CN100497535C - Y-type molecular sieve for directly adsorbing and removing bisbenzothiophene from oil and its preparing method - Google Patents
Y-type molecular sieve for directly adsorbing and removing bisbenzothiophene from oil and its preparing method Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 11
- JGJGLMZEXTZURL-UHFFFAOYSA-N neodymium nickel Chemical compound [Ni].[Nd] JGJGLMZEXTZURL-UHFFFAOYSA-N 0.000 claims abstract description 5
- JLMHVMIMUYHBRQ-UHFFFAOYSA-N neodymium zinc Chemical compound [Zn].[Nd] JLMHVMIMUYHBRQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 49
- 238000005342 ion exchange Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000295 fuel oil Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 241000545067 Venus Species 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 241001076960 Argon Species 0.000 claims description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 2
- 235000013876 argon Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 55
- 239000011701 zinc Substances 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- RAASUWZPTOJQAY-UHFFFAOYSA-N Dibenz[a,c]anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C3=CC=CC=C3C2=C1 RAASUWZPTOJQAY-UHFFFAOYSA-N 0.000 abstract 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract 2
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 abstract 1
- 229930192474 thiophene Natural products 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 description 48
- 239000000243 solution Substances 0.000 description 37
- 229910021536 Zeolite Inorganic materials 0.000 description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- 239000010457 zeolite Substances 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- 239000012263 liquid product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- -1 dibenzothiophene organic compounds Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000894006 Bacteria Species 0.000 description 1
- 229910002530 Cu-Y Inorganic materials 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
- 150000001206 Neodymium Chemical class 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to molecular sieve used to absorb and remove dibenzanthracene thiophene sulfur coated organic compound. It is Y molecular sieve which contains copper, or zinc, or silver, or copper-zinc, or zinc-neodymium, or nickel-neodymium. It can be directly used to absorb and remove dibenzanthracene thiophene without preoxidation. This can simplify operation process, reduce cost. The 1g adsorbent can make the sulfur content of the 50ml sulfur coated solution reduce from 500ppm to 1ppm, 1000ppm to 15ppm, 1200ppm to 60ppm, 1500ppm to 220ppm. The sulfur removing quantity for each gram of the molecular sieve can reach 1.4mmol. The invention discloses its preparing method.
Description
Technical field
The present invention relates to the ion-exchanged of Y zeolite, the present invention also relates to the adsorbing and removing of dibenzothiophene organic compounds containing sulfur.
Background technology
In order to reduce environmental pollution, new automobile exhaust emission standard has had strict more requirement to the sulphur content in the fuel oil, and therefore, the sulfide in the deep removal fuel oil (particularly aromatic yl sulfide) becomes worldwide urgent problem.The metropolitan atmospheric pollution of China at present is very serious, becomes the key issue that social sustainable development needs to be resolved hurrily.In the metropolitan at home atmospheric pollution, motor vehicle emission accounts for sizable ratio, therefore presses for the clean fuel of producing low-sulfur, low alkene and low aromatic hydrocarbons, reduces the vehicle emission of harmful substances from the source.
According to China's automobile emission regulation requirement, began to carry out the standard that is equivalent to Europe I in 2000.Began to carry out the standard that is equivalent to Europe II in 2004.Rose in 2010 and come into effect automobile emissions standards in line with international standards.Beijing is owing to will host the Olympic Games, and the date of implementing relevant criterion further shifts to an earlier date.It is generally acknowledged that emission standard and employed fuel oil specification that automobile will reach are closely related.The standard of the motor spirit of domestic current and diesel oil still has the gap of bigger gap, particularly diesel oil bigger with the oil specification that " international fuel oil standard " II requires at present.For the fuel oil production, particularly Sulfur-Containing Crude and the device of mixing refining heavy oil of China, sulphur content is all defective.Therefore the alkene and the sulphur content that reduce in the oil product become the key that gasoline, diesel quality improve in China.On the other hand, for diesel production, the hydrogenation scarce capacity is that to cause diesel quality oxidative stability to occur poor, sulphur content height, the major cause of problem such as cetane value is low.
