner skewness of mesoporous material like this, thereby cause mesoporous wall uneven thickness, the unequal problem in aperture (chemical industry journal, 57 (4): 751 (2006)).
Mesoporous aluminoshilicate is the mesoporous material that contains the micro porous molecular sieve structure cell on a kind of hole wall, compare with mesopore molecular sieve, its hole wall is thicker and be crystalline state, its better heat stability and acid density are bigger, can be used for the research and the application of catalytic field, but this mesoporous aluminoshilicate uses as the diesel deep desulfurization sorbent material never.(Chem.Mater.，2002，14:1144-1148；J.Phys.Chem.B，2005，109，12277-12286；J.Am.Chem.Soc.，2001，123:5014-5021)。
Summary of the invention
The purpose of this invention is to provide mesoporous aluminoshilicate and use as the diesel deep desulfurization sorbent material, this desulfuration adsorbent has higher desulfuration efficient than simple micro porous molecular sieve and mesopore molecular sieve.
Mesoporous aluminoshilicate of the present invention can use as the diesel deep desulfurization sorbent material.
The diesel oil that with sulphur content is 50ppm～500ppm contacts with the desulfuration adsorbent of the mesoporous aluminoshilicate material of transition metal exchange, wherein the ratio of the desulfuration adsorbent of diesel oil and mesoporous aluminoshilicate material is 5mL/g～50mL/g, is preferably 15mL/g～30mL/g; The temperature of diesel oil is room temperature～200 ℃ during absorption, the special restriction of pressure nothing when diesel oil contacts with desulfuration adsorbent, can be normal pressure to the pressure that is lower than 0.5MPa, be preferably normal pressure; The reactor that adopts when diesel oil contacts with desulfuration adsorbent can be fixed bed type reactor, stirred-tank reactor, fluidized bed reactor or moving-burden bed reactor.The time that described diesel oil contacts with sorbent material can decide according to reactor, was generally 0.1～3 hour, and fixed-bed reactor, weight hourly space velocity is 5～300 hours
-1
Described mesoporous aluminoshilicate is the mesoporous aluminoshilicate of transition metal exchange.
Described transition metal can be copper, silver, nickel, zinc or any mixture between them, and the content of transition metal is 3～40 weight %, is preferably 10～20 weight %.
The mesoporous aperture of mesoporous aluminoshilicate of the present invention is 2～100nm, wherein on the mesoporous aluminoshilicate hole wall micro porous molecular sieve structure cell is arranged, and this micro porous molecular sieve structure cell can be Y zeolite, L type molecular sieve, beta molecular sieve or type ZSM 5 molecular sieve.
The advantage of the desulfuration adsorbent of mesoporous aluminoshilicate material provided by the invention is that sorbent material contains meso-hole structure and contain the micro porous molecular sieve structural unit on mesoporous boring ratio; The sorbent material aperture is big, acidity is that number is many; Effective to diesel oil, gasoline absorbing desulfurization, be that the diesel oil of 50～500ppm contacts with sorbent material with sulphur content, the sulphur content of diesel oil can be reduced to 30ppm even 0ppm.
Embodiment
Following examples are used to illustrate the present invention, but these embodiment do not limit the present invention in any form.
Embodiment 1. produces the mesoporous aluminoshilicate solid adsorbent
Synthesizing of y-type zeolite presoma: with 0.446kg NaAlO
2, 1.619kg NaOH and 4.012L H
2The O heated and stirred adds the 7.094L water glass solution and is stirred to the solution clarification to dissolving, and solution was transferred in the beaker ageing 24 hours, obtains the y-type zeolite presoma.
1.09kg cetyl trimethylammonium bromide (CTAB) heated and stirred is dissolved in the 1.44L water, in CTAB solution, add 12L ammoniacal liquor, add the aged y-type zeolite precursor solution of 4.5L then, regulate pH to 9～10 with the 10wt% sulphuric acid soln, stirred in 2 hours reactors of packing in 100 ℃ crystallization 48 hours, product obtains mesoporous aluminoshilicate MAS through suction filtration, drying, roasting.
