CN1286562C - Normal paraffin isomerization catalyst and its preparing method - Google Patents
Normal paraffin isomerization catalyst and its preparing method Download PDFInfo
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- CN1286562C CN1286562C CN 200410029870 CN200410029870A CN1286562C CN 1286562 C CN1286562 C CN 1286562C CN 200410029870 CN200410029870 CN 200410029870 CN 200410029870 A CN200410029870 A CN 200410029870A CN 1286562 C CN1286562 C CN 1286562C
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- phosphorus
- beta zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 22
- 239000012188 paraffin wax Substances 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010457 zeolite Substances 0.000 claims abstract description 29
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011574 phosphorus Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- -1 aluminum alkoxide Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000008043 acidic salts Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002101 lytic effect Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QSKKXNSTGHZSQB-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.[Pt+2] QSKKXNSTGHZSQB-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an isomerization catalyst for normal alkane, which is prepared from 0.01 to 2.0 mass% of VIII group metal, 0.2 to 1.0 mass% of phosphorus and a composite carrier, wherein the composite carrier is prepared from 10 to 80 mass% of mordenite, 10 to 80 mass% of Beta zeolite and 10 to 50 mass% of alumina. The catalyst is suitable for the isomerization reaction of alkane containing more than 7 C atoms and has high activity and isomerization selectivity, and the liquid yield of an isomerization product is high.
Description
Technical field
The present invention is a kind of catalyst for normal paraffin isomerization and preparation method thereof, specifically, is a kind of catalyst for normal paraffin isomerization that contains zeolite component and preparation method thereof.
Background technology
At present, with C
5, C
6N-alkane changes into isoparaffin, is the effective ways of producing the clean gasoline of high-octane rating, low-sulfur, no aromatic hydrocarbons and alkene.Isomerization method for light hydrocarbon commonly used is to carry out hydroisomerization reaction with the zeolite type bifunctional catalyst at 220～300 ℃.The difunctional isomerization catalyst of described zeolite type mainly is meant with the crystalline silicate to be carrier, and aluminium oxide or other refractory oxide are binding agent, and supported V III family metal mainly is the catalyst of platinum or palladium preparation.The carrier of this class catalyst has acid function, can impel normal alkane isomerization, and used Zeolite support mainly contains X type zeolite, y-type zeolite and modenite.Because be subjected to the restriction of catalyst performance, above-mentioned catalyst can only be used for C
4～C
6The isomerization reaction of n-alkane.For C
7Above n-alkane, if use above-mentioned catalyst to carry out isomerization reaction, then the cracking catalyst activity is too high, and it is low to cause the liquid of product to be incorporated, and the selectivity of process is low.
CN1304793A discloses a kind of middle temp isomerizing catalyst, and this catalyst carrier is the mixture of zirconia and tungsten oxide and H β, and metal active constituent is a platinum.Its carrier adopts the mechanical mixing preparation, introduces platinum with infusion process in complex carrier.This catalyst can obviously improve middle temperature (240～280 ℃) the isomerization selectivity of normal heptane, keeps advantages of high catalytic activity simultaneously.
Carrier is to be selected from the oxide of Nd, Ce or Cr and the compound that H β forms in the disclosed middle temp isomerizing catalyst of CN1305871A, and metal active constituent is Pt in the catalyst.This catalyst adopts mechanical mixing to prepare complex carrier equally, adopts infusion process to introduce platinum.This catalyst can improve the isomerization product yield of normal heptane in middle temperature (240～280 ℃) reaction, has advantages of high catalytic activity simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst for normal paraffin isomerization and preparation method, this catalyst has higher activity and isomerization selectivity, and activity stability is good, and method for preparing catalyst is simple, easy operating.
Catalyst for normal paraffin isomerization provided by the invention comprises the VIII family metal of 0.01～2.0 quality %, phosphorus and the complex carrier of 0.2～1.0 quality %, and described complex carrier comprises the modenite of 10～80 quality %, the Beta zeolite of 10～80 quality % and the aluminium oxide of 10～50 quality %.
The present invention carries out modification with phosphorus to complex carrier and makes catalyst, and it is minimum to make the lytic activity of catalyst reduce to, and therefore, can improve the liquid yield of normal alkane isomerization product, improves isomerization selectivity and enhanced activity stability.
