CN103041844B - Isomerization catalyst containing modified mordenite and application thereof - Google Patents
Isomerization catalyst containing modified mordenite and application thereof Download PDFInfo
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- CN103041844B CN103041844B CN201110313264.9A CN201110313264A CN103041844B CN 103041844 B CN103041844 B CN 103041844B CN 201110313264 A CN201110313264 A CN 201110313264A CN 103041844 B CN103041844 B CN 103041844B
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- modenite
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- halogen
- isomerization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 33
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 24
- 150000002367 halogens Chemical class 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 7
- -1 C12 alkane Chemical class 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 238000009992 mercerising Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical group CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical class CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QSKKXNSTGHZSQB-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.[Pt+2] QSKKXNSTGHZSQB-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses an isomerization catalyst containing modified mordenite and an application thereof. The catalyst is prepared from the following components in percentage by weight: 0.01-5% of noble metal element in the group VIII, 10-80% of phosphorus-modified mordenite, 0.1-10% of additives and the balance of binder containing 0.5-5.0% of halogen, wherein the weight of phosphorus in the modified mordenite accounts for 0.1-10%. The catalyst is used for the isomerization of C4-C12 alkane, has the characteristics of high catalytic activity and high isoolefine selectivity and can be used for producing the high-octane gasoline blending component.
Description
Technical field
The present invention relates to a kind of catalyst for isomerizing light hydrocarbon and application thereof, in particular, the present invention relates to a kind of isomerization catalyst containing modified mordenite and the application of this catalyst in the reaction of C4 ~ C12 alkane isomerization.
Background technology
Under certain conditions, n-alkane is the undesirable components in oil product, and the isomerization reaction of n-alkane is the important reaction in petroleum refining process.Especially mix in the catalytic gasoline of refining residual oil, sulphur and olefin(e) centent are all higher.Carry out hydrodesulfurization and Olefin decrease to gasoline, sulfur content can be down to 10 below μ g/g, olefin(e) centent is down to below 10v%, but reduces octane number greatly simultaneously.To not losing or situation decline low-sulfur, the olefin(e) centent of little loss octane number, then need to carry out selective hydrogenation cracking or isomerization.The RON of isoparaffin is higher than the n-alkane of same carbon number a lot.Such as, nC
6rON be 24.8, and 2,2-dimethyl C
4be 91.8; NC
7be 0, trimethyl C
4be 112.1, dimethyl C
5be 81 ~ 93.Obvious hydroisomerizing is more effective to octane value recovering.In China's gasoline, more than 80% from catalytically cracked gasoline component, and hydroisomerizing seems particularly important for raising octane number.Therefore by small-molecular-weight (C
5/ C
6) n-alkane change into isoparaffin to improve the octane number of light oil distillate, thus the octane number tool improving gasoline is of great significance.
Catalyst plays the role of a nucleus in n-alkane hydroisomerization technology.One of conventional isomerization method for light hydrocarbon more than 250 DEG C, carries out hydroisomerization reaction with zeolite type bifunctional catalyst.Hydroisomerisation catalysts is bifunctional catalyst, not only has hydrogenation-dehydrogenation activity but also have acid active.The difunctional isomerization catalyst of described zeolite type mainly refers to crystalline silicate to be carrier, and aluminium oxide or other refractory oxide are binding agent, load VIII race metal, mainly the catalyst prepared of platinum or palladium.The carrier of this kind of catalyst has acid function, can impel normal alkane isomerization, and carrier used at present mainly contains X-type zeolite, y-type zeolite and modenite.Acid carrier must have the effect of following several respects: the effective surface area increasing catalyst; Suitable pore structure is provided; Acid centre is provided; Improve the mechanical strength of catalyst; Improve the heat endurance of catalyst; Increase the poison resistance of catalyst; Save the consumption of metal component, reduce costs.Different molecular sieve and the solid acid, acidic oxide etc. of similar molecular sieve are commonly used to do acidic components, but are carrier mainly with molecular sieve in actual production and in studying, and because it has larger specific area, have the duct of suitable pore volume Sum fanction simultaneously.Common aluminosilicate-type molecular sieve is as Y, β, ZSM-5, ZSM-22, ZSM-11, ZSM-23 etc.; SAPO molecular sieve analog is as SAPO-11, SAPO-31, SAPO-41 etc.Wherein, remove the application such as cationic Y zeolite, beta-molecular sieve, modenite comparatively wide, this is main because they have the molecular sieve pore passage of stronger acidic character and distinctive geometrical rule.Metal component is the source of hydrogenation-dehydrogenation activity, and hydrogenation of olefins can be capped to avoid coking and acid centre rapidly by it, thus plays the effect of protection acid centre, and hygrogenating isomerization reaction is carried out smoothly.Metal component is generally selected from VIII race and VI B race element in the periodic table of elements, can be divided into noble metal and base metal two class.The former is based on (Pt), (Pd) etc., and use mainly with metal simple-substance form, the latter mainly contains molybdenum (Mo), (Ni), (Co), (W) etc., uses, can improve activity and the stability of catalyst like this mainly with the oxide morphology be combined with each other.Precious metal catalyst activity is the highest, only needs the hydroisomerizing that just can increase substantially bifunctional catalyst on a small quantity active.
