CN108786860B - Light alkane isomerization catalyst, preparation method and application - Google Patents
Light alkane isomerization catalyst, preparation method and application Download PDFInfo
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- CN108786860B CN108786860B CN201710305621.4A CN201710305621A CN108786860B CN 108786860 B CN108786860 B CN 108786860B CN 201710305621 A CN201710305621 A CN 201710305621A CN 108786860 B CN108786860 B CN 108786860B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 42
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title description 21
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000012188 paraffin wax Substances 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 36
- 239000012018 catalyst precursor Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 19
- 238000005660 chlorination reaction Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000002902 bimodal effect Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003058 platinum compounds Chemical class 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 230000002860 competitive effect Effects 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims 1
- VVKBUFYSWPMDNG-UHFFFAOYSA-N nitroxyl anion platinum(2+) Chemical compound N(=O)[Pt]N=O VVKBUFYSWPMDNG-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 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
- QRDXAXVMXIPGDB-UHFFFAOYSA-N 2-methylpropane;prop-1-ene Chemical group CC=C.CC(C)C QRDXAXVMXIPGDB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CDNBBXKOCUDMCC-UHFFFAOYSA-N but-1-ene;2-methylpropane Chemical compound CCC=C.CC(C)C CDNBBXKOCUDMCC-UHFFFAOYSA-N 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- -1 isobutane Chemical compound 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A light paraffin isomerization catalyst contains gamma-Al2O3A carrier and active components with the following content calculated by taking the carrier as a reference: 0.05 to 1.0 mass% of platinum and TiO20.01-2.0 mass% of chlorine, 2-12 mass% of chlorine, and gamma-Al2O3The carrier is distributed in a double-peak hole mode with large and small holes, the diameter of the largest possible holes of the small holes is 6-10 nm, and the diameter of the largest possible holes of the large holes is 12-20 nm. The catalyst has high isomerization activity and selectivity.
Description
Technical Field
The invention relates to a normal paraffin isomerization catalyst, a preparation method and application thereof, in particular to a light normal paraffin isomerization catalyst, a preparation method and application thereof.
Background
Isomerization of light paraffins generally refers to the isomerization of C4～C8The process of converting normal paraffin into isomeric paraffin. The isomerization product of n-butane, i.e. isobutane, is a raw material for important petrochemical processes such as isobutane dehydrogenation, isobutane-butene alkylation, isobutane-propylene co-oxidation and the like. C5、C6The octane value of the normal paraffin is lower, the octane value of the generated oil obtained after isomerization is obviously improved, and the isomerized generated oil has the characteristics of low sulfur content, no aromatic hydrocarbon and olefin, small difference value (only about 2 units) between the research method octane value and the motor method octane value, low density and the like, is an important blending component of the automobile gasoline, and is used for improving the gasolineThe distribution of the octane value of the oil fraction has important functions of improving the front-end octane value of the gasoline and improving the starting performance of the automobile.
In recent years, along with the continuous acceleration of the upgrading pace of gasoline in China and the rapid development of the petrochemical industry, the importance of light alkane isomerization as a technology for producing clean gasoline blending components and high-quality light hydrocarbon raw materials is increasingly highlighted.
The catalyst is the core of light paraffin isomerization technology, and the existing light paraffin isomerization technology can be divided into medium-temperature molecular sieve isomerization, solid super-strong acid isomerization and low-temperature isomerization according to different catalyst systems. The medium-temperature molecular sieve isomerization takes a Pt or Pd-loaded molecular sieve (usually mordenite or beta molecular sieve) as a catalyst, and the reaction temperature is 240-280 ℃. The solid superacid isomerization is usually carried out by taking Pt-loaded sulfated zirconia as a catalyst and the reaction temperature is 170-210 ℃. The low temperature isomerization is usually carried out by taking Pt-loaded chloridized alumina as a catalyst, and the reaction temperature is 120-200 ℃.
CN201210055961.3 discloses a straight-chain paraffin isomerization catalyst, which comprises a composite macroporous alumina carrier and platinum with the content of 0.01-2.0 mass percent calculated by taking the carrier as a reference, wherein the pore volume of the macroporous alumina is 1.0-1.8 ml/g. The catalyst is prepared by mixing macroporous alumina, chlorine-containing aluminum sol and hydrochloric acid, extruding into strips, and impregnating platinum-carrying with chloroplatinic acid solution.