Though traditional hydrodesulfurization process has removed good effect to alkyl sulfur compounds in gasoline, the diesel oil and mercaptan, but aromatic yl sulfide (as thionaphthene, dibenzothiophene etc., their are present in the middle of the diesel oil) but is difficult under the typical hydroconversion condition and removes more.And hydrogenation process also can reduce octane value, and hydrogen consumption increases, and running cost rises.Therefore in recent years, people have attempted the sulfur method under a lot of non-hydroconversion conditions, as simple absorption (referring to F.M.Collins, A.R.Lucy, C.Sharp, J.Mole.Catal.A, 117 (1997) 397), extraction (referring to T.Coates, Euro.Chem.News, July 2001, p.23), bacterium living beings degraded (referring to J.J.Kilbane, Trends Biotech., 7 (1989) 97) or the like.With respect to traditional hydrodesulfurization process, the adsorbing and removing that utilizes special pore structure of molecular sieve and characterization of adsorption to carry out organic sulfide has special advantages, not only need not to consume hydrogen, and the positively charged ion on the duct variable size of molecular sieve, surface, duct can exchange, also can introduce specific metal ion on the framework of molecular sieve, thus its characterization of adsorption of modulation.These have constituted the basis of patent of the present invention.
Summary of the invention
The modification Na-Y molecular sieve and the method for making thereof that the purpose of this invention is to provide the direct adsorbing and removing dibenzothiophene of a kind of energy sulfurous organic compound.
Technical scheme of the present invention is as follows:
A kind of from oil product the modification Na-Y molecular sieve of adsorbing and removing dibenzothiophene, it is to contain copper, zinc or silver, the Na-Y molecular sieve that perhaps contains copper-zinc, zinc-neodymium or nickel-neodymium simultaneously, above-mentioned containing be single/the Na-Y molecular sieve of bimetal component in, its metal content is 0.9～10.4% of a total mass.
A kind of prepare above-mentioned from oil product the method for the modification Na-Y molecular sieve of adsorbing and removing dibenzothiophene, it is made up of the following step:
Step 1. is washed commodity Na-Y type molecular sieve 2 hours at 60 ℃ with distilled water, and molecular sieve/quality ratio=20:100 filters;
Step 3. places the salts solution of corresponding single or two component metals with the molecular sieve of step 2 gained, and acetate or nitrate are adopted in its copper, zine ion exchange, and Ag ion exchange adopts nitrate; Acetate solution is all adopted in copper-zine ion exchange, and nitrate solution is all adopted in zinc-neodymium or nickel-neodymium ion exchange.Carry out ion-exchange 4～48 hours at 20～60 ℃, exchange finish after-filtration and oven dry;
Step 4. is the roasting 15～18 hours in 450 ℃ of argons or helium-atmosphere of the molecular sieve of step 3 gained, promptly makes the Na-Y molecular sieve of adsorbing and removing dibenzothiophene from fuel oil that contains single or bimetal component ion-exchanged.
In the above-mentioned Na-Y molecular sieve ion-exchanged, the concentration of silver salt solution can be 0.014～0.070mol/L, the concentration of copper salt solution can be 0.004～0.042mol/L (venus crystals) or 0.104mol/L (cupric nitrate), the concentration of zinc solution can be 0.004～0.042mol/L (zinc acetate) or 0.004mol/L (zinc nitrate), the concentration of nickel salt solution is 0.004mol/L (nickelous nitrate), and the concentration of neodymium salts solution is 0.002mol/L (neodymium nitrate).
The Na-Y molecular sieve that contains single or the modification of bimetal ionic constituent of the present invention is adsorbing and removing dibenzothiophene and need not dibenzothiophene is carried out pre-oxidation treatment (such as dibenzothiophene is become corresponding sulphones with hydrogen peroxide oxidation earlier in the presence of 12-phospho-wolframic acid (TPA) and Tetrabutyl amonium bromide) directly, both simplify operating process, reduced cost again.
The test procedure that removes the dibenzothiophene sulfocompound with molecular sieve adsorption of the present invention is as follows:
1. get an amount of dibenzothiophene and be dissolved in the octane, the sulfur-bearing sample that is made into sulphur content and is 500～1500ppm is directly used in next step adsorption desulfurize.
2. in above-mentioned sulfur-bearing liquid, add a certain amount of molecular sieve, reflux in 60 ℃ and stirred 0.5～24 hour, filter.
3. liquid product is with its sulphur content of ANTK-9000 sulphur analysis-e/or determining.
It is not only directly related with the duct size of molecular sieve that molecular sieve removes the ability of sulfide, and also with the structural performance of molecular sieve closely related (metal ion of introducing on the metal ion of hole surface and the skeleton), and the self-characteristic of organic sulfide is closely related.Molecular sieve of the present invention can make sulphur content reduce to 1ppm from 500ppm, reduces to 15ppm from 1000ppm, reduces to 60ppm from 1200ppm, reduces to 220ppm from 1500ppm, and the desulfurization amount of every mol sieve can reach 1.4mmol.
Description of drawings
Fig. 1 is the XRD figure of Y molecular sieve of the present invention.
