CN1165376C - Faujasite molecular sieve composition and its preparing process - Google Patents
Faujasite molecular sieve composition and its preparing process Download PDFInfo
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- CN1165376C CN1165376C CNB011198214A CN01119821A CN1165376C CN 1165376 C CN1165376 C CN 1165376C CN B011198214 A CNB011198214 A CN B011198214A CN 01119821 A CN01119821 A CN 01119821A CN 1165376 C CN1165376 C CN 1165376C
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- molecular sieve
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- rare earth
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 99
- 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 99
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000012013 faujasite Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 34
- -1 rare earth ions Chemical class 0.000 claims abstract description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 3
- 239000007864 aqueous solution Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910017717 NH4X Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- 229910021536 Zeolite Inorganic materials 0.000 description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 25
- 239000010457 zeolite Substances 0.000 description 25
- 239000012065 filter cake Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000004411 aluminium Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- 239000002253 acid Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000004846 x-ray emission Methods 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002594 sorbent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
一种具有八面沸石结构的分子筛组合物，其特征在于该组合物含有交换有稀土离子的八面沸石和外加的铝，其中以RE2O3计的稀土元素的含量为1-20重量%；以Al2O3计的外加的铝的含量为0.5-10重量%。本发明提供的富含铝和稀土的分子筛组合物酸量明显增加，可用于汽油脱硫等领域。A molecular sieve composition with a faujasite structure , characterized in that the composition contains faujasite exchanged with rare earth ions and added aluminum, wherein the content of rare earth elements calculated as RE2O3 is 1-20% by weight ; Al 2 O 3 added aluminum content of 0.5-10% by weight. The molecular sieve composition rich in aluminum and rare earth provided by the invention has significantly increased acidity and can be used in the fields of gasoline desulfurization and the like.
Description
Technical field
The invention relates to a kind of preparation method with combination of molecular sieve of faujusite structure.
Background technology
In catalytic cracking process, in order to obtain high yield, stop bracket gasoline, contained type-Y high silicon zeolite must be able to keep crystalline structure intact in the cracking catalyst, and has characteristics such as very high heat and hydrothermal stability, acid strong and sour density are low.When preparing the superstable gamma-type supersiliceous zeolite by modification, normally the NaY zeolite is handled, reduce the aluminium content in the former zeolite, improve the silica alumina ratio of zeolite framework, reduce lattice constant, thereby reduce sour density, improve the heat and the hydrothermal stability of zeolite.For realizing this purpose, the technology of comparative maturity has hydrothermal dealumination and various chemical dealuminizations etc., as with the reaction of NaY zeolite and ammonium fluosilicate solution, with sequestrant reaction (as EDTA etc.) and SiCl
4Or other halide vapor reaction or the like.Because catalytic cracking has critical role in petroleum refining industry, and the dealuminzation of y-type zeolite is to solve the active and stable key of cracking catalyst, therefore, people have given sizable attention to the Y zeolite dealuminzation for a long time, and adopt the prepared in various methods high-Si Y-type molecular sieve is the past main research work always.
Through the molecular sieve that obtains after the dealumination treatment, its sour density reduces, and can suppress hydrogen transfer reactions, thereby produce stop bracket gasoline, but because the aluminium atom on the framework of molecular sieve is an acid sites, the removal of framework aluminum means the forfeiture of acid sites, and its sour density and total acid content are reduced.The removal of framework of molecular sieve aluminium not only makes zeolitic acid center reduced number, also can make environment redistribution in remaining acid site in the zeolite, the change that causes strength of acid to distribute.Because the catalytic activity of molecular sieve, absorption property, ion-exchange capacity etc. are decided by the aluminium content in the molecular sieve to a great extent, therefore, in order to improve the acid amount of molecular sieve, increase its sour density, can in molecular sieve, introduce aluminium to reach the purpose of its above-mentioned performance of modulation.