USP4,232,181, GB1039246, GB1189850, USP4,665, the preparation method of such catalyst all described in detail by 272 patent documents such as grade, but due to the application of temperature of zeolite type bifunctional catalyst higher, and under high temperature, the equilibrium concentration of isomerized products is lower, particularly to n-hexane, higher reaction temperature will affect the concentration of 2,2-dimethylbutanes (2,2-DMB) in isomerized products, and 2,2-DMB has very high octane number, if its concentration reduces, will directly affect the octane number of isomerized products.Therefore improve the acidity of modenite further, the stereoselectivity improving it seems very necessary.
US6198015 proposes a kind of hydroisomerization catalyst, and the carrier that it is characterized by catalyst is made up of NU-10 molecular sieve and binding agent.US4440871, US5135638 and CN1392099A propose a kind of hydroisomerization catalyst, it is characterized in that adopting SAPO-11 molecular sieve and the molecular sieve carried noble metal platinum of nanometer SAPO-11.CN86102384A etc. are for C
4~ C
7the isomerization of straight-chain low-carbon hydrocarbon proposes a kind of hydroisomerization catalyst, it is characterized in that catalyst carrier is made up of modified mordenite and binding agent.However, the preparation of more highly active hydroisomerization catalyst, also also exists very large improvement space, and be especially applicable to the composite synthetic technology of catalyst carrier and scheme day by day when maturation, this improvement can be achieved.
Summary of the invention
For the deficiencies in the prior art, the invention provides and be a kind ofly carrier with modified mordenite and hydroisomerization catalyst adding auxiliary agent and its preparation method and application.This catalyst is used for the isomerization process of low-carbon alkanes, has catalytic activity and the selective high of isomeric olefine, can effectively improve the octane number improving them.
The present invention is containing modified mordenite isomerization catalyst, by weight percentage, this catalyst has following composition: the binding agent of the VIIIth race's precious metal element 0.01% ~ 5%, P Modification modenite 10% ~ 80%, auxiliary agent 0.1% ~ 10%, surplus halogen-containing 0.5% ~ 5.0%, wherein the weight content of P elements in P Modification modenite is 0.1% ~ 10.0%.
In catalyst of the present invention, phosphorus-containing compound load becomes P Modification modenite on modenite, and halogen mixes as binding agent with inorganic refractory oxide, and VIII race's precious metal element and auxiliary agent adopt infusion process load.
In catalyst of the present invention, the SiO of P Modification modenite
2/ Al
2o
3mol ratio is 5 ~ 70, and be preferably 10 ~ 60, the content of P Modification modenite is preferably 20% ~ 70% in catalyst by weight percentage; Described P Modification modenite is the h-type zeolite containing P elements.The zeolite of direct synthesis generally contains the cation of alkali metal or alkaline-earth metal, method by roasting after the ammonium ion exchange of routine obtains h-type zeolite, then load P elements obtains P Modification modenite, also can pass through conventional modification, as hydrothermal treatment consists, acid treatment etc.The weight content of P elements in P Modification modenite is preferably 0.5% ~ 5.0%.In the mixture of the described binding agent containing halogen, the weight content (in butt) of halogen is preferably 1.0% ~ 3.0%; Described halogen is one or more in fluorine, chlorine and bromine, is preferably chlorine.In catalyst of the present invention, the VIIIth race's precious metal element is preferably platinum and/or palladium, most preferably is platinum, and content is in the catalyst preferably 0.1% ~ 3.0% in metal.Described auxiliary agent rhenium and/or tin, weight content is in the catalyst preferably 0.5% ~ 5.0% in metal.Described inorganic refractory oxide is be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide and/or kaolin, is more preferably aluminium oxide.