CN201410295731.3 discloses a normal paraffin isomerization catalyst and a preparation method thereof, wherein the catalyst comprises 0.1-1.0% of metal Pt, 2-5% of element Cl and the balance of gamma-Al2O3The catalyst is prepared through impregnating Pt, reducing and adding AlCl3The inorganic chlorination is carried out by a sublimation method, and then the organic chlorination agent is used for processing.
CN201510502815.4 discloses a normal paraffin low-temperature isomerization catalyst and a preparation method thereof, wherein the catalyst is prepared from 0.1-1.0% of metal Pt, 5.0-10.0% of element Cl and the balance of gamma-Al2O3The catalyst adopts a liquid-phase impregnation chlorination mode to introduce chlorine, namely AlCl3Organic solvent of (2)Liquid immersion reduced Pt/gamma-Al2O3And then carrying out temperature programming to cure the chlorinating agent. The organic solvent in the organic solution is chloroform and/or ethyl acetate.
Cn201310502862.x discloses a method for preparing a catalyst for isomerization of alkanes, comprising the following steps: the alumina carrier is soaked in solution containing VIII family metal compound, the soaked solid is dried, roasted or treated with water and chlorine, soaked in alkane solution containing alkyl aluminum chloride and dried in the presence of inert gas and in anhydrous condition to obtain the catalyst. The alkyl aluminum chloride used for introducing chlorine by the method has activity , is easy to react with oxygen and trace water, needs to be dried under the conditions of inert gas and no water, and is complex to operate.
Disclosure of Invention
The invention aims to provide a light paraffin isomerization catalyst, a preparation method and application thereof.
The light alkane isomerization catalyst provided by the invention comprises gamma-Al2O3A carrier and active components with the following content calculated by taking the carrier as a reference:
0.05 to 1.0 mass% of platinum,
TiO20.01 to 2.0 mass%,
2 to 12% by mass of chlorine,
the gamma-Al2O3The carrier is distributed in a double-peak hole mode with large and small holes, the diameter of the largest possible holes of the small holes is 6-10 nm, and the diameter of the largest possible holes of the large holes is 12-20 nm.
The invention uses gamma-Al with bimodal pore distribution2O3The catalyst is used for light alkane isomerization reaction, has higher isomerization activity and selectivity, can reduce chlorine loss in the reaction process, and prolongs the one-way service life of the catalyst.
Drawings
FIG. 1 shows gamma-Al prepared in examples of the present invention and comparative examples2O3X-ray diffraction of the support(XRD) pattern.
FIG. 2 is a view showing γ -Al prepared in example 1 of the present invention2O3Pore distribution map of support ZT-1.
FIG. 3 is a graph of the pore distribution of catalyst A prepared in example 1 of the present invention.
FIG. 4 is a view showing γ -Al prepared in example 2 of the present invention2O3Pore distribution map of support ZT-2.
FIG. 5 is a pore distribution plot of catalyst B prepared according to example 2 of the present invention.
Detailed Description
The invention selects the bimodal gamma-Al with appropriate proportion of macropore distribution2O3The catalyst is prepared by loading active components as a carrier, and under the isomerization reaction condition of low temperature and high airspeed, reaction materials can be effectively diffused to the surface of the catalyst, so that the active center in the catalyst is fully utilized, and in addition, the introduction of the titanium component can further improve the isomerization activity and selectivity; the method for introducing chlorine into the catalyst is simple, the loss of chlorine in the preparation process of the catalyst is less, the loss of chlorine in the reaction process of the catalyst is correspondingly reduced, and the service life is prolonged.
Gamma-Al as catalyst of the invention2O3The carrier has bimodal pore distribution of small pores and large pores, the most probable pore diameter of the small pores is preferably 6-9.5 nm, and the most probable pore diameter of the large pores is preferably 12-16 nm.
The gamma-Al2O3The pore volume of the carrier is preferably 0.60 to 0.8ml/g, more preferably 0.6 to 0.7 ml/g.
The gamma-Al2O3In the carrier, the mass ratio of the small-hole alumina to the large-hole alumina is preferably 0.1-10, and more preferably 0.2-5.
The catalyst of the invention preferably has the following active component content:
0.1 to 0.5 mass% of platinum,
TiO20.02 to 1.0 mass%,
4 to 10 mass% of chlorine.