USP 4,597, and 956 have reported the method for using aluminum soluble salt to remove soluble fluorine-containing impurity from Si-Al molecular sieve, and these impurity are difficult for removing with ordinary method.This method is to use (NH
4)
2SiF
6Solution is to NH
4Y molecular sieve carries out aluminium-eliminating and silicon-replenishing and prepares in the super steady Y process, adds aluminum soluble salts such as Tai-Ace S 150, aluminum nitrate, aluminum chloride, can remove fluorine-containing impurity effectively, and the molecular sieve thermostability is improved.
USP 4,943,545th, will contain the high silica alumina ratio molecular sieve and the NH of non-framework aluminum
4F, HF or NH
4The reactant aqueous solution of fluorochemicals such as F HF is exchanged into ammonium type molecular sieve, then after roasting makes the molecular sieve that catalytic activity, ion-exchange performance and degree of crystallinity all are improved.USP 5,118, the 482nd, lack in the aluminum molecular screen toward skeleton by the dipping aluminum soluble salt earlier and introduce non-framework aluminum, the ammonia soln that adds pH=9-12 then in the above-mentioned molecular sieve, stirring, slurrying, kept 16 hours at 60-90 ℃, through drip washing, oven dry, roasting, the non-framework aluminum in the molecular sieve is changed into framework aluminum.USP 4,943,545 and USP 5,118,482 skeleton is lacked aluminum molecular screen, carry out calorize as the high silica alumina ratio molecular sieve behind the hydrothermal aging and handle, make aluminum ion reenter framework of molecular sieve, belong to calorize process again.
CN 1060976A has introduced a kind of preparation method who contains the ultrastable Y of amorphous alumina, and this method is that aluminium glue is introduced in NaY or the HNaY zeolite, carries out ammonium ion exchange, filtration and hydrothermal calcine through conventional hydrothermal method again and makes and contain the amorphous Al of the heavy % of 5-30
2O
3The USY zeolite.With the USY zeolite facies ratio that conventional hydrothermal method is made, adopt the USY of method for preparing to have higher crystallization reservation degree.
Hou Jun etc. (petroleum journal (refining of petroleum) 1993,9 (4), 50) adopt aluminium salt pair H
2SiF
6The skeleton silicon-rich Y-shaped molecular sieve of liquid phase aluminium-eliminating and silicon-replenishing method preparation carries out modification, and the product crystalline phase that obtains is pure, Na
+, F
-Content is low, and the B acid site is more, and the L acid site still less.
ES 2134070 A1 disclose the method for the USY molecular sieve of a kind of load P, Al, and this method adopts ion-exchange techniques earlier, makes NH by NaY
4Y floods aluminium salt and phosphoric acid then respectively, at last again with (NH
4)
2SO
4Carry out ion-exchange and make finished product.Its cracking activity of molecular sieve after the modification and anti-coking performance all are improved.
Summary of the invention
The purpose of this invention is to provide a kind of combination of molecular sieve with faujusite structure and preparation method thereof, this combination of molecular sieve has higher acid site density, has higher desulfurization degree when being used for gasoline desulfur.
Combination of molecular sieve with faujusite structure provided by the invention contains exchange the faujusite of rare earth ion and the aluminium that adds, and its middle-weight rare earths is (with RE
2O
3Meter) content is 1-20 weight %, preferred 3-16 weight %; The aluminium that adds is (with Al
2O
3Meter) content is 0.5-10 weight %, preferred 1-8 weight %.
Said faujusite is framework si-al ratio (SiO in the combination of molecular sieve provided by the invention
2/ Al
2O
3Mol ratio) be 2.2-3.0, X type zeolite and the framework si-al ratio of preferred 2.5-2.9 are 4.0-17.0, the y-type zeolite of preferred 4.5-16.0.
Said rare earth mainly is present on the cationic exchange position of molecular sieve with the form of ionic state in the combination of molecular sieve provided by the invention, said rare earth is the rare earth ion of the exchange cation that can be used as molecular sieve known of those of ordinary skills, comprise, for example, lanthanum, cerium, praseodymium, neodymium, samarium, yttrium etc., or their mixture.Generally in industrial practical application use based on La and/or Ce and contain the lucium of a small amount of other rare earth (as yttrium, neodymium, praseodymium, samarium etc.), wherein the content of La is 5-90 weight %, is preferably 10-50 weight %; The content of Ce is 10-95 weight %, is preferably 50-90 weight %; Other content of rare earth is preferably less than 10 weight % less than 20 weight %.
