WO2015092812A2 - A modified faujasite zeolite - Google Patents
A modified faujasite zeolite Download PDFInfo
- Publication number
- WO2015092812A2 WO2015092812A2 PCT/IN2014/000731 IN2014000731W WO2015092812A2 WO 2015092812 A2 WO2015092812 A2 WO 2015092812A2 IN 2014000731 W IN2014000731 W IN 2014000731W WO 2015092812 A2 WO2015092812 A2 WO 2015092812A2
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- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- modified
- faujasite zeolite
- modified faujasite
- ranges
- Prior art date
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000010457 zeolite Substances 0.000 title claims abstract description 200
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 183
- 239000012013 faujasite Substances 0.000 title claims abstract description 132
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 50
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 40
- 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 abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 230000002152 alkylating effect Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkali metal acetate Chemical class 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims description 14
- 229910052792 caesium Inorganic materials 0.000 claims description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 229910052701 rubidium Inorganic materials 0.000 claims description 12
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 claims description 7
- 239000006200 vaporizer Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052706 scandium Inorganic materials 0.000 claims description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- IBTDLPRFBAMMJB-UHFFFAOYSA-M [Fr+].CC([O-])=O Chemical compound [Fr+].CC([O-])=O IBTDLPRFBAMMJB-UHFFFAOYSA-M 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 229910052730 francium Inorganic materials 0.000 claims description 3
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
Definitions
- the present disclosure relates to a modified faujasite zeolite.
- the present disclosure also relates to a process for preparing a modified faujasite zeolite.
- Zeolites are crystalline metallosilicates mainly aluminosilicates based on alkali or alkaline earth metals with an uniform pore size which may be represented by an empirical formula M 2 O.Al 2 0 3 .xSi0 2 .yH 2 0 wherein M represents an alkali metal cation, x is an integer from 2.5 to 6, and y is an integer from 6 to 9.
- zeolites These pores of uniform size create a ring system which allows the zeolite to selectively interact with the molecules of particular dimensions and shapes.
- the size of the ring system in zeolites depends on the number of Oxygen atoms present in the ring system.
- the zeolites having intermediate to large size ring . system are used for various applications in the industry. For instance, large pore zeolites such as faujasite zeolites X and ultrastable Y are widely used in petroleum refining processes such as FCC and hydrocracking.
- US20110270006 discloses a process for preparing the metal exchanged zeolite by reacting cesium hydroxide (CsOH) as a first promoter and nitrate of the second promoter selected from the group consisting of Fe, Cr, Ce, Mo, Sn, Bi, Ag, Cu, and combinations thereof with a zeolite substrate.
- CsOH cesium hydroxide
- US5015796 discloses a process for preparing an alkaline earth metal exchanged zeolites by reacting nitrates of alkaline earth metals with zeolites.
- US4483936 discloses a zeolite catalyst comprising at least one alkali metal selected from the group consisting of Cs, K, and Rb; at least one metal selected from the Group of metals consisting of Li, Ce, Cr, and Ag; and at least one member selected from the group consisting of boron and phosphorus. It also discloses a process for the preparation of said zeolite catalyst. In the process, hydroxide of the alkali metal is reacted with a zeolite to obtain a partially modified zeolite which is reacted with Boron phosphate and then with nitrate of metal to obtain said catalyst composition.
- US4463204 discloses a zeolite selected from the group consisting of sodium form of zeolite X or Y exchanged first with potassium and then with cesium.
- the sodium in the zeolite is at least 90% exchanged for potassium and cesium.
- the processes of the prior art includes the use of metal nitrates and/or metal hydroxides for exchanging the metal present in the zeolite and imparting acidic/basic property to the zeolite.
- the drawbacks associated with the processes involving the use of metal nitrates is that nitrate ions generated during the reaction cause corrosion of the equipment being used. Further, the nitrate ions impart high acidity to the zeolite which requires a large quantity of water to remove acidity and balance acidic-basic property of the zeolite. Washing the zeolite with a large quantity of water has a disadvantage of leaching alkali metal cation. Due to this concurrent existence of drawbacks the required balance of acidic and basic properties in the resulting zeolite cannot be achieved. The processes involving the use of metal hydroxides for preparing zeolites with balanced acidic and basic properties also suffer from the drawbacks similar to the process involving the use of alkali metal nitrates.