The preparation method of the catalyst provided by the invention comprises the following steps:
(1) will be provided withUniformly mixing two kinds of pseudo-boehmite powder with most probable pore diameters of 5-7.5 nm and 9-18 nm respectively, adding a peptizing agent aqueous solution, uniformly mixing, forming, drying and roasting to obtain the gamma-Al with bimodal pore distribution2O3A carrier, a carrier and a water-soluble polymer,
(2) mixing gamma-Al2O3Impregnating carrier with aqueous solution containing titanium compound, drying and roasting to obtain Ti-containing gamma-Al2O3A carrier, a carrier and a water-soluble polymer,
(3) the gamma-Al prepared in the step (2) is added2O3Impregnating carrier with aqueous solution containing platinum compound, drying, roasting, reducing with hydrogen gas to obtain catalyst precursor,
(4) subliming AlCl carried by hydrogen for the catalyst precursor obtained in the step (3)3Chlorination is carried out at 450-700 ℃.
The step (1) of the method is gamma-Al2O3The preparation method of the carrier comprises the steps of uniformly mixing two kinds of pseudo-boehmite powder, wherein the mass ratio of the two kinds of pseudo-boehmite powder is preferably 0.1-10, adding an aqueous solution of a peptizing agent, and uniformly kneading, wherein the peptizing agent is preferably at least one of nitric acid, acetic acid, citric acid, oxalic acid and formic acid, the concentration of an acid-containing aqueous solution is preferably 2-10% by mass, and the mass ratio of the acid-containing aqueous solution to the pseudo-boehmite powder is preferably 0.3-1.0. The shape of the shaped body may be a strip, pellet, tablet, granule or microsphere, preferably a strip, to be suitable for a fixed bed reactor. Drying and roasting the formed material to obtain the gamma-Al2O3And (3) a carrier. (1) The roasting temperature is preferably 500-650 ℃.
(1) The pore volume of the pseudo-boehmite powder with the most probable pore diameter of 5-7.5 nm is preferably 0.3-0.5 ml/g, and the pore volume of the pseudo-boehmite powder with the most probable pore diameter of 9-18 nm is preferably 0.54-0.8 ml/g.
The step (2) of the method is titanium-containing gamma-Al2O3And (3) preparing the carrier, and introducing titanium by adopting an impregnation method. The titanium-containing compound is preferably at least one of titanium sulfate, titanium sulfite and titanium oxalate. The titanium-containing compound during impregnationAqueous solution with gamma-Al2O3The mass ratio of the carrier is preferably 0.5 to 2.0.
The step (3) of the method is a step of preparing a catalyst precursor, wherein platinum is loaded on a carrier and reduced, and the platinum-containing compound used for preparing the impregnation liquid is preferably chloroplatinic acid, platinum tetrachloride, ammonium chloroplatinate or dinitroso diammineplatinum. Preferably, the aqueous solution containing the platinum compound further contains a competitive adsorbent, and the competitive adsorbent is preferably one or more of hydrochloric acid, trichloroacetic acid and nitric acid. Quality of impregnating solution and gamma-Al used in impregnating process2O3The mass ratio of the carrier is preferably 0.5 to 2.0.
In the method, the temperature for drying the impregnated solid is preferably 80-140 ℃, more preferably 100-130 ℃, the drying time is preferably 5-30 h, more preferably 8-24 h, the roasting temperature is preferably 450-650 ℃, more preferably 480-600 ℃, and the roasting time is preferably 1-10 h, more preferably 3-5 h.
The reduction is carried out in hydrogen flow, the volume ratio of gas to agent in the reduction process is preferably 300-1500, the reduction temperature is preferably 400-600 ℃, more preferably 450-580 ℃, and the reduction time is preferably 1-10 hours, more preferably 3-5 hours.
The step (4) of the process is to chlorinate the catalyst precursor to bring the chlorine content to the desired level. The chlorine loading method is to use sublimed AlCl3The catalyst precursor is treated. Mixing the AlCl3Heating to sublimation temperature above 178 deg.C, and adding H2Carrying sublimed AlCl as carrier gas3The steam is contacted with the catalyst precursor for chlorination, and the chlorination temperature is preferably 480-650 ℃.
