CN101747930B - Method for preparing desulfurizer - Google Patents
Method for preparing desulfurizer Download PDFInfo
- Publication number
- CN101747930B CN101747930B CN200810220011.5A CN200810220011A CN101747930B CN 101747930 B CN101747930 B CN 101747930B CN 200810220011 A CN200810220011 A CN 200810220011A CN 101747930 B CN101747930 B CN 101747930B
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- CN
- China
- Prior art keywords
- desulfurizing agent
- washing
- molecular sieve
- solution
- desulfurizer
- Prior art date
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- 238000000034 method Methods 0.000 title abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002808 molecular sieve Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- -1 molecular sieve metal oxide Chemical class 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000002594 sorbent Substances 0.000 abstract 3
- 238000003795 desorption Methods 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000003502 gasoline Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- SGDMQXAOPGGMAH-UHFFFAOYSA-N phenol;thiophene Chemical compound C=1C=CSC=1.OC1=CC=CC=C1 SGDMQXAOPGGMAH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical class CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
In order to solve the problems of inadequate desulfurization depth, low sulfur capacity of a sorbent, poor regeneration performance, and the like of a desulfurizer existing in the prior art, the invention provides a preparation method of a desulfurizer. The method uses a nano-rare earth doped mesoporous molecular sieve as a main body, assembles metal-oxide guest molecules in the surface of the nano molecular sieve and a porous channel and prepares a high-selectivity sorbent of mesoporous molecular sieve metal oxide. The adsorption desulfurizer has large desulfurization depth, and the sorbent has high sulfur capacity and can reuse by simple heating desorption activation regeneration.
Description
Technical field
The present invention relates to the preparation method of gasoline desulfur product, be specifically related to a kind of preparation method who utilizes the desulfurizing agent of non-elemental sulfur component in the effective adsorbed gasoline of molecular sieve.
background technology
The sulphur-containing exhaust gas producing after organic sulfur compound burning in gasoline has caused serious harm to environment.Solve the pollution problem of vehicle exhaust to environment, basic method is from source, to improve the production technology of fuel, reduces sulfur content in gasoline to produce low sulfur content clean gasoline.
Except Hydrobon, refining industry is used some non-hydrogen addition technologies at present, adsorption desulfurize technology, abstraction desulfurization technology and biological desulfurizing technology etc. such as gasoline, diesel oil, because they have the feature of environmental protection, efficient, small investment, thereby there is wide technical development space and the market space, wherein especially most with prospects with adsorption desulfurize.The advantages such as that this technology has is simple to operate, small investment, efficient, environmental protection and adsorbent can be regenerated, it is fully contacting by fuel oil and adsorbent, the sulfur-containing compounds such as the thiophene phenol in fuel oil, thioether, disulphide, mercaptan are adsorbed on adsorbent, thereby the content of sulphur in reduction fuel oil, and can substantially keep the octane of fuel oil or Cetane number constant.But the desulfurizing agent using in prior art is generally zeolite or active carbon, ubiquity desulfurization depth not, the sulfur capacity of adsorbent is lower, and the problem such as regenerability is bad, thereby greatly limited its commercial Application.
summary of the invention
Lower for solving the desulfurizing agent desulfurization depth existing in prior art sulfur capacity inadequate, adsorbent, and the problems such as regenerability is bad, the invention provides a kind of preparation method of adsorption desulfurizing agent, it adopts nano rare earth doped mesoporous molecular sieve is main body, metal oxide guest molecule is assembled in the surface and duct of nano molecular sieve, prepares composite mesoporous molecular sieve metal oxide efficient selective adsorbent.
The preparation method of adsorption desulfurizing agent provided by the invention comprises:
(a) heating condition under by Eu
2o
3powder is dissolved in red fuming nitric acid (RFNA), the nitric acid that heating evaporation is excessive;
(b) product of step (a) is dissolved in to absolute ethyl alcohol, then adds ethyl orthosilicate to mix, obtain organic phase solution;
(c) above-mentioned organic phase solution being joined to mass fraction is 1.2% trimethyl cetyl ammonium bromide NH
3-NH
4nO
3in solution, room temperature is standing, until react completely;
(d), after sedimentation and filtration step (c) being produced, washing, at 800 ℃ of calcining 5h, obtain white powder standby;
(f) by TiCl
4with the volume ratio of 1: 25, join in absolute ethyl alcohol and carry out alcoholysis, obtain containing Ti (OC
2h
5)
4ethanolic solution;
(g) step (f) is obtained containing Ti (OC
2h
5)
4ethanolic solution mix with the white powder that step (d) obtains, solvent evaporated, then add absolute ethanol washing, stirring, and by ethanol evaporate to dryness; Drip after excessive concentrated ammonia liquor, then dry out solvent; At 500 ℃ of calcining 2h, obtain desulfurizing agent subsequently.