- a modified faujasite zeolite comprising at least one zeolite selected from the group consisting of sodium form of faujasite zeolite X and sodium form of faujasite zeolite Y exchanged with at least two alkali metals selected from the group consisting of lithium (Li), potassium (K), rubidium (Rb), cesium (Cs) and franc ium (Fr), wherein,
- the molar ratio of silica to alumina present in the modified faujasite zeolite ranges between 1 : 1 and 1:15,
- the amount of sodium in the modified faujasite zeolite is in the range of 3 to 10 wt%
- the particle size of said modified faujasite zeolite ranges between 20 and 200 micron
- the modified faujasite zeolite is in the form selected from the group consisting of pellets, extradites, extrudates, spheres, granules and tablets, wherein the particle size of the modified faujasite zeolite in said form ranges between 0.05 and 10 mm.
- the molar ratio of silica to alumina present in the modified faujasite zeolite ranges between 1:1 and 1:1.2
- the modified faujasite zeolite of the present disclosure further comprises at least one promoter selected from the group of cations consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), lanthanum (La), boron (B), scandium (Sc), ytterbium (Y), zirconium (Zr), niobium (Nb), cerium (Ce), neodymium (Nd), copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), gallium (Ga) and indium (In) in an amount ranging between 0.01 and 15 wt%.
- the pore diameter of the modified faujasite zeolite ranges between 15 and 40 angstrom.
- the surface area of the modified faujasite zeolite ranges between 200 and 600 m 2 /g.
- the weight ratio of first alkali metal to the second alkali metal ranges between 1:2.5 and 2.5:1.
- a modified faujasite zeolite wherein the zeolite is the sodium form of faujasite zeolite X and the alkali metals are potassium (K) in an amount ranging between 0.1 and 25 wt%, rubidium (Rb) in an amount ranging between 0.1 and 40 wt% and cesium (Cs) in an amount ranging between 0.1 and 37 wt%, wherein, the molar ratio of silica to alumina present in the modified faujasite zeolite ranges between 1:1 and 1:1.2; and the amount of sodium in the modified faujasite zeolite is in the range of 3 to 10 wt%
- a modified faujasite zeolite wherein the zeolite is the sodium form of faujasite zeolite X and the alkali metals are rubidium (Rb) in an amount ranging between 0.5 and 50 wt% and cesium (Cs) in an amount ranging between 0.2 and 40 wt%, wherein, the molar ratio of silica to alumina present in the modified faujasite zeolite ranges between 1:1 and 1:1.2; and the amount of sodium in the modified faujasite zeolite is in the range of 3 to 10 wt%.
- Rb rubidium
- Cs cesium
- a process for preparing a modified faujasite zeolite comprising the following steps: i. treating at least one faujasite zeolite, at least once, with at least one first alkali metal acetate in the presence of a liquid medium to obtain an alkali metal exchanged faujasite zeolite,
- the particle size of said modified faujasite zeolite ranges between 20 and 200 micron; the amount of sodium in the modified faujasite zeolite is in the range of 3 to 10 wt%; the sum total of at least two alkali metals in said modified faujasite zeolite is in the range of 0.1 wt% and 97 wt%; and the ratio of said first alkali metal to the second alkali metal ranges between 1 :2.5 and 2.5:1.
- the modified faujasite zeolite obtained by the process of the present disclosure is in the form selected from the group consisting of pellets, extradites, extrudates, spheres, granules and tablets, wherein the particle size of the modified faujasite zeolite in said form ranges between 0.05 and 10 mm.
- the modified faujasite zeolite obtained by the process of the present disclosure is characterized by the pore diameter in the range of 15 arid 40 angstrom and the surface area in the range of 200 and 600 m 2 /g.
- the process of the present disclosure further comprises a method step of adding at least one promoter in an amount ranging between 0.01 and 15 wt%.
- the promoter is selected from the group of cations consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), lanthanum (La), boron (B), scandium (Sc), ytterbium (Y), zirconium Zr, niobium (Nb), cerium (Ce), neodymium (Nd), copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), gallium (Ga) and indium (In).