Description of drawings
Fig. 1 is the stability experiment result of catalyst of the present invention.
The specific embodiment
Carrier is the complex carrier that contains two kinds of zeolite component in the catalyst of the present invention, and with phosphorus complex carrier is carried out modification, again supported V III family metal active constituent.Preferred 0.2～0.6 quality % of phosphorus content in the catalyst.
Also comprise aluminium oxide in the described complex carrier, preferred 15.0～40.0 quality % of its content.The high purity aluminium oxide that preferred aluminum alkoxide hydrolysis makes, this high purity aluminium oxide is selected from high-carbon (C
4Above) aluminum alkoxide the hydrolysis high purity aluminium oxide or the low-carbon (LC) (C that make
4Below) high purity aluminium oxide that makes of aluminum alkoxide hydrolysis, or the mixture of the two, the method preparation that the high purity aluminium oxide that described low-carbon alkoxy aluminium hydrolysis makes adopts CN1032951A to announce.
Preferred 30.0～75.0 quality % of Beta zeolite content in the complex carrier.The silica of modenite and Beta zeolite is 5～80, and preferred 10～60.
Preferred platinum of VIII family metal or palladium in the described catalyst, the preferred 0.05-0.8 quality of its content %.
Method for preparing catalyst provided by the invention comprises h-mordenite, Hydrogen Beta zeolite and aluminium hydroxide mixing aftershaping, make complex carrier after drying, the roasting, with phosphorus-containing compound solution impregnation complex carrier, VIII family metal is introduced in dry, roasting again.
Described h-mordenite, Hydrogen Beta zeolite adopt the routine techniques preparation.As na-pretreated zeolite is carried out ion-exchange with acid or acidic salt solution under 90～95 ℃,, be preferably less than the h-type zeolite of 0.08 quality % to make sodium content less than 0.3 quality %.Hydrochloric acid is generally selected in acid used in the ion exchange process for use, and its concentration is preferably 0.1～5.0 mol, and used acidic salt solution is generally selected ammonium chloride solution for use.Described ion exchange process can repeat repeatedly, till the silica of zeolite reaches requirement.
After the forming method that the preparation catalyst adopts preferably mixes in proportion h-mordenite and Hydrogen Beta zeolite and aluminium oxide, adding rare nitric acid or extrusion aids such as acetic acid, citric acid mixes and pinches, and then extrusion molding, 20～150 ℃ of dryings, 450～650 ℃ of roastings make complex carrier.The carrier of extrusion molding is stripe shape preferably, also can be other shape, as sheet shape, cloverleaf pattern.The method of carrier moulding also can adopt the method for dripping ball or spin to make the ball-type carrier except that extrusion molding.
The described phosphorus-containing compound of above-mentioned preparation method is selected from phosphoric acid, hydrophosphate or dihydric phosphate, also can be the sodium salt or the sylvite of hydrophosphate or dihydric phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.The solid liquid/than being 1～10 of control phosphorus-containing compound solution during dipping, 10～100 ℃ of dipping temperatures, preferred 0.5～10 hour of dip time, dipping is filtration afterwards, gained solid drying, roasting is promptly got the complex carrier of phosphorus modification.
The present invention adopts the method for dipping to introduce VIII family metal in complex carrier, and the amount of flooding the solution of the used VIII of containing family metal should make bullion content wherein satisfy desired bullion content in the catalyst.Flood the used preferred chloroplatinic acid of compound, the acid of chlorine palladium, platinum ammonium complex ion, the palladium ammonium complex ion that contains VIII family metal.The volume ratio of maceration extract and carrier preferred 3～12: 1, dipping back carrier drying, roasting make catalyst.
Baking temperature described in the catalyst preparation process is 100～120 ℃, and sintering temperature is 450～650 ℃.
Catalyst of the present invention is applicable to C
7The hydroisomerization reaction of above n-alkane.Suitable isomerization reaction condition is 200～300 ℃ of temperature, preferred 220～290 ℃; Pressure 0.5～3.0MPa, preferred 1.0-2.0MPa; Charging mass space velocity 0.2～10.0 hour
-1, preferred 0.5～3.0 hour
-1Hydrogen/hydrocarbon mol ratio 0.5～10.0, preferred 1～8.0.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalyst of the present invention.