The said aluminium that adds generally evenly exists on the surface of zeolite with the form of deposition attitude oxide compound in the combination of molecular sieve provided by the invention, its introducing method be with zeolite with the aqueous solution of aluminum contained compound flood reaction or with alkali with the al deposition in the solution on zeolite, filter then and roasting.
The preparation method of combination of molecular sieve provided by the invention comprises: to be selected from NaY, NH
4Y, HY, NaX, NH
4The faujusite of any among X and the HX carries out rare earth exchanged according to ordinary method with rare earths salt, obtains content of rare earth (with RE
2O
3Meter) be the faujusite of 1-20 weight %; The aqueous solution of gained rare-earth type faujusite and aluminum contained compound room temperature to 100 ℃ reaction 0.2-3 hour, preferably 50-95 ℃ of reaction 1-2 hour, is filtered, make the gained combination of molecular sieve contain the Al that adds of 0.5-10 weight %
2O
3, then at 400-700 ℃ of roasting 1-4 hour.
Among the preparation method of combination of molecular sieve provided by the invention after making the faujusite of required content of rare earth, also gained rare-earth type faujusite can be mixed with aluminum salt solution and with alkali with the al deposition in the solution on zeolite, filter then and roasting.
The preparation method of combination of molecular sieve provided by the invention can also be included in and carry out after the rare earth exchanged the step of molecular sieve at 500-750 ℃ of roasting 1-4 hour.
The aqueous solution of said aluminum contained compound can be a kind of in the aqueous solution of solubility aluminum contained compounds such as Tai-Ace S 150, exsiccated ammonium alum, aluminum nitrate, aluminum chloride, sodium metaaluminate among the preparation method of combination of molecular sieve provided by the invention, also can be several mixing solutionss that obtain that mix mutually in them, the concentration of aluminium has no particular limits, and is generally 0.1-4M.
The invention is characterized in that both having contained more rare earth in the molecular sieve for preparing thus also contains the aluminium that adds, and the distribution uniform of aluminium, the analytical results of transmission electron microscope-energy dispersive spectrum (TEM-EDS) shows that the aluminium content of different microcells in the same molecular sieve is basic identical.
The combination of molecular sieve that is rich in aluminium and rare earth provided by the invention is compared with the rare-earth type faujusite of not introducing aluminium, and the acid amount obviously increases, and sweetening effectiveness is better when being used for gasoline desulfur; Compare with not containing the faujusite that adds aluminium containing of rare earth, sweetening effectiveness is better when being used for gasoline desulfur.
Combination of molecular sieve provided by the invention can be used as multiple hydrocarbon conversion reactions activity of such catalysts component, or as sorbent material and ion-exchange material etc.Particularly this combination of molecular sieve has adsorption desulfurize performance preferably during as sorbent material, can be applicable to the adsorption desulfurize of catalytically cracked gasoline etc.
Embodiment
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
In each embodiment and Comparative Examples, the content of aluminium, silicon, rare earth etc. is measured (used instrument is a Rigaku 3271E type Xray fluorescence spectrometer) with x ray fluorescence spectrometry (XRF) in the products molecule sieve; X-ray diffraction (XRD) data are measured (Cu Ka radiation, operating voltage 40KV, working current 40mA) by SIEMENS D5005 type X-ray diffractometer; Aluminium in the crystal grain top layer, content of rare earth adopt transmission electron microscope-energy dispersive spectrum to measure (be the TEM-EDS method, used instrument is a JEOLJEM-2000FXII type analysis instrument, and acceleration voltage is 120KV); NH is adopted in acidimetric estimation
3-TPD method is measured the ammonia amount of desorption with thermal conductivity cell detector (TCD), and adopts acid base titration to draw the total acid content of every gram sample.Adopt x-ray fluorescence method to measure the variation of organic sulfur content in the gasoline of absorption front and back.