- the method steps of treating and retreating are carried out at a temperature ranging between 70 and 130 °C for a time period ranging between 2 and 10 hours.
- the faujasite zeolite is selected from the group consisting of sodium form of faujasite zeolite X and sodium form of faujasite zeolite Y.
- the molar ratio of silica to alumina present in the modified faujasite zeolite ranges between 1:1 and 1: 15.
- the first alkali metal acetate and the second alkali metal acetate are selected from the group consisting of lithium acetate (CH3COOLi), potassium acetate (CH3COOK), rubidium acetate (CH3COORb), cesium acetate (CH3COOCs) and francium acetate (CH3COOFr).
- the liquid medium is selected as deionized distilled water.
- the method step of drying is carried out at a temperature ranging between 100 °C and 140 °C for a time period in the range of 8 to 20 hours.
- the method step of calcination is carried out at a temperature ranging between 450 °C and 600 °C for a time period in the range of 2 and 8 hours in the presence of at least one gas selected from the group consisting of air and nitrogen.
- a process for alkylating at least one alkyl group present on an aromatic compound comprising the following steps: i. mixing an aromatic compound comprising at least one alkyl group, alkanol and passing through a vaporizer at a temperature range of 125 to 250 °C to produce the vapors of reaction mixture, and
- the process of the present disclosure comprises a pre-step of activating the modified faujasite zeolite by heating at a temperature of 400 °C and 600 °C for a time period of 0.5 and 6 hours under inert conditions.
- the aromatic compound comprising at least one alkyl group is represented by a Formula I,
- R is selected from the group consisting of CI to C5 alkyl group, and n is an integer ranging between 1 and 6.
- the alkanol is represented by a Formula II,
- R' is selected from the group consisting of CI to CIO straight chain or branched or cyclic alkyl group.
- the aromatic compound comprising at least one alkyl group is toluene, the alkanol is methanol and the alkylated alkyl aromatic compound is styrene.
- the inventors of the present disclosure developed a novel modified faujasite zeolite.
- the modified faujasite zeolite comprises at least one zeolite exchanged with at least two alkali metals.
- the zeolite is selected from the group consisting of sodium form of faujasite zeolite X and sodium form of faujasite zeolite Y whereas the alkali metal is selected from the group consisting of lithium (Li), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
- the sodium metal present in the sodium form of faujasite zeolites is at least partially exchanged with the alkali metals.
- the amount of sodium retained in the zeolite plays an important role in maintaining the balance between acidic and basic properties of the modified zeolite.
- the inventors after several experiments optimized the amount of sodium in the modified zeolite in the range of 3 to 10 wt% to obtain desired balance of acidic and basic properties.
- the modified zeolite of the present invention is characterized by silica to alumina molar ratio in the range of 1: 1 to 1:15 and particle size in the range of 20 to 200 micron. Typically, the silica to alumina molar ratio ranges between 1 : 1 and 1 : 1.2.
- the modified faujasite zeolite of the present disclosure is in the form selected from the group consisting of pellets, extradites, extrudates, spheres, granules and tablets and the particle size of the modified faujasite zeolite in said form ranges between 0.05 and 10 mm.
- the properties of the modified zeolite depend on the extent to which the balance between surface acidity and basicity is achieved.
- the balance between surface acidity and basicity is achieved by imparting at least two alkali metals to the sodium form of zeolite X or Y in an amount ranging between 0.1 % and 97 wt%.
- the properties of the modified faujasite zeolite of the present disclosure depend largely on the balance of acidic and basic properties which is the result of exchange of at least two alkali metals, it will be evident to express the molar ratio of the first alkali metal to the second alkali metal. Accordingly, the weight ratio of the first alkali to the second alkali metal ranges between 1 :2.5 and 2.5: 1.
- Further balance of surface acidity and basicity may be imparted to the modified faujasite zeolite of the present disclosure by using at least one promoter selected from the group of cations consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), lanthanum (La), boron (B), scandium (Sc), ytterbium (Y), zirconium (Zr), niobium (Nb), cerium (Ce), neodymium ( d), copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), gallium (Ga) and indium (In) in an amount ranging between 0.01 and 15 wt%.