(1) preparation complex carrier
Get 100 gram sodium type modenites, its composition sees Table 1, handles 3 hours at 93 ℃ with the HCl of 600 milliliter of 1 mol, filters, washs to filtrate with deionized water and be neutrality, and SiO is made in 600 ℃ of roastings 6 hours
2/ Al
2O
3Mol ratio 23.4 (fluorescence spectrum method for measuring), sodium content are the h-mordenite of 0.056 quality %.
Get 100 gram sodium type Beta zeolites (Fushun No.3 Petroleum Factory's production), its composition sees Table 1, makes the Hydrogen Beta zeolite that sodium content is 0.08 heavy % by above-mentioned ion-exchange process.
With the composition of above-mentioned processing such as h-mordenite, Hydrogen Beta zeolite and high purity aluminium oxide (the SB powder of table 1, Germany CONDEA company produces) be that 40: 40: 20 ratio mixes in the butt mass ratio, the salpeter solution that added volume ratio and be 1: 1 mixes to be pinched, add nitric acid and solid powder volume ratio be 1: 1.6, extruded moulding, 120 ℃ of dryings 2 hours, 550 ℃ of roastings made complex carrier a in 4 hours.
(2) introduce the phosphorus constituent element
Get 20 gram complex carrier a, with the KH of 100 milliliter of 0.5 mol
2PO
4In 60 ℃ of dippings 3 hours, to filter, wash to filtrate with deionized water and be neutral, the complex carrier of phosphorus modification is made in 550 ℃ of roastings 4 hours.
(3) introduce the platinum constituent element
Get 20 gram complex carrier a, flooded 24 hours with the platinum acid chloride solution of 7.5 milliliters of 8.6 milligrams of Pt/ milliliters, 120 ℃ of dryings 4 hours, roasting made catalyst A in 4 hours in 550 ℃ of air, and the composition of catalyst A sees Table 2, and wherein phosphorus content is recorded by fluorescence method.
Example 2
Method by example 1 prepares complex carrier, and the butt mass ratio of different is h-mordenite, Hydrogen Beta zeolite and high purity aluminium oxide is 20: 60: 20, and the complex carrier note that makes is made b.
Get 20 gram complex carrier b, with the KH of 150 milliliter of 0.5 mol
2PO
4In 60 ℃ of dippings 3 hours, to filter, wash to filtrate with deionized water and be neutral, the complex carrier of phosphorus modification is made in 550 ℃ of roastings 4 hours.Press the method in 1 (3) step of example again and introduce platinum, make catalyst E, its composition sees Table 2.
Example 3
Method by example 1 prepares complex carrier, and the butt mass ratio of different is h-mordenite, Hydrogen Beta zeolite and high purity aluminium oxide is 60: 20: 20, and the complex carrier note that makes is made c.
Get 20 gram complex carrier c, with the KH of 80 milliliter of 0.5 mol
2PO
4In 60 ℃ of dippings 3 hours, to filter, wash to filtrate with deionized water and be neutral, the complex carrier of phosphorus modification is made in 550 ℃ of roastings 4 hours.Press the method in 1 (3) step of example again and introduce platinum, make catalyst F, its composition sees Table 2.
Example 4
Get 20 gram complex carrier a, introduce the complex carrier that the phosphorus constituent element makes the phosphorus modification by the method for example 1, the chlorine palladium acid solution with 5 milliliters of 20 milligrams of Pd/ milliliters flooded 24 hours then, 120 ℃ of dryings 4 hours, roasting made catalyst B in 4 hours in 550 ℃ of air, and its composition sees Table 2.
Comparative Examples 1
Get 20 gram complex carrier a, flooded 24 hours with the platinum acid chloride solution of 7.5 milliliters of 8.6 milligrams of Pt/ milliliters, 120 ℃ of dryings 4 hours, roasting made catalyst C in 4 hours in 550 ℃ of air, and its composition sees Table 2.
Comparative Examples 2
Get 20 gram complex carrier a, flooded 24 hours with the chlorine palladium acid solution of 5 milliliters of 20 milligrams of Pd/ milliliters, 120 ℃ of dryings 4 hours, roasting made catalyst D of the present invention in 4 hours in 550 ℃ of air, and its composition sees Table 2.