The method that the framework si-al ratio of molecular sieve is measured (D.W.Breck and E.M.Flanigen, Molecular Sieves, Society of Chemical Industry, London, 1968) according to the Breck-Flanigen method in the combination of molecular sieve is measured.Total Al of the combination of molecular sieve product that the weight percentage of the aluminium that adds in the combination of molecular sieve records according to xrf method
2O
3Content deducts total Al of raw molecule sieve
2O
3Content obtains.
Embodiment 1
(Chang Ling oil-refining chemical factory catalyst plant is produced, and silica alumina ratio is 5.1, the Al that XRF records with 30 gram NaY molecular sieves
2O
3Content is 24 weight %, down with) be dispersed in the RECl that 300ml concentration is 10% (weight)
3(weight percentage of each composition is in its total amount of rare earth: Ce
2O
363%, La
2O
325%, Pr
6O
112.1%, Nd
2O
35.0%, Sm
2O
30.5%, other 4.4%, down with) in the aqueous solution,, filter 90 ℃ of exchanges 1 hour down, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of preparation 500mL0.5M
3)
3The aqueous solution mixes the rare earth Y type molecular sieve that obtains with above-mentioned aluminum salt solution, reacted 1 hour down at 90 ℃, filters, and filter cake is through water wash, and oven dry 550 ℃ of following roastings 2 hours, obtains faujusite structural molecule screen composition of the present invention.
Comparative Examples 1
30 gram NaY molecular sieves are dispersed in the RECl that 300ml concentration is 10% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake obtains rare earth Y type molecular sieve through water wash, oven dry, 550 ℃ of following roastings 2 hours.
Comparative Examples 2
30 gram NaY molecular sieves are dispersed in the NH that 300ml concentration is 10% (weight)
4In the Cl aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of the about 0.5M of preparation 500mL
3)
3The aqueous solution mixes the Y zeolite that obtains with above-mentioned aluminum salt solution, reacted 1 hour down at 90 ℃, filters, and filter cake is through water wash, and oven dry 550 ℃ of following roastings 2 hours, is not contained the Y zeolite composition of rare earth.
Embodiment 2
30 gram NaY molecular sieves are dispersed in the NH that 300ml concentration is 10% (weight)
4In the Cl aqueous solution, exchange 1 hour down at 90 ℃, filter, filter cake is through water wash.
Molecular sieve after the above-mentioned ammonium exchange is dispersed in the RECl that 300ml concentration is 10% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 650 ℃ of following roastings 2 hours.The AlCl of preparation 500mL 0.5M
3The aqueous solution is with rare earth Y type molecular sieve and the above-mentioned AlCl that obtains
3Aqueous solution 90 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 650 ℃ of following roastings 2 hours.
Embodiment 3
(Chang Ling oil-refining chemical factory catalyst plant is produced, and trade names are SRY, and silica alumina ratio is 7.24, the Al that XRF records with 30 gram super-stable Y molecular sieves
2O
3Content is 13 weight %) be dispersed in the RECl that 300ml concentration is 10% (weight)
3In the aqueous solution, exchange 1 hour down at 90 ℃, filter, filter cake is through water wash, oven dry.The Al of preparation 500mL 0.5M
2(SO
4)
3The aqueous solution is with rare-earth type ultra-steady Y molecular sieve and the above-mentioned Al that obtains
2(SO
4)
3Aqueous solution 95 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 600 ℃ of following roastings 2 hours.
Embodiment 4
30 gram NaY molecular sieves are dispersed in the RECl that 300ml concentration is 12% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of preparation 500mL 1M
3)
3The aqueous solution is with rare earth containing zeolite and the above-mentioned Al (NO that obtains
3)
3Aqueous solution was at room temperature reacted 1 hour, filtered, and filter cake is through water wash, and oven dry 500 ℃ of following roastings 3 hours, obtains combination of molecular sieve of the present invention.