(4) Step (2) using AlCl3In the chlorination of the catalyst precursor, AlCl3And the catalyst precursor is preferably 0.05 to 2.0, more preferably 0.1 to 1.5, in mass ratio, and the chlorination time is preferably 0.5 to 2.0 hours.
The volume ratio of the hydrogen to the catalyst precursor gas/agent in the chlorination process is preferably 100-2000, more preferably 200-1000. After the chlorination is finished, H is used2And blowing the catalyst to reduce the temperature to below 50 ℃.
The catalyst is suitable for isomerization reaction of light alkane, and the method for isomerizing the light alkane by using the catalyst comprises the step of enabling the light alkane to contact and react with the catalyst under the conditions of 100-300 ℃, 2.0-7.0 MPa (absolute pressure) and 0.01-5.0 hydrogen/hydrocarbon molar ratio.
The isomerization reaction of the light alkane by using the catalyst of the invention is preferably carried out at the temperature of 100-200 ℃, the pressure of 2.0-5.0 MPa, the hydrogen/hydrocarbon molar ratio of 0.05-1.0, and the mass space velocity of the light alkane in contact with the catalyst is 0.5-10.0 hr-1More preferably 1.0 to 7.0hr-1。
The light alkane is preferably C4～C8Such as n-butane, n-pentane, n-hexane, n-heptane, n-octane, either as pure n-alkanes or as n-alkane-containing materials, such as C-rich materials5/C6Reforming topping oil of normal alkane.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
The specific surface area and pore volume of pseudo-boehmite powder, support and catalyst in the examples and comparative examples were measured using a Micromeritics ASAP2400 static nitrogen auto-adsorber. The determination method comprises the following steps: degassing a sample at 300 ℃ and 1.33Pa for 4h, contacting liquid nitrogen with the sample at-196 ℃, statically achieving adsorption equilibrium, calculating specific surface area and pore volume by a BET method according to the difference between the nitrogen gas inflow and the volume of nitrogen gas remained in a gas phase after adsorption, and calculating the pore size distribution by using a BJH formula.
The Pt content of the catalyst is measured by adopting an Shimadzu UV2401PC ultraviolet-visible spectrophotometer, a sample is firstly dissolved by hydrochloric acid, and then is complexed by stannous chloride, and the Pt content is measured by a colorimetric method.
And (3) measuring the content of Ti in the catalyst by adopting an inductively coupled plasma spectrometer (ICP), dissolving a sample by using aqua regia, diluting the sample to a proper concentration by using deionized water, and measuring the content of Ti by using the ICP.
The Cl content of the catalyst is measured by adopting a Switzerland Vanton potentiometric titrator 905, a sample is firstly dissolved by NaOH to extract chloride ions, and then silver nitrate is used for titration to measure the Cl content.
Example 1
(1) Preparation of gamma-Al2O3Carrier
60.0g of pseudo-boehmite powder NB-1 (manufactured by Sasol Corp., alumina content: 75 mass%) and 40.0g of pseudo-boehmite powder NB-2 (manufactured by Sasol Corp., alumina content: 78 mass%) were mixed uniformly, and the physical properties of NB-1 and NB-2 are shown in Table 1. Adding 49.0g of 3 mass% nitric acid aqueous solution into the powder, stirring, kneading uniformly, extruding, drying at 120 deg.C for 10 hr, and calcining at 550 deg.C for 4 hr to obtain gamma-Al2O3The XRD pattern of the support ZT-1 is shown in FIG. 1, the specific surface area and the pore volume are shown in Table 2, the pore distribution is shown in FIG. 2, and it can be seen that ZT-1 is distributed in a bimodal manner, and the most probable pore diameters are respectively 8.2nm and 15.6 nm.
(2) Preparation of titanium-containing gamma-Al2O3Carrier
Adding 50.0gZT-1 into 33.0g aqueous solution containing 0.0751g titanium sulfate, soaking at 25 deg.C for 4h, drying the soaked solid at 120 deg.C for 15h, and calcining at 550 deg.C for 4h to obtain titanium-containing gamma-Al2O3And (3) a carrier.
(3) Preparation of catalyst precursor
30.0g of the titanium-containing gamma-Al prepared above was added2O3The carrier was added to 30.0g of an aqueous solution containing 0.1575g of chloroplatinic acid and 3 mass% hydrochloric acid, immersed at 25 ℃ for 1h, then the water in the solution was evaporated to dryness, dried at 130 ℃ for 10h, calcined at 510 ℃ for 4h, and reduced with hydrogen at 500 ℃ for 4h at a gas/agent volume ratio of 800 to prepare a catalyst precursor.