Example 5
This example carries out evaluation test to catalyst performance.
The 7 gram catalyst of in the small stationary bed bioreactor, packing into, catalyst volume is 11 milliliters, and 450 ℃ fed hydrogen reducing 2 hours, fed normal heptane then under 220 ℃, 1.6MPa condition and carried out isomerization reaction, and the reaction feed mass space velocity is 1.2 hours
-1, hydrogen/hydrocarbon mol ratio is 4.Reaction result sees Table 3.
As shown in Table 3, the catalyst of the present invention's preparation is compared with the comparative catalyst under higher reaction temperature, still have higher isomerization selectivity, and lytic activity is relatively low under same reaction temperature, and pyrolysis product is mainly C
3～C
4Hydrocarbon.That is to say, use catalyst of the present invention to carry out the normal heptane isomerization reaction, can obtain higher liquid yield, produce more high octane gasoline component.
Example 6
The stability of this example evaluate catalysts.
The 7 gram catalyst A of packing in the small stationary bed bioreactor are warming up to 450 ℃, feed hydrogen reducing 2 hours, feed normal heptane then under 255 ℃, 1.6MPa condition and carry out isomerization reaction, reaction feed mass space velocity 1.2 hours
-1, hydrogen/hydrocarbon mol ratio is 4, react 600 hours the results are shown in Figure 1.As shown in Figure 1, make catalyst of the present invention carry out the normal heptane isomerization reaction, in 600 hours course of reaction, C7 conversion ratio and isomerization rate all remain in the metastable number range, illustrate that catalyst of the present invention has extraordinary stability.
Table 1
| Title | Form quality % | SiO 2/Al 2O 3Mol ratio | |||||
| SiO 2 | Al 2O 3 | Na 2O | P 2O 5 | Fe 2O 3 | Cl | ||
| Modenite | 79.0 | 12.0 | 8.0 | 0.3 | 0.12 | 0.2 | 11.2 |
| The Beta zeolite | 93.2 | 5.55 | 4.7 | - | - | - | 28.6 |
Table 2
| Instance number | The catalyst numbering | Carrier is formed, quality % | P content, quality % | Platinum content, quality % | Palladium content, quality % | ||
| Modenite | The Beta zeolite | Aluminium oxide | |||||
| 1 | | 40 | 40 | 20 | 0.38 | 0.32 | - |
| 2 | | 20 | 60 | 20 | 0.55 | 0.32 | - |
| 3 | | 60 | 20 | 20 | 0.22 | 0.32 | - |
| 4 | | 40 | 40 | 20 | 0.37 | - | 0.5 |
| 5 | | 40 | 40 | 20 | - | 0.32 | - |
| 6 | | 40 | 40 | 20 | - | - | 0.5 |
Table 3
| Catalyst | Reaction temperature, ℃ | C 7Conversion ratio, quality % | Selectivity of product, quality % | |
| ∑iC 7 | C 1～C 6 | |||
| A | 240 | 38.1 | 100 | 0 |
| 250 | 66.5 | 95.4 | 4.6 | |
| 255 | 72.9 | 90.7 | 9.3 | |
| 260 | 77.9 | 80.2 | 19.8 | |
| 270 | 84.3 | 70.1 | 29.9 | |
| 280 | 89.2 | 59.6 | 40.4 | |
| 285 | 95.7 | 53 | 47.0 | |
| B | 240 | 19.3 | 100 | 0 |
| 250 | 27.8 | 100 | 0 | |
| 260 | 36.1 | 100 | 0 | |
| 270 | 46.3 | 96.3 | 3.7 | |
| 280 | 63.5 | 89.9 | 10.1 | |
| 285 | 71.6 | 85.1 | 14.9 | |
| E | 240 | 49.2 | 96.6 | 3.4 |
| 250 | 73.2 | 88.8 | 11.2 | |
| 260 | 87 | 67.9 | 32.1 | |
| 270 | 100 | 42 | 58 | |
| F | 240 | 33.1 | 100 | 0 |
| 250 | 46 | 97.8 | 2.2 | |
| 260 | 58.6 | 92.8 | 7.2 | |
| 270 | 69 | 82.7 | 17.3 | |
| 280 | 79.4 | 75.3 | 24.7 | |
| C | 230 | 78.