It is the isomerization reaction being suitable for small-molecular-weight n-alkane that catalyst of the present invention is applicable to catalytic reaction, particularly C4 ~ C12 alkane isomerization reaction, is best suited for the reaction of C5-C7 alkane isomerization.The form using catalyst can be fixed bed, also can be fluid bed.Catalytic process is: first reduced by catalyst, and reasonable reducing condition is: temperature 550 ~ 650 DEG C, 5 ~ 15 hours recovery times.It is 200 ~ 350 DEG C that isomerization reaction temperature controls, and is preferably 230 ~ 300 DEG C; Pressure is 1.0 ~ 3.0MPa, is preferably 0.5 ~ 2.0 MPa; Feed weight air speed is 0.2 ~ 10.0h
-1, be preferably 0.5 ~ 5.0h
-1; Hydrogen hydrocarbon mol ratio (hydrogen and alkane mol ratio) is 0.5 ~ 10.0, is preferably 1.0 ~ 8.0.
The key component of catalyst of the present invention is the modenite of P elements modification and the binding agent containing halogen.Owing to selecting P elements, modification is carried out to molecular sieve, acted on by the sour position of phosphorus and molecular sieve, such acid strength of molecular sieve that can make reduces, the lytic activity of catalyst is down to minimum, avoid the side reaction such as coking and carbon distribution of strong acidic site, the activity of catalyst and stability are all significantly improved.With the Acidity of time modulation molecular sieve surfaces externally and internally and the pore passage structure of molecular sieve.Make the acid site intensity on molecular sieve surface and acid strength distribution meet alkane isomerization reaction requirement to the modulation object of acidity, improve the heterogeneous activity of catalyst; Owing to containing aluminium oxide or silica in binding agent, through halogen modified binding agent, can produce a large amount of L acid sites, L acid position electron acceptor can affect, and can improve the isomerization reaction performance of catalyst.Catalyst of the present invention adds again auxiliary agent rhenium and/or tin, and can improve the decentralization of noble metal component by introducing auxiliary agent, this may be because auxiliary agent can form alloy phase with noble metal, thus avoids the gathering of metal.Catalyst can not only be made to provide more active sites, and can content of metal be reduced, reduce Catalyst Production cost.
Detailed description of the invention
There is provided a kind of concrete preparation method of catalyst of the present invention below, but be not limited thereto method, concrete steps are:
(1) preparation of P Modification modenite: by the aqueous impregnation h-mordenite of phosphorus-containing compound, then through conventional drying and roasting, obtain P Modification modenite;
(2) by material thick for abundant to aluminium hydroxide, halogen compounds, peptizing agent and deionized water epoxy glue melt into, as the binding agent of preparation catalyst of the present invention;
(3) binding agent modified mordenite obtained for step (1), step (2) obtained, extrusion aid become plastic paste, extruded moulding with the abundant kneading of water, through super-dry and roasting, obtain catalyst carrier of the present invention;
(4) VIII element and auxiliary agent are loaded in the obtained catalyst carrier of step (3), through super-dry and roasting, obtain catalyst of the present invention.
In step (1), described phosphorus-containing compound is selected from phosphoric acid, hydrophosphate or dihydric phosphate, as ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) etc.Gu control the liquid of phosphorus-containing compound solution/than being 1 ~ 10(unit during dipping: mL solution/g solid), dipping temperature 10 ~ 90 DEG C, dip time 1 ~ 24 hour.