(4) Preparation of the catalyst
With H2Sublimed AlCl as carrier gas3The vapors are introduced into a reactor containing 20.0g of catalyst precursor, the catalyst precursor is chlorinated, and AlCl3The dosage of the (B) is 10.0g, the chlorination temperature is 520 ℃, the chlorination time is 1H, H2The gas/solvent volume ratio to the catalyst precursor was 600, and the introduction of H was continued after the chlorination had ended2The temperature was lowered to room temperature to obtain catalyst A, whose active component content (the same applies below), specific surface area and pore volume, calculated on the basis of the carrier, are shown in Table 2, and pore distribution is shown in FIG. 3.
Example 2
(1) Preparation of gamma-Al2O3Carrier
30.0g of pseudo-boehmite powder NB-3 (manufactured by Sasol Corp., alumina content: 74 mass%) and 70.0g of pseudo-boehmite powder NB-4 (manufactured by Sasol Corp., alumina content: 72 mass%) were mixed uniformly, and the physical properties of NB-3 and NB-4 are shown in Table 1. Adding 50.0g of 3.5 mass% nitric acid aqueous solution into the powder, stirring, kneading uniformly, extruding into strips, drying at 120 deg.C for 12h, and calcining at 550 deg.C for 4h to obtain gamma-Al2O3The XRD pattern of the carrier ZT-2 is shown in figure 1, the pore distribution is shown in figure 4, and the carrier ZT-2 is distributed in a bimodal mode, and the most probable pore diameters are respectively 6.6nm and 12.7 nm.
(2) Preparation of Ti-containing gamma-Al2O3Carrier
Adding 60.0g ZT-2 into 42.0g aqueous solution containing 0.2880g titanium sulfite, soaking at 25 deg.C for 4 hr, drying the soaked solid at 120 deg.C for 6 hr, and calcining at 550 deg.C for 3 hr to obtain titanium-containing gamma-Al2O3And (3) a carrier.
(3) Preparation of catalyst precursor
35.0g of the titanium-containing gamma-Al prepared above was added2O3The carrier was added to 35.0g of an aqueous solution containing 0.0882g of chloroplatinic acid and 2.5 mass% hydrochloric acid, immersed at 25 ℃ for 1h, then the water in the solution was evaporated to dryness, dried at 140 ℃ for 8h, calcined at 510 ℃ for 4h, and reduced with hydrogen at 500 ℃ for 4h, the gas/agent volume ratio upon reduction being 1000, to prepare a catalyst precursor.
(4) Preparation of the catalyst
With H2Sublimed AlCl as carrier gas3The vapors are introduced into a reactor containing 10.0g of catalyst precursor, the catalyst precursor is chlorinated, AlCl3The dosage of the (B) is 8.0g, the chlorination temperature is 520 ℃, the chlorination time is 1H, H2The gas/agent volume ratio of the catalyst precursor is 500, and H is continuously introduced after the chlorination is finished2The temperature is reduced to room temperature, catalyst B is prepared, the content of active components, the specific surface area and the pore volume which are calculated by taking the carrier as the reference are shown in Table 2, and the pore distribution is shown in FIG. 5.
Comparative example 1
A catalyst was prepared by following the procedure of example 1, except that the titanium introducing step of step (2) was not conducted, and the active component content, specific surface area and pore volume of the obtained catalyst C were as shown in Table 2.
Comparative example 2
A catalyst was prepared by following the procedure of example 2, except that the titanium introducing step of step (2) was not conducted, and the active component content, specific surface area and pore volume of the obtained catalyst D were as shown in Table 2.
Comparative example 3
The catalyst was prepared as in example 1, except that in step (1), only pseudo-boehmite powder NB-1 was used to prepare gamma-Al2O3The XRD pattern of the support ZT-3 is shown in figure 1, and the most probable pore diameter, specific surface area and pore volume are shown in table 2.
The catalyst was prepared by the method of steps (1), (2) to (4) using ZT-3 as a carrier to obtain catalyst E, the active component content, specific surface area and pore volume of which are shown in Table 2.