Contrast sorbent material 1 is Cu (I)-Y, and contrast sorbent material 2 is Cu (I)-MCM-41.
Adopt ion-exchange with transition metal ion Cu (I) NaY, MAS and MCM-41 to be carried out modification, the method for ion-exchange is as follows: at the Cu of 0.5mol/L (NO
3)
2Aqueous solution normal temperature exchanges 24 hours down, and the ratio of the aqueous solution and metal-salt is 10mL/g, and then reduction, investigates transition metal Cu modification to the adsorbents adsorb Effect on Performance.
The sweetening power of the mesoporous aluminoshilicate solid adsorbent of preparation in the embodiment 2. test implementation examples 1
Sorbent material among the embodiment 1 of amount shown in following and contrast sorbent material 1 and 2 are encased in the stirred autoclave that diameter is 200ml, add catalytic cracking diesel oil 120ml, the diesel oil sulphur content is 270ppm, the amount of sorbent material is 6g, churning time 1 hour, diesel oil total sulfur adopt WK-2B microcoulomb analyser to analyze: the sulphur content of product is respectively 15ppm (sorbent material of the present invention), 189ppm (sorbent material 1) and 142ppm (sorbent material 2).
Embodiment 3
A certain amount of tetraethyl ammonium hydroxide aqueous solution, silica-gel powder, sodium metaaluminate and sodium hydroxide are mixed according to mass ratio 3:7:2:0.8, drip the bismuth salts solution in the stirring, be made into the crystallization glue, solution was transferred in the beaker ageing 24 hours, obtain the zeolite beta presoma.
1.32kg cetyl trimethylammonium bromide (CTAB) heated and stirred is dissolved in the 1.49L water, in CTAB solution, add 10L ammoniacal liquor, add the aged zeolite beta precursor solution of 4.5L then, regulate pH to 9～10 with the 10wt% sulphuric acid soln, stirred in 2 hours reactors of packing in 100 ℃ crystallization 48 hours, product obtains mesoporous aluminoshilicate MAS-β through suction filtration, drying, roasting.
Use the sulfocompound in this loading type Ni-MAS-β adsorbents adsorb straight-run diesel oil (hydrogenating desulfurization diesel oil).The diesel oil total sulfur adopts WK-2B microcoulomb analyser (Jiangsu Electrical Analysis Instrument Factory) analysis: initial total sulfur content is 293.13mg/L.After the adsorbents adsorb, the sulphur content of diesel oil drops to 39.78mg/L from 293.13mg/L.Sulfur removal rate is 86.43%.
Diesel oil sulphur component distributes and adopts gas-chromatography-atomic emission spectrum (GC-AED) analysis: total sulfur content is 286.455mg/L, is 39.733mg/L through the total sulfur content after the desulfurization, and total decreasing ratio is 86.13%.The forward and backward analytical results of diesel fuel desulfurization is listed in the 2nd, 3 perpendicular hurdles of table 1.