The preparation method of the binding agent described in step (2) can mix simultaneously, and namely the predecessor of inorganic refractory oxide, halogen-containing solution, peptizing agent and water are fully mixed, peptization becomes thick material.Prepare halogen-containing solution compound used be selected from hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid one or more, be preferably hydrochloric acid and/or ammonium chloride, be more preferably ammonium chloride.Also substep mixing can be adopted, namely first halogen contained compound is fully mixed with the precursor of inorganic refractory oxide, and then fully mix with peptizing agent and water, peptization becomes thick material, wherein halogen contained compound be selected from hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid one or more, be preferably hydrochloric acid and/or ammonium chloride, be more preferably ammonium chloride.Inorganic refractory oxide is be selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, be preferably aluminium oxide and/or kaolin, be more preferably aluminium oxide, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit in aluminium stone one or more.
Peptizing agent described in step (2) is inorganic acid or organic acid, is preferably inorganic acid, is more preferably hydrochloric acid and nitric acid, most preferably is nitric acid; Wherein the mass concentration of salpeter solution used is 1.0% ~ 30.0%, and be preferably 1.0% ~ 5.0%, consumption is that plastic block is as the criterion can make kneading material.
Extrusion aid described in step (3) is the material being conducive to extruded moulding, can be selected from graphite, starch, cellulose and sesbania powder one or more, be preferably sesbania powder, by weight percentage, its amount added is 0.5% ~ 10% of carrier butt weight, is preferably 1% ~ 5%.
The mode that step (4) noble metal and auxiliary agent are added in catalyst can adopt infusion process or ion-exchange, is preferably infusion process.Can step impregnation be adopted, also can adopt and flood simultaneously.Conventional activity component impregnation solution is the aqueous solution containing active metal soluble compound, such as platinum acid chloride solution, platinum ammonium complex solution, palladium ammonium complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof, described rhenium-containing auxiliary agent is perrhenic acid, and stanniferous auxiliary agent is butter of tin or stannous chloride solution.
Step (1), (3) and the drying condition described in (4) are that normal temperature ~ 300 DEG C keep 1h ~ 48h, and step (1), step (3) can be identical with the drying condition described in step (4), also can be different.The roasting condition of step (1), (3) and (4) is 400 DEG C ~ 800 DEG C and keeps 0.5h ~ 10.0h, and step (1), step (3) can be identical with the roasting condition described in step (4), also can be different.
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.And with small fixed reaction unit, isomeric hexane reaction test is carried out to catalyst provided by the invention and comparative catalyst.Loaded by isomerization catalyst in small fixed reactor, charge weight is 10 milliliters, is warming up to 600 DEG C, passes into hydrogen reducing 4 hours, then 250 DEG C, pass into n-hexane under 1.47MPa condition and carry out isomerization reaction, reaction feed weight space velocity is 1.0h
-1, hydrogen hydrocarbon mol ratio is 2.7, reaction result in table 2, the isomerization rate in table 2 and selective by the following method calculate (weight content):
Isomerization rate=(isomery C
6hexane content in content/product) * 100%
Isomerisation selectivity=(in 2,2DMB content/product hexane content) * 100%.
embodiment 1 (if do not have special indicating below, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1) phosphate aqueous solution of (1) configuration 0.5mol/L, then adopts method and the modenite (SiO of incipient impregnation
2/ Al
2o
3mol ratio is 18), 80 DEG C of dippings are after 2 hours, and through 120 DEG C of oven dry, in 550 DEG C of air, roasting 5 hours, obtains modified mordenite, be designated as S-1, and wherein the weight content of P elements in zeolite is 1.5%.
(2) be that 10%(is in halogen by 200 gram mass concentration) ammonium chloride solution, 450 grams of (in aluminium oxide) aluminium hydroxides (SB that German Condean company produces), 1000ml water and 60ml red fuming nitric acid (RFNA)s (mass concentration is 66.5%), fully mix.Obtain the adhesive (in butt) that halogen weight content is 3.2%.
(3) get the obtained modified mordenite of 120 grams of steps (1), the binding agent that 100 grams of (2) steps obtain, 6 grams of sesbania powder become plastic paste with the abundant kneading of appropriate water, extruded moulding (diameter 1.5 millimeters), drying 16 hours at 100 DEG C, then in air atmosphere, 550 DEG C of roastings obtain catalyst carrier of the present invention in 4 hours, and bearer number is ES-1.