Embodiment 5
(Lanzhou oil-refining chemical factory catalyst plant is produced, and silica alumina ratio is 13.95, the Al that XRF records with 30 gram super-stable Y molecular sieves
2O
3Content is 10 weight %) be dispersed in the RECl that 300ml concentration is 12% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.The AlCl of preparation 500mL 1M
3The aqueous solution is with rare earth Y type molecular sieve and the above-mentioned AlCl that obtains
3Aqueous solution 90 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 550 ℃ of following roastings 2 hours.
Embodiment 6
30 gram NaY molecular sieves are dispersed in the RECl that 300ml concentration is 12% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.The Al of preparation 500mL 1M
2(SO
4)
3The aqueous solution is with rare earth containing zeolite and the above-mentioned Al that obtains
2(SO
4)
3Aqueous solution 90 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 550 ℃ of following roastings 2 hours.Adopt the TEM-EDS method, 10 microcells of picked at random, the surface-element of measuring this combination of molecular sieve distributes, and it the results are shown in table 1.As seen from Table 1, aluminium content is more approaching everywhere in the sample, and the distribution uniform of aluminium in the molecular sieve is described.
The element distribution (TEM-EDS method mensuration) on table 1 molecular sieve surface
Constituent content (in oxide compound) (weight %)
Check point 123456789 10
Al
2O
3 22.3 22.4 22.4 23.8 22.9 21.9 22.0 23.2 23.7 23.7
SiO
2 62.2 61.4 62.5 58.0 63.1 62.7 59.6 63.4 62.9 61.1
RE
2O
3 15.3 16.3 14.9 18.2 13.9 15.2 15.1 13.1 13.6 14.0
Embodiment 7
30 gram NaY type molecular sieves are dispersed in the RECl that 300ml concentration is 15% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of preparation 500mL 2M
3)
3The aqueous solution is with rare earth containing zeolite and the above-mentioned Al (NO that obtains
3)
3Aqueous solution 60 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 550 ℃ of following roastings 2 hours.
Embodiment 8
30 gram NaY molecular sieves are dispersed in the RECl that 300ml concentration is 15% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.The NaAlO of preparation 500mL 3M
2The aqueous solution is with rare earth containing zeolite and the above-mentioned NaAlO that obtains
2Aqueous solution 90 ℃ of down reactions 1 hour, is filtered, and filter cake obtains combination of molecular sieve of the present invention through water wash, oven dry, 550 ℃ of following roastings 2 hours.
Embodiment 9
With 30 gram NaX type molecular sieve (commercial goods, the Al that XRF records
2O
3Content is 28 weight %, down with) be dispersed in the RECl that 300ml concentration is 10% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of preparation 500mL 0.5M
3)
3The aqueous solution is with rare earth X type molecular sieve and the above-mentioned Al (NO that obtains
3)
3Aqueous solution was reacted 1 hour down at 90-95 ℃, filtered, and filter cake is through water wash, and oven dry 550 ℃ of following roastings 2 hours, obtains combination of molecular sieve of the present invention.
Embodiment 10
30 gram NaX type molecular sieves are dispersed in the RECl that 300ml concentration is 15% (weight)
3In the aqueous solution, 90 ℃ of down exchanges 1 hour, filter, filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.The NH of preparation 500mL 1M
4Al (SO
4)
2The aqueous solution is with rare earth X type molecular sieve and the above-mentioned NH that obtains
4Al (SO
4)
2Aqueous solution was reacted 1 hour down at 90 ℃, filtered, and filter cake is through water wash, and oven dry 550 ℃ of following roastings 2 hours, obtains combination of molecular sieve of the present invention.
Table 2 has provided the XRF results of elemental analyses of the combination of molecular sieve that embodiment 1-10 and Comparative Examples 1 and 2 obtain.By table 2 data as can be seen, through the sample after the processing of aluminium salt, its Al
2O
3Content increases, and shows to have more aluminum ion in the sieve sample.