| Sulfide | Sulphur content mg/L before handling | Sulphur content mg/L after the desulfurization of Ni-MAS-β sorbent material |
| C 4C 6H 5C 4H 4S | 16.991 | 1.791 |
| C 5，C 6C 6H 5C 4H 4S | 24.854 | 3.540 |
| DBT | 23.42 | 2.600 |
| C 1DBT or C 6BT | 17.535 | 0.998 |
| 4-CH 3DBT | 28.887 | 2.114 |
| C 1DBT?or?C 6BT | 40.024 | 4.890 |
| 4-C 2H 5DBT | 4.592 | 1.007 |
| 4，6-DMDBT | 18.634 | 1.939 |
| 2，4-DMDBT | 11.814 | 2.136 |
| 2，6-DMDBT | 14.350 | 3.823 |
| 2,8-or 3,8-or 3,7-DMDBT | 12.375 | 2.525 |
| 1，9-DMDBT | 16.490 | 3.759 |
| 2，3-DMDBT | 15.722 | 1.680 |
| C 2DBT | 7.818 | 1.02 |
| 1，2-DMDBT | 9.549 | 0.524 |
| C 3DBT | 4.895 | 0.498 |
| 2，4，6-TMDBT | 6.837 | 1.795 |
| C 3DBT | 5.052 | 1.269 |
| 2，4，8-TMDBT | 6.359 | 1.830 |
| Total sulfur content, mg/L | 286.455 | 39.733 |
Embodiment 4. produces the mesoporous aluminoshilicate solid adsorbent
Synthesizing of y-type zeolite presoma: with 0.446kgNaAlO
2, 1.619kg NaOH and 4.012L H
2The O heated and stirred adds the 7.094L water glass solution and is stirred to the solution clarification to dissolving, and solution was transferred in the beaker ageing 24 hours, obtains the y-type zeolite presoma.
With 1.64kg three block tensio-active agent P123[Poly (ethylene glycol)
20-Poly (propyleneglycol)
20-Poly (ethylene glycol)
20] heated and stirred is dissolved in the 1.42L water, in P123 solution, add 12L ammoniacal liquor, add the aged y-type zeolite precursor solution of 4.5L then, regulate pH to 9～10 with the 10wt% sulphuric acid soln, stirred in 2 hours reactors of packing in 100 ℃ crystallization 24 hours, product obtains mesoporous aluminoshilicate MAS through suction filtration, drying, roasting.
The building-up process of mesoporous molecular sieve SBA-15 is: under the certain temperature condition, with three block tensio-active agent P123[Poly (ethylene glycol)
20-Poly (propylene glycol)
20-Poly (ethyleneglycol)
20] be dissolved in appropriate amount of deionized water, to wherein adding tetraethoxysilance (TEOS), hydrochloric acid (HCl), continue to stir tempestuously certain hour, the teflon-lined reactor crystallization of packing into certain hour, filter, wash and drying, 550 ℃ of calcinings 5 hours, remove template at last, the white powder that obtains is SBA-15.
Contrast sorbent material 3 is Ag-Y, and contrast sorbent material 4 is Ag-SBA-15.
Adopt ion-exchange with transition metal ion Ag NaY, MAS and SBA-15 to be carried out modification, the method for ion-exchange is as follows: at the AgNO of 0.5mol/L
3Aqueous solution normal temperature exchanges 24 hours down, and the ratio of the aqueous solution and metal-salt is 10mL/g, and then reduction, investigates the Transition Metal Ag modification to the adsorbents adsorb Effect on Performance.
It is in 2 centimetres the fixed-bed reactor that adsorbent A g-MAS and contrast sorbent material 3 and contrast sorbent material 4 are encased in diameter, constantly adds diesel oil, and air speed is 1h
-1The diesel oil sulphur content is 270ppm, the amount of sorbent material is 6g, the diesel oil total sulfur adopts WK-2B microcoulomb analyser to analyze: the sulphur content of 1 hour product of adsorption time is 5ppm (sorbent material of the present invention), 89ppm (contrast sorbent material 3) and 62ppm (contrast sorbent material 4), when the reaction times is 1.5 hours in the diesel product sulphur content be 15ppm (sorbent material of the present invention), 127ppm (contrast sorbent material 3) and 92ppm (contrasting sorbent material 3).
Embodiment 5
With the MAS of preparation among the embodiment 1, the method through wet impregnation prepares NiO-MAS.Preparation process is: the NiCl of 10gMAS and 10ml1mol/l
2Solution mixes, and stirs, and places 12 hours, 550 ℃ roastings of 12 hours, 100 ℃ dryings 5 hours in air.The diesel oil thorough mixing of the 189ppm that NiO-MAS sorbent material and the volume of 5g is 40ml obtains the diesel product that sulphur content is 0ppm.