(4) 100 grams of ES-1 are used containing perrhenic acid and H
2ptCl
6the saturated dipping of solution, and then 100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h in air atmosphere, the obtained catalyst of the present invention containing 1.2wt%, 0.6wt%Pt, is numbered E-1, and its catalyst composition is in table 1, and reaction result is in table 2.
embodiment 2
The preparation of catalyst E-2 of the present invention
The preparation process of catalyst E-2 of the present invention is with embodiment 1, and difference is to replace ammonium chloride with ammonium bromide, and replace phosphoric acid with ammonium dihydrogen phosphate aqueous solution, the catalyst of the present invention prepared, is numbered E-2, and its catalyst composition is in table 1, and reaction result is in table 2.
embodiment 3
The preparation of catalyst E-3 of the present invention
The preparation process of catalyst E-3 of the present invention is with embodiment 1, and difference is to replace phosphoric acid with ammonium dibasic phosphate aqueous solution, and the catalyst of the present invention prepared, is numbered E-3, and its catalyst composition is in table 1, and reaction result is in table 2.
embodiment 4 ~ 7
The preparation of catalyst E-4 ~ E-7 of the present invention
The preparation process of catalyst E-4 ~ E-7 of the present invention is with embodiment 1, and difference phosphorus-containing compound used, molecular sieve, halogen are different with the amount of rhenium, the catalyst E-4 ~ E-7 of the present invention prepared, and its catalyst composition is in table 1, and reaction result is in table 2.
comparative example 1
The preparation of comparative catalyst C-1 of the present invention.
The preparation method of catalyst is with embodiment 1, and difference is that molecular sieve used is without the process of the phosphorus-containing compound aqueous solution, and be numbered C-1, the composition of its catalyst is in table 1, and reaction result is in table 2.
comparative example 2
Prepared by comparative catalyst C-2 of the present invention.
The preparation method of catalyst is with embodiment 2, and difference is that molecular sieve used is without the process of the phosphorus-containing compound aqueous solution, also not containing halogen in adhesive.Be numbered C-2, its physico-chemical property is in table 1, and reaction result is in table 2.
comparative example 3
Prepared by comparative catalyst C-3 of the present invention.
The preparation method of catalyst is with embodiment 6, and difference is that molecular sieve used is without the process of the phosphorus-containing compound aqueous solution, not containing halogen in binding agent.Also not containing auxiliary agent in catalyst, be numbered C-3, its physico-chemical property is in table 1, and reaction result is in table 2.
The main physico-chemical property (weight percentage) of table 1 catalyst
| Catalyst | Phosphorus element-containing/modified molecular screen, % | Halogen/binding agent, % | Pt,% | Auxiliary agent, % | Pd,% |
| E-1 | 1.5/50.0 | 3.2/ surplus | 0.3 | 0.8⑦ | - |
| E-2 | 1.5/50.0 | 1.8/ surplus | - | 1.2⑦ | 0.4 |
| E-3 | 1.5/50.0 | 1.5/ surplus | 0.4 | 1.5⑧ | - |
| E-4 | 5.0/30.0 | 0.8/ surplus | 0.2 | 2.3⑦ | 0.2 |
| E-5 | 4.1/60.0 | 2.2/ surplus | 1.0 | 3.8⑧ | 0.1 |
| E-6 | 2.3/70.0 | 1.1/ surplus | - | 5.0⑦ | 1.5 |
| E-7 | 3.9/80.0 | 4.6/ surplus | 1.3 | 2.7⑧ | -- |
| C-1 | 0/50.0 | 1.5/ surplus | 1.0 | 2.1⑦ | 0.3 |
| C-2 | 0/30.0 | 0/ surplus | 0.8 | 3.1⑧ | 0.4 |
| C-3 | 0/70.0 | 0/ surplus | 1.5 | - | 1.8 |
note:table 1 Middle molecule sieve is h-mordenite, is aluminium oxide except particularly pointing out binding agent.
Phosphorus element content with modified molecular screen weight for benchmark; Modified molecular screen content take catalyst weight as benchmark; Content of halogen take weight of binder as benchmark; Binder content take catalyst weight as benchmark; In E-3, binding agent is 30wt% kaolin and remainder alumina, 7. refers to auxiliary agent rhenium, 8. refers to auxiliary agent tin.