- the performance of the modified faujasite zeolite also depends on the pore diameter and the surface area of the modified faujasite zeolite. To obtain achieve optimum performance of the modified faujasite zeolite the pore diameter of the modified faujasite zeolite ranges between 15 and 40 angstrom and the surface area of the modified faujasite zeolite ranges between 200 and 600 m 2 /g.
- the modified faujasite zeolite that possesses improved properties comprises sodium form of faujasite zeolite X exchanged with potassium in an amount ranging between 0.1 and 25 wt%, rubidium in an amount ranging between 0.1 and 40 wt%, and cesium in ah amount ranging between 0.1 and 37 wt%.
- the amount of sodium present in the zeolite exchanged with potassium, rubidium and cesium ranges between 3 and 10 wt% and the molar ratio of silica to alumina ranges between 1:1 and 1: 1.2.
- Another, modified faujasite zeolite that possesses improved properties comprises sodium form of faujasite zeolite X exchanged with rubidium in an amount ranging between 0.5 and 50 wt%, and cesium in an amount ranging between 0.2 and 40 wt%.
- the amount of sodium present in the zeolite exchanged with rubidium and cesium ranges between 3 and 10 wt% and the molar ratio of silica to alumina ranges between 1 : 1 and 1 : 1.2.
- sodium form of zeolite X, sodium form of zeolite Y or a combination thereof is treated with at least one; first alkali metal acetate in the presence of a liquid medium to obtain an alkali metal exchanged faujasite zeolite.
- the zeolite may be treated with the first alkali metal acetate only once or iteratively till the required degree of alkali metal is exchanged for sodium metal.
- the alkali metal exchanged faujasite zeolite obtained after first treatment is then again treated with at least one second alkali metal acetate in the presence of a liquid medium to obtain slurry containing a modified faujasite zeolite.
- the alkali metal exchanged faujasite zeolite is also treated with the second alkali metal acetate only once or iteratively till the required exchange of alkali metal is attained.
- the liquid medium used in both the steps is deionized distilled water.
- the alkali metal acetate used in the first and the second step obviates the shortcomings related to the use of alkali metal hydroxides and nitrates.
- the alkali metal acetate for the purpose of the present disclosure is selected from the group consisting of lithium acetate (CH3COOLi), potassium acetate (CH3COOK), rubidium acetate (CH3COO b), cesium acetate (CH3COOCs) and francium acetate (CH3COOFr).
- the first and the second step are independently carried out a temperature ranging between 70 and 130 °C for a time period ranging between 2 and 10 hours.
- the promoter selected from the group of cations consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), lanthanum (La), boron (B), scandium (Sc), ytterbium (Y), zirconium Zr, niobium (Nb), cerium (Ce), neodymium (Nd), copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), gallium (Ga) and indium (In) may be added before, during or after the first step and the second step.
- the amount in which promoter is added ranges between 0.01 and 15 wt%.
- the slurry containing the modified faujasite zeolite obtained in the second step is separated in the third step to obtain a residue containing the modified faujasite zeolite.
- the separation may be executed by using any technique known to a person skilled in the art.
- the residue containing the modified faujasite zeolite is obtained by filtration.
- the residue containing the modified faujasite zeolite is washed with deionized distilled water and dried at a temperature ranging between 100 and 140 °C for a time period ranging between 8 and 20 hours.
- the dried modified faujasite zeolite is then subjected to calcination to obtain the modified faujasite zeolite.
- the calcination is carried out at a temperature ranging between 450 and 600 °C for a time period ranging between 2 and 8 hours in the presence of air or nitrogen or combination thereof.
- the modified faujasite zeolite obtained according to the process of the present disclosure is characterized by the molar ratio of silica to alumina in the range of 1:1 to 1:15, preferably 1:1 and 1:1.2.
- the modified faujasite zeolite is also characterized by the presence of 3 and 10 wt% of sodium and the particle size of 20 and 200 micron.
- the sum total of at least two alkal i metals in the modified faujasite zeolite obtained by the process of the present disclosure ranges between 0.1 wt% and 97 wt% and the ratio of first alkali metal to the second alkali metal ranges between 1:2.5 and 2.5:1.