Comparative example 4
The catalyst was prepared as in example 1, except that in step (1), only pseudo-boehmite powder NB-2 was used to prepare gamma-Al2O3The XRD pattern of the support ZT-4 is shown in figure 1, and the most probable pore diameter, specific surface area and pore volume are shown in table 2.
The catalyst was prepared by the method of steps (1), (2) to (4) using ZT-4 as a support to obtain catalyst F, whose active component content, specific surface area and pore volume are shown in Table 2.
Comparative example 5
The catalyst was prepared as in example 2, except that only the pseudo-boehmite powder NB-3 was used in the preparation of γ -Al in the step (1)2O3The XRD pattern of the support ZT-5 is shown in figure 1, and the most probable pore diameter, specific surface area and pore volume are shown in table 2.
The catalyst was prepared by the method of steps (2) to (4) of example 2 using ZT-5 as a support to obtain catalyst G, whose active component content, specific surface area and pore volume are shown in Table 2.
Comparative example 6
The catalyst was prepared as in example 2, except that only the pseudo-boehmite powder NB-4 was used in the preparation of γ -Al in the step (1)2O3Carrying out carrier preparation to obtain a carrier ZT-6, wherein an XRD pattern of the carrier ZT-6 is shown in the figure1, the most probable pore diameter, specific surface area and pore volume are shown in Table 2.
The catalyst was prepared by the method of steps (2) to (4) of example 2 using ZT-6 as a carrier to obtain catalyst H, whose active component content, specific surface area and pore volume are shown in Table 2.
Examples 3 to 10
The following examples examine catalyst C5/C6Isomerization reaction performance.
The catalyst of the present invention and the comparative catalyst were evaluated on a small fixed bed reaction apparatus using a mixed hydrocarbon containing 20 mass% of n-pentane and 80 mass% of n-hexane as a raw material under the following evaluation conditions: the reaction temperature is 130 ℃, the reaction pressure (gauge pressure) is 3.0MPa, and the feed mass space velocity is 2.0hr-10.25 hydrogen/hydrocarbon molar ratio and 10h reaction time, the average result of 10h being shown in Table 3.
In Table 3
C5Isomerization ratio (mass of isopentane in product/C in product)5Mass of alkane) × 100%;
C6isomerization ratio (1- (mass of n-hexane in product/C in product)6Mass of alkane)) × 100%;
C6selectivity (mass of 2, 2-dimethylbutane in product/C in product)6The mass of the alkane) × 100%
As can be seen from Table 3, the catalyst of the present invention has a higher C than the comparative catalyst5Isomerization ratio, C6Isomerization ratio and C6And (4) selectivity.
Examples 11 to 18
The following examples examine the n-butane isomerization reaction performance of the catalyst.
In the purity of>99.8% by mass of n-butane as a reaction raw material, the catalyst of the present invention and the comparative catalyst were evaluated on a small fixed bed reactor under the following conditions: 170 deg.C, 3.0MPa, and feed mass air speed of 5.0hr-1The hydrogen/hydrocarbon molar ratio was 0.1, the reaction time was 5h, and the results are given in Table 4, taking the average of 5 h.
In Table 4
N-butane conversion ═(mass of n-butane in the raw material-mass of n-butane in the product)/mass of n-butane in the raw material) × 100%;
isobutane selectivity (mass of isobutane in product/(mass of n-butane in raw material-mass of n-butane in product)) × 100%
As can be seen from Table 4, the catalyst of the present invention has higher n-butane conversion and isobutane selectivity than the comparative catalyst.
Example 19
This example examines C for catalyst A of the invention and catalyst C prepared in comparative example 15/C6And (3) isomerization reaction stability.
A mixed hydrocarbon containing 20 mass% of n-pentane and 80 mass% of n-hexane was used as a raw material, and the catalyst was evaluated in a small fixed bed reactor under the following conditions: the reaction temperature is 130 ℃, the reaction pressure (gauge pressure) is 3.0MPa, and the feed mass space velocity is 2.0hr-1Hydrogen/hydrocarbon molar ratio of 0.25, continuously reacting for 800 hours under the condition, analyzing the product composition on line every 2 hours in the reaction process, and obtaining C5Isomerization ratio, C6Isomerization ratio and C6The selectivity and results are shown in Table 5.