Trimethyl cetyl ammonium bromide NH in step (c) wherein
3-NH
4nO
3pH be 9.5; Described in step (d), washing is to use methanol wash.
The atom number ratio of Ti in resulting desulfurizing agent: Eu is 0.4: 1,8.5: 1,13.9: 1 or 22.2: 1, is preferably 8.5: 1.The atom number ratio of Eu in resulting desulfurizing agent: Si is 1: 10.
The adsorption desulfurizing agent that utilizes the inventive method to prepare, when the atom number ratio of Ti in desulfurizing agent: Eu is 0.4: 1,8.5: 1,13.9: 1 or 22.2: 1, desulfurization adsorbance is very big, the amount of absorption thiophene phenol reaches respectively 19.3,41.0,15.4,11.4mg/100mg.Wherein, that absorption property is best is Ti: the atom number ratio of Eu is 8.5: 1 o'clock, and (1: 110, g/g), the sulfur-bearing of merchantable gasoline was reduced in 150ppm by 270ppm, meets gasoline state III standard with it, to process commercially available 93# (or 97#) gasoline.Therefore the adsorption desulfurizing agent desulfurization depth sulfur capacity large, adsorbent that, utilizes the inventive method to prepare is higher.In addition, adsorption desulfurizing agent prepared by the present invention can be regenerated by simple heating desorptive activation, reuses.
The specific embodiment
One, the preparation of adsorption desulfurizing agent of the present invention
Heating condition under by Eu
2o
3powder is dissolved in appropriate red fuming nitric acid (RFNA), the nitric acid that heating evaporation is excessive.Product is dissolved in after absolute ethyl alcohol, is mixing with appropriate ethyl orthosilicate (w (Si)=28.4%), obtain organic phase solution (Eu: Si=1 wherein: 10).Organic phase solution is carefully poured over to 1.2% trimethyl cetyl ammonium bromide NH
3-NH
4nO
3on the aqueous phase solution of solution (pH:9.5), can observe white precipitate in slow generation, reaction is carried out at two-phase interface.Standing 48h at room temperature, until react completely.Gained solid product is carried out to suction filtration, by methanol wash, then is placed in Muffle furnace, in 800 ℃ of calcining 5h, after cooling white powder.
With TiCl
4be added drop-wise to absolute ethyl alcohol (1: 2.5V/V), carry out alcoholysis, then by obtain containing Ti (OC
2h
5)
4ethanolic solution transfer in volumetric flask, and use absolute ethyl alcohol constant volume.According to the specific pore volume of nano rare earth doped mesoporous molecular sieve, be 1.5cm
3/ g and TiO
2density, the pore volume that calculates mesopore molecular sieve is occupied 1/4,1/2,3/4 and 4/4 4 kind of situation.Pipette respectively different volumes containing Ti (OC
2h
5)
4ethanolic solution and appropriate gained white powder mutually mix, solvent evaporated subsequently, then add appropriate absolute ethyl alcohol, washing, stirs, and by ethanol evaporate to dryness.Drip after excessive concentrated ammonia liquor, dry moisture.Place it in again in the Muffle furnace of 500 ℃ calcination 2h.The cooling rear TiO that obtains respectively
2molecular sieves compound material (desulfurizing agent), its specific surface is respectively 440,204, and 100 and 70m
2/ g.