- the modified faujasite zeolite of the present disclosure is in the form selected from the group consisting of pellets extradites, extrudates, spheres, granules and tablets and the particle size of the modified faujasite zeolite in said form ranges between 0.05 and 10 mm. Still further, the modified faujasite zeolite obtained by the process of the present disclosure has a pore diameter in the range of 15 to 40 angstrom and the surface area in the range of 200 and 600 m 2 /g.
- R is selected from the group consisting of CI to C5 alkyl group, and n is an integer ranging between 1 and 6.
- R' is selected from the group consisting of CI to CIO straight chain or branched or cyclic alkyl group.
- the mixture of an aromatic compound of formula I and alkanol of formula II is fed to the vaporizer at a temperature of 125 to 250 °C to produce the vapors of a reaction mixture. Then the vapors of the reaction mixture are brought in the contact with the modified faujasite zeolite of the present disclosure in a catalytic amount at a temperature in the range of 250 to 600 °C and at a pressure ranging between 1 atm and 5 atm to obtain an alkylated alkyl aromatic compound.
- the progress of the reaction, selectivity for the desired product and yield of the product depends on the ratio of the reactants. Accordingly, the ratio of the aromatic compound of formula I to the alkanol of formula II ranges between 1:10 and 10: 1.
- the modified faujasite zeolite before mixing with aromatic compound of formula I and alkanol of formula II may be optionally, activated by heating at a temperature of 400 and 600 °C for a time period of 0.5 and 6.0 hours under inert conditions. Inert conditions during activation of the modified faujasite zeolite may be maintained by using inert gas which includes but is not limited to nitrogen.
- the modified faujasite zeolite of the present disclosure is used in a catalytic amount to selectively prepare styrene by reacting toluene and methanol.
- the process involving the use of the modified faujasite zeolite of the present disclosure exhibits high methanol conversion with selectivity for styrene in the range of 60 to 82%.
- Cs-Rb-Na-X zeolite prepared as described in example 1 was mixed with 50 mL solution containing 0.071 g of boric acid in de-ionized distilled water under continuous stirring to obtain Cs-Rb-Na-X zeolite comprising 1 wt% boron oxide.
- the promoter loaded catalyst was dried at 120 °C for 16 h followed by calcination at 540 °C for 6 h.
- Example 3 Preparation of Cs-Rb-Na-X zeolite comprising lanthanum (promoter)
- Cs-Rb-Na-X zeolite prepared as described in example 1 was mixed with 50 mL solution containing 0.0776 g of lanthanum acetate salt in de-ionized distilled water under continuous stirring to obtain Cs-Rb-Na-X zeolite comprising 1 wt% lanthanum oxide.
- the promoter loaded catalyst was dried at 120 °C for 16 h followed by calcination at 540 °C for 6 h.
- Rb-Cs-Na-X zeolite prepared as described in example 4 was mixed with 50 mL solution containing 0.071 g of boric acid in de-ionized distilled water under continuous stirring to obtain Rb-Cs-Na-X zeolite comprising 1 wt% boron oxide.
- the promoter loaded catalyst was dried at 120 °C for 16 h followed by calcination at 540 °C for 6 h.
- Rb-Cs-K-Na-X zeolite prepared as described in example 6 was mixed with 50 mL solution containing 0.071 g of boric acid in de-ionized distilled water under continuous stirring to obtain Rb-Cs-K-Na-X zeolite comprising 1 wt% boron oxide.
- the promoter loaded catalyst was dried at 120 °C for 16 h followed by calcination at 540 °C for 6 h.
- the resulting slurry was filtered and washed with warm deionized distilled water.
- the filter cake was dried in an oven at 120 °C for 16 h and calcined in a temperature programmed furnace at 540 °C for 6 h in air.
- Examples 9-16 Synthesis of styrene using zeolites of examples 1 to 8
- Comparative example 1-4 Synthesis of styrene using zeolites exchanged with one alkali metal
- the modified faujasite zeolite of the present disclosure i.e., a zeolite exchanged with at least two alkali metals exhibits enhanced selectivity for styrene.
- the word "comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
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|---|---|---|---|
| IN3676/MUM/2013 | 2013-11-22 | ||
| IN3676MU2013 IN2013MU03676A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 2013-11-22 | 2014-11-24 |
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