Table 2 evaluating catalyst result (percentage by weight)
| Catalyst | Product < C 5，% | Product 22DMB, % | Product nC 6，% | Conversion ratio, % | Isomerization rate, % | Isomerisation selectivity, % |
| E-1 | 0.83 | 18.53 | 15.89 | 84.12 | 83.98 | 18.68 |
| E-2 | 0.62 | 18.08 | 17.3 | 82.7 | 82.60 | 18.20 |
| E-3 | 0.87 | 17.58 | 16.19 | 83.82 | 83.68 | 18.73 |
| E-4 | 0.81 | 17.00 | 17.08 | 82.93 | 82.79 | 17.15 |
| E-5 | 0.64 | 18.23 | 16.32 | 83.68 | 83.58 | 18.35 |
| E-6 | 0.84 | 18.63 | 16.51 | 83.49 | 83.35 | 18.79 |
| E-7 | 0.77 | 17.68 | 16.77 | 83.23 | 83.1 | 17.82 |
| C-1 | 1.18 | 6.7 | 21.27 | 78.73 | 78.48 | 6.78 |
| C-2 | 1.17 | 5.6 | 22.36 | 77.64 | 77.38 | 5.67 |
| C-3 | 1.25 | 4.80 | 42.24 | 57.76 | 57.23 | 4.9 |
In table 2,22DMB is 2,2-methybutane; NC
6for n-hexane.
As can be seen from Table 2, compared with being the catalyst prepared of carrier with modenite, catalyst prepared by the present invention has higher conversion ratio and isomerisation selectivity.And the component output being less than C5 is also lower, that is carries out light hydrocarbon isomerization reaction with catalyst of the present invention, higher liquid yield can be obtained, more high-knock rating gasoline can be produced.
Claims (9)
1. the isomerization catalyst containing modified mordenite, it is characterized in that, in catalyst weight percent, catalyst consists of: the binding agent of the VIIIth race's precious metal element 0.01% ~ 5%, P Modification modenite 10% ~ 80%, auxiliary agent rhenium and/or tin 0.1% ~ 10%, surplus halogen-containing 0.5% ~ 5.0%; Wherein the weight content of P elements in P Modification modenite is 0.1% ~ 10.0%.
2. according to catalyst according to claim 1, it is characterized in that: phosphorus-containing compound load becomes P Modification modenite on modenite, halogen mixes as binding agent with inorganic refractory oxide, and VIII race's precious metal element and auxiliary agent adopt infusion process load.
3. according to catalyst according to claim 1, it is characterized in that: the SiO2/Al2O3 mol ratio of P Modification modenite is 5 ~ 70, in catalyst weight percent, the content of P Modification modenite is 20% ~ 70%, and described P Modification mercerising boils
Stone is the h-type zeolite containing P elements.
4. according to the catalyst described in claim 1 or 3, it is characterized in that: the weight content of P elements in P Modification modenite is 0.5% ~ 5.0%.
5. according to catalyst according to claim 1, it is characterized in that: in the mixture of the binding agent containing halogen, the weight content of halogen counts 1.0% ~ 3.0% with butt.
6. according to the catalyst described in claim 1 or 5, it is characterized in that: halogen is one or more in fluorine, chlorine and bromine.
7. according to catalyst according to claim 1, it is characterized in that: the VIIIth race's precious metal element is platinum and/or palladium, and content in the catalyst counts 0.1% ~ 3.0% with metal.
8. the application of catalyst described in the arbitrary claim of claim 1 to 7 in the reaction of C4 ~ C12 alkane isomerization.
9. according to application according to claim 8, it is characterized in that: isomerization reaction temperature is 200 ~ 350 DEG C, pressure is 1.0 ~ 3.0MPa, and feed weight air speed is 0.2 ~ 10.0h-1, and hydrogen hydrocarbon mol ratio is 0.5 ~ 10.0.
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| CN1384176A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Reforming catalyst containing molecular sieve |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Synthesis method of nanometer mordenite molecular sieve |
| CN101091920A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing composite molecular sieve of ZSM 5/ mordenite |
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| CN1384176A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Reforming catalyst containing molecular sieve |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Synthesis method of nanometer mordenite molecular sieve |
| CN101091920A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing composite molecular sieve of ZSM 5/ mordenite |
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