Two, the using method of adsorption desulfurizing agent of the present invention
First desulfuration adsorbent is put into a container or desulfurizing filter, then analog gasoline or commercially available 93# (or 97#) gasoline that will desulfurization be poured and stir or filters into.In the experiment of iso-butane analog gasoline, record molecular sieves compound material (desulfurizing agent), when the atom number ratio of Ti: Eu is 0.4: 1,8.5: 1,13.9: 1 or 22.2: 1, amount of its absorption thiophene phenol reaches respectively 19.3,41.0,15.4,11.4mg/100mg desulfurizing agent.Evidence, what absorption property was best is as Ti: when the atom number ratio of Eu is 8.5: 1.The desulfurizing agent that adopts the inventive method to prepare is processed commercially available 93# (or 97#) gasoline, and (1: 110, g/g), the sulfur-bearing of merchantable gasoline was reduced in 150ppm by 270ppm, meets gasoline state III standard.
In addition, adsorption desulfurizing agent of the present invention can at 200 ℃ of temperature, heat desorptive activation regeneration in 2 hours by simple heating, can reuse.。
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. a method of preparing desulfurizing agent, it comprises:
(a) heating condition under by Eu
2o
3powder is dissolved in red fuming nitric acid (RFNA), the nitric acid that heating evaporation is excessive;
(b) product of step (a) is dissolved in to absolute ethyl alcohol, then adds ethyl orthosilicate to mix, obtain organic phase solution;
(c) above-mentioned organic phase solution is joined to the NH that mass fraction is 1.2% trimethyl cetyl ammonium bromide
3-NH
4nO
3in solution, room temperature is standing, until react completely;
(d), after sedimentation and filtration step (c) being produced, washing, at 800 ℃ of calcining 5h, obtain white powder standby;
(f) by TiCl
4with the volume ratio of 1 ︰ 25, join in absolute ethyl alcohol and carry out alcoholysis, obtain containing Ti (OC
2h
5)
4ethanolic solution;
(g) step (f) is obtained containing Ti (OC
2h
5)
4ethanolic solution mix with the white powder that step (d) obtains, solvent evaporated, then add absolute ethanol washing, stirring, and by ethanol evaporate to dryness; Drip after excessive concentrated ammonia liquor, then dry out solvent; At 500 ℃ of calcining 2h, obtain desulfurizing agent subsequently;
Wherein in resulting desulfurizing agent, the atom number of Ti:Eu ratio is 0.4:1,8.5:1,13.9:1 or 22.2:1;
In addition, in resulting desulfurizing agent, the atom number of Eu:Si ratio is 1:10.
2. the method for claim 1, is characterized in that, the NH of trimethyl cetyl ammonium bromide in step (c)
3-NH
4nO
3pH be 9.5.
3. the method for claim 1, is characterized in that, described in step (d), washing is to use methanol wash.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220011.5A CN101747930B (en) | 2008-12-15 | 2008-12-15 | Method for preparing desulfurizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220011.5A CN101747930B (en) | 2008-12-15 | 2008-12-15 | Method for preparing desulfurizer |
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| Publication Number | Publication Date |
|---|---|
| CN101747930A CN101747930A (en) | 2010-06-23 |
| CN101747930B true CN101747930B (en) | 2014-03-19 |
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|---|---|---|---|
| CN200810220011.5A Expired - Fee Related CN101747930B (en) | 2008-12-15 | 2008-12-15 | Method for preparing desulfurizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117065723B (en) * | 2023-09-20 | 2024-03-12 | 湖南浩润科技有限公司 | Desulfurizing agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1519297A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司 | A kind of fuel oil desulfurization adsorbent and preparation method thereof |
| JP2005052779A (en) * | 2003-08-06 | 2005-03-03 | Chiyoda Corp | Metal oxide coated alumina composite oxide |
| CN101314727A (en) * | 2008-06-25 | 2008-12-03 | 南京工业大学 | A kind of desulfurization method of gasoline |
-
2008
- 2008-12-15 CN CN200810220011.5A patent/CN101747930B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1519297A (en) * | 2003-01-24 | 2004-08-11 | 中国石油化工股份有限公司 | A kind of fuel oil desulfurization adsorbent and preparation method thereof |
| JP2005052779A (en) * | 2003-08-06 | 2005-03-03 | Chiyoda Corp | Metal oxide coated alumina composite oxide |
| CN101314727A (en) * | 2008-06-25 | 2008-12-03 | 南京工业大学 | A kind of desulfurization method of gasoline |
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| Publication number | Publication date |
|---|---|
| CN101747930A (en) | 2010-06-23 |
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