Embodiment
Embodiment 1
With the first 60 ℃ of agitator treatings 2 hours in 100ml distilled water of Y zeolite 20g, filter; Is 60 ℃ of ion-exchange 1 hour in the NaCl solution of 3.0mol/L with washed molecular sieve in 100ml concentration, amounts to 6 times, filters.With 60 ℃ of hot washes 3 times, use absolute ethanol washing again 3 times, in 100 ℃ of oven dry 24 hours, get Na
+The exchange Y zeolite.With 3.0g Na
+The exchange Y zeolite is 20 ℃ of lucifuge ion-exchange 2 hours in the silver nitrate solution of 0.014mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Ag-Y (I) in 18 hours in 450 ℃ of argon atmosphers again.It is 0.9% that XRF measures Ag content.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml,,, filter in 60 ℃ of stirrings 24 hours that reflux to wherein adding the above-mentioned Ag of the containing adsorbent of molecular sieve of 1.0g.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 8ppm from 500ppm.Desulfurization amount is 538 μ mol sulphur/g molecular sieves.
With 14.6g Na
+The exchange Y zeolite is 20 ℃ of lucifuge ion-exchange 2 hours in the silver nitrate solution of 0.067mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Ag-Y (II) in 18 hours in 450 ℃ of argon atmosphers again.It is 1.2wt% that XRF measures Ag content.The 1.2153g dibenzothiophene is dissolved in the solution that is mixed with 1500ppm in the 200ml octane.Get this solution of 50ml,,, filter in 60 ℃ of stirrings 0.5 hour that reflux to wherein adding the above-mentioned Ag of the containing adsorbent of molecular sieve of 1.0g.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 300ppm from 1500ppm.Desulfurization amount 1.32mmol sulphur/g molecular sieve.
Embodiment 3
With 15.1g Na
+The exchange Y zeolite is 20 ℃ of lucifuge ion-exchange 2 hours in the silver nitrate solution of 0.070mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Ag-Y (III) in 18 hours in 450 ℃ of argon atmosphers again.It is 3.3wt% that XRF measures Ag content.The 0.9722g dibenzothiophene is dissolved in the solution that is mixed with 1200ppm in the 200ml octane.Get this solution of 50ml,,, filter in 20 ℃ of stirrings 24 hours that reflux to wherein adding the above-mentioned Ag of the containing adsorbent of molecular sieve of 1.0g.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 140ppm from 1200ppm.Desulfurization amount 1.16mmol sulphur/g molecular sieve.
Embodiment 4
With 3.3g Na
+The exchange Y zeolite is 60 ℃ of ion-exchange 24 hours in the acetic acid zinc solution of 0.100mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Zn-Y in 18 hours in 450 ℃ of helium-atmospheres again.It is 10.4wt% that ICP measures Zn content.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Zn2 of 1.0g
+The exchange Y zeolite.In 60 ℃ of stirrings 24 hours that reflux, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 75ppm from 500ppm.Desulfurization amount is 466 μ mol sulphur/g molecular sieves.
Embodiment 5
With 3.3g Na
+The exchange Y zeolite is 60 ℃ of ion-exchange 24 hours in the copper nitrate solution of 0.104mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Cu-Y in 18 hours in 450 ℃ of helium-atmospheres again.It is 8.0wt% that ICP measures Cu content.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Cu of 1.0g
2+The exchange Y zeolite.In 60 ℃ of stirrings 24 hours that reflux, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 113ppm from 500ppm.Desulfurization amount is 425 μ mol sulphur/g molecular sieves.
Embodiment 6
With 2.7g Na
+The exchange Y zeolite is respectively in the mixing solutions of 0.042mol/L and 0.042mol/L 60 ℃ of ion-exchanges 2 hours, totally 2 times in its venus crystals of 100ml and zinc acetate concentration.Exchange finish after-filtration, oven dry, roasting got CuZn-Y (I) in 18 hours in 450 ℃ of argon atmosphers again.It is 4.1wt% that ICP measures Cu content, and Zn content is 4.1wt%.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Cu of 1.0g
2+And Zn
2+The exchange Y zeolite.In 60 ℃ of stirrings 24 hours that reflux, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 10ppm from 500ppm.Desulfurization amount is 538 μ mol sulphur/g molecular sieves.
Embodiment 7
With 2.7g Na
+The exchange Y zeolite is respectively in the mixing solutions of 0.004mol/L and 0.004mol/L 60 ℃ of ion-exchanges 2 hours, totally 2 times in its venus crystals of 100ml and zinc acetate concentration.Exchange finish after-filtration, oven dry, roasting got CuZn-Y (II) in 15 hours in 450 ℃ of argon atmosphers again.It is 1.9wt% that ICP measures Cu content, and Zn content is 2.1wt%.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Cu of 1.0g
2+And Zn
2+The exchange Y zeolite.In 60 ℃ of stirrings 24 hours that reflux, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 120ppm from 500ppm.Desulfurization amount is 417 μ mol sulphur/g molecular sieves.