Embodiment 6
With the NaY molecular sieve, the method through wet impregnation prepares NiO-Y.Preparation process is: the NiCl of 10gY and 10ml1mol/l
2Solution mixes, and stirs, and places 12 hours, 550 ℃ roastings of 12 hours, 100 ℃ dryings 5 hours in air.The diesel oil thorough mixing of the 179ppm that NiO-Y sorbent material and the volume of 5g is 50ml obtains the diesel product that sulphur content is 14ppm.
Embodiment 7
With the MAS of preparation among the embodiment 1, the method through the rare earth ion exchange prepares RE-MAS.Preparation process is: the RECl of 10gMAS and 10ml1mol/l
3Solution mixes, and stirs, and places 12 hours, 550 ℃ roastings of 12 hours, 100 ℃ dryings 5 hours in air.The diesel oil thorough mixing of the 179ppm that RE-MAS sorbent material and the volume of 5g is 50ml through about 1 hour, obtains the diesel product that sulphur content is 5ppm.
Claims (10)
1. application of meso-porous aluminosilicate, it is characterized in that: this mesoporous aluminoshilicate can use as the diesel deep desulfurization sorbent material.
2. purposes according to claim 1, it is characterized in that: the diesel oil that with sulphur content is 50ppm～500ppm contacts with the desulfuration adsorbent of mesoporous aluminoshilicate material, wherein the ratio of the desulfuration adsorbent of diesel oil and mesoporous aluminoshilicate material is 5mL/g～50mL/g, and the temperature of diesel oil is room temperature～200 ℃ during absorption.
3. purposes according to claim 2 is characterized in that: the ratio of the desulfuration adsorbent of described diesel oil and mesoporous aluminoshilicate material is 15mL/g～30mL/g.
4. according to claim 1,2 or 3 described purposes, it is characterized in that: the desulfuration adsorbent of described mesoporous aluminoshilicate material can be reduced to 30ppm to 0ppm with the sulphur content of diesel oil.
5. according to claim 1,2 or 3 described purposes, it is characterized in that: described mesoporous aluminoshilicate is the mesoporous aluminoshilicate of transition metal exchange; The content of described transition metal is 3～40 weight %.
6. purposes according to claim 4 is characterized in that: described mesoporous aluminoshilicate is the mesoporous aluminoshilicate of transition metal exchange; The content of described transition metal is 3～40 weight %.
7. purposes according to claim 5 is characterized in that: described transition metal is copper, silver, nickel, zinc or any mixture between them.
8. purposes according to claim 6 is characterized in that: described transition metal is copper, silver, nickel, zinc or any mixture between them.
9. according to claim 1,2,3 or 6 described purposes, it is characterized in that: the mesoporous aperture of described mesoporous aluminoshilicate is 2～100nm, wherein on the mesoporous aluminoshilicate hole wall micro porous molecular sieve structure cell is arranged, this micro porous molecular sieve structure cell is Y zeolite, L type molecular sieve, beta molecular sieve or type ZSM 5 molecular sieve.
10. purposes according to claim 5, it is characterized in that: the mesoporous aperture of described mesoporous aluminoshilicate is 2～100nm, wherein on the mesoporous aluminoshilicate hole wall micro porous molecular sieve structure cell is arranged, this micro porous molecular sieve structure cell is Y zeolite, L type molecular sieve, beta molecular sieve or type ZSM 5 molecular sieve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974340A (en) * | 2020-08-27 | 2020-11-24 | 中国石油大学(北京) | Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon |
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- 2007-09-03 CN CNA2007101212799A patent/CN101381621A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111974340A (en) * | 2020-08-27 | 2020-11-24 | 中国石油大学(北京) | Desulfurization adsorbent, preparation method thereof and method for deeply desulfurizing hydrocarbon |
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