As can be seen from Table 5, catalyst A of the present invention has higher stability than comparative catalyst C.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
Claims (17)
1. A light paraffin isomerization catalyst contains gamma-Al2O3A carrier and active components with the following content calculated by taking the carrier as a reference:
0.05 to 1.0 mass% of platinum,
TiO20.01 to 1.0 mass%,
2 to 12% by mass of chlorine,
the gamma-Al2O3The carrier is distributed in a double-peak hole mode with large and small holes, the diameter of the largest possible holes of the small holes is 6-10 nm, and the diameter of the largest possible holes of the large holes is 12-20 nm.
2. The catalyst of claim 1, wherein said γ -Al is2O3In the carrier, the diameter of the most probable pore of the small pore is 6-9.5 nm, and the diameter of the most probable pore of the large pore is 12-16 nm.
3. Catalyst according to claim 1 or 2, characterized in that the γ -Al is2O3The pore volume of the carrier is 0.60-0.80 ml/g.
4. Catalyst according to claim 1 or 2, characterized in that the γ -Al is2O3In the carrier, the mass ratio of the small holes to the large-hole alumina is 0.1-10.
5. The catalyst according to claim 1 or 2, characterized in that the active component content is:
0.1 to 0.5 mass% of platinum,
TiO20.02 to 0.5 mass%,
4 to 10 mass% of chlorine.
6. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) uniformly mixing two kinds of pseudo-boehmite powder with most probable pore diameters of 5-7.5 nm and 9-18 nm respectively, adding a peptizing agent aqueous solution, uniformly mixing, forming, drying and roasting to obtain the gamma-Al with bimodal pore distribution2O3A carrier, a carrier and a water-soluble polymer,
(2) mixing gamma-Al2O3Impregnating carrier with aqueous solution containing titanium compound, drying and roasting to obtain Ti-containing gamma-Al2O3A carrier, a carrier and a water-soluble polymer,
(3) the gamma-Al prepared in the step (2) is added2O3Impregnating carrier with aqueous solution containing platinum compound, drying, roasting, reducing with hydrogen gas to obtain catalyst precursor,
(4) subliming AlCl carried by hydrogen for the catalyst precursor obtained in the step (3)3Chlorination is carried out at 450-700 ℃.
7. The method according to claim 6, wherein the calcination temperature in step (1) is 500 to 650 ℃.
8. The method according to claim 6, wherein the pore volume of the pseudo-boehmite powder with the most probable pore diameter of 5 to 7.5nm in step (1) is 0.3 to 0.5ml/g, and the pore volume of the pseudo-boehmite powder with the most probable pore diameter of 9 to 18nm is 0.54 to 0.8 ml/g.
9. The method according to claim 6, wherein the mass ratio of the two kinds of pseudo-boehmite powder in the step (1) is 0.1-10, and the forming method is extrusion molding.
10. The method according to claim 6, wherein the peptizing agent in step (1) is at least one selected from the group consisting of nitric acid, acetic acid, citric acid, oxalic acid and formic acid.
11. The method according to claim 6, wherein the titanium-containing compound in the step (2) is at least one of titanium sulfate, titanium sulfite and titanium oxalate.
12. The method according to claim 6, wherein the platinum-containing compound in step (3) is chloroplatinic acid, platinum tetrachloride, ammonium chloroplatinate or dinitrosoplatinum.
13. The method according to claim 6, wherein the aqueous solution containing platinum compound in step (3) further contains a competitive adsorbent selected from one or more of hydrochloric acid, trichloroacetic acid and nitric acid.
14. The method of claim 6, wherein said step (4) comprises using AlCl3In the chlorination of the catalyst precursor, AlCl3And the catalyst precursor is 0.05-2.0 by mass, and the chlorination time is 0.5-2.0 hours.
15. A light alkane isomerization method, which comprises the step of contacting and reacting light alkane with the catalyst of claim 1 under the conditions of 100-300 ℃, 2.0-5.0 MPa and hydrogen/hydrocarbon molar ratio of 0.01-5.0.
16. The method of claim 15, wherein the light alkane is contacted with the catalyst at a mass space velocity of 0.5 to 10.0hr-1。
17. The process of claim 15, wherein the light alkane is C4～C8Of (a) an alkane.
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| Publication number | Publication date |
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| CN108786860A (en) | 2018-11-13 |
| RU2018116071A3 (en) | 2022-02-01 |
| RU2018116071A (en) | 2019-10-28 |
| MY189119A (en) | 2022-01-26 |
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