Embodiment 8
With 2.5g Na
+The exchange Y zeolite is respectively in the mixing solutions of 0.002mol/L and 0.004mol/L 60 ℃ of ion-exchanges 2 hours, totally 2 times in its neodymium nitrate of 100ml and zinc nitrate concentration.Exchange finish after-filtration, oven dry, roasting got NdZn-Y in 18 hours in 450 ℃ of argon atmosphers again.It is 2.1wt% that ICP measures Nd content, and Zn content is 2.2wt%.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Nd of 1.0g
3+And Zn
2+The exchange Y zeolite.In 60 ℃ of backflow stirring reactions 24 hours, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 56ppm from 500ppm.Desulfurization amount is 488 μ mol sulphur/g molecular sieves.
Embodiment 9
With 2.5g Na
+The exchange Y zeolite is respectively in the mixing solutions of 0.002mol/L and 0.004mol/L 60 ℃ of ion-exchanges 2 hours, totally 2 times in its neodymium nitrate of 100ml and nickelous nitrate concentration.Exchange finish after-filtration, oven dry, roasting got NdNi-Y in 18 hours in 450 ℃ of argon atmosphers again.It is 1.9wt% that ICP measures Nd content, and Ni content is 2.2wt%.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml, to wherein adding the above-mentioned Nd of 1.0g
3+And Ni
2+The exchange Y zeolite.In 60 ℃ of backflow stirring reactions 24 hours, filter.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 140ppm from 500ppm.Desulfurization amount is 394 μ mol sulphur/g molecular sieves.
With 3.4g Na
+The exchange Y zeolite is 20 ℃ of lucifuge ion-exchange 24 hours in the silver nitrate solution of 0.063mol/L in 100ml concentration, totally 2 times.Exchange finish after-filtration, oven dry, roasting got Ag-Y (IV) in 18 hours in 450 ℃ of helium-atmospheres again.It is 4.6wt% that XRF measures Ag content.The 0.4051g dibenzothiophene is dissolved in the solution that is mixed with 500ppm in the 200ml octane.Get this solution of 50ml,,, filter in 60 ℃ of stirrings 24 hours that reflux to wherein adding the above-mentioned Ag of the containing adsorbent of molecular sieve of 1.0g.With liquid product its sulphur content of ANTK-9000 sulphur analysis-e/or determining.Sulphur content is reduced to 2ppm from 500ppm.Desulfurization amount is 547 μ mol sulphur/g molecular sieves.
Claims (2)
1. the Na-Y ion-exchanged molecular sieve of an adsorbing and removing dibenzothiophene, it is characterized in that: it is the Y molecular sieve that contains copper-zinc, zinc-neodymium or nickel-neodymium, its metal content is 0.9～10.4% of a total mass.
2. method for preparing the Na-Y ion-exchanged molecular sieve of the described adsorbing and removing dibenzothiophene of claim 1 is characterized in that it is made up of the following step:
Step 1. is washed commodity Na-Y type molecular sieve 2 hours at 60 ℃ with distilled water, and molecular sieve/quality ratio=20:100 filters;
Step 2. is to carry out ion-exchange at 60 ℃ in the 3mol/L NaCl solution with the washed molecular sieve of step 1 in concentration, totally 6 times, and each 1 hour, filter, the molecular sieve that obtains is used absolute ethanol washing, drying more earlier with 60 ℃ of hot washes;
Step 3. places the molecular sieve of step 2 gained the salts solution of corresponding pair of component metal, acetate solution is adopted in its copper-zine ion exchange, nitrate solution is adopted in zinc-neodymium or nickel-neodymium ion exchange, the concentration of venus crystals solution is 0.004～0.042mol/L, the concentration of acetic acid zinc solution is 0.004～0.042mol/L, the concentration of nickel nitrate solution is 0.004mol/L, the concentration of neodymium nitrate solution is 0.002mol/L, carry out ion-exchange 4～48 hours at 20～60 ℃, exchange finish after-filtration and oven dry;
Step 4. is the roasting 15～18 hours in 450 ℃ of argons or helium-atmosphere of the molecular sieve of step 3 gained, promptly makes the Na-Y molecular sieve of adsorbing and removing dibenzothiophene from fuel oil that contains bimetal component ion-exchanged.
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| US5843300A (en) * | 1997-12-29 | 1998-12-01 | Uop Llc | Removal of organic sulfur compounds from FCC gasoline using regenerable adsorbents |
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