Table 2. combination of molecular sieve product elementary composition
| The combination of molecular sieve sample | Constituent content (in oxide compound) | ||||
| Total Al 2O 3(weight %) | SiO 2(weight %) | RE 2O 3(weight %) | Skeleton SiO 2/Al 2O 3(mol ratio) | The Al that adds 2O 3(weight %) | |
| Embodiment 1 | 25 | 69 | 5.2 | 4.68 | 1 |
| Embodiment 2 | 25 | 69 | 5.0 | 4.68 | 1 |
| Embodiment 3 | 20 | 71 | 7.6 | 7.24 | 7 |
| Embodiment 4 | 26 | 67 | 5.8 | 4.96 | 2 |
| Embodiment 5 | 15 | 78 | 5.4 | 13.95 | 5 |
| Embodiment 6 | 26 | 66 | 7.0 | 5.01 | 2 |
| Embodiment 7 | 26 | 66 | 7.9 | 5.11 | 2 |
| Embodiment 8 | 27 | 66 | 6.2 | 5.11 | 3 |
| Embodiment 9 | 33 | 53 | 12.7 | 2.75 | 5 |
| Embodiment 10 | 34 | 53 | 12.3 | 2.89 | 6 |
| Comparative Examples 1 | 24 | 71 | 4.8 | 4.69 | 0 |
| Comparative Examples 2 | 26 | 73 | 0 | 4.68 | 2 |
Embodiment 11
Present embodiment has provided the application of combination of molecular sieve of the present invention aspect absorption.This molecular sieve can be used as sorbent material, is applied to the adsorption desulfurize of catalytically cracked gasoline etc.
The combination of molecular sieve that embodiment 1-10 and Comparative Examples 1 and 2 are made is through compressing tablet, after pulverize, sieve (20-40 order), drying is 4 hours under 120 ℃, place moisture eliminator then, after reducing to room temperature, accurately take by weighing a certain amount of sorbent material, pour into and be equipped with in advance in the Erlenmeyer flask of FCC gasoline that sulphur content is 1216ppm (agent-oil ratio is 1: 5), whip attachment 5 hours ceaselessly under the room temperature.With sintered filter funnel oil solid two is separated, employing x ray fluorescence spectrometry (brief note is xrf method) is measured the variation of organosulfur in the gasoline of absorption front and back, calculates the adsorptive capacity and the desulfurization degree of sorbent material respectively.
Table 3 has provided the absorption property of this modified molecular screen to organosulfur in the gasoline.From table 3 data as can be seen, compare, be significantly increased through the absorption property of the molecular sieve after the modification to organosulfur in the gasoline with the molecular sieve before the modification.
Table 3 has also provided the NH of partially modified back molecular sieve
3The acid determination data of-TPD.As can be seen, behind the introducing aluminium, it is to NH in the molecular sieve
3Adsorptive capacity increase, the acid amount obviously increases, and illustrates on the molecular sieve of unit weight to have more acid sites, therefore, the catalytic activity of molecular sieve, absorption property, ion-exchange capacity etc. all will be improved greatly after the modification.
The organosulfur absorption property of table 3. modified molecular screen
Molecular sieve combination total acid content adsorptive capacity desulfurization degree
Matter sample (mmol/g) is (wt%) (mg/g)
Embodiment 1 1.924 3.06 50.4
Embodiment 2 1.760 2.97 48.8
Embodiment 3 1.743 3.00 49.4
Embodiment 4 1.893 3.06 50.3
Embodiment 5 1.467 2.42 36.8
Embodiment 6 1.601 2.58 42.4
Embodiment 7 1.408 2.40 39.4
Embodiment 8 1.516 2.30 37.8
Embodiment 9 1.572 2.49 40.1
Embodiment 10 1.395 2.38 38.8
Comparative Examples 1 1.188 2.37 38.9
Comparative Examples 2 1.290 2.25 34.7
Claims (6)
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| CN1322925C (en) * | 2004-02-27 | 2007-06-27 | 中国石油化工股份有限公司 | A hydrocarbon cracking catalyst with desulfurization function and its preparation method |
| CN1322926C (en) * | 2004-02-27 | 2007-06-27 | 中国石油化工股份有限公司 | A molecular sieve composition with desulfurization effect and its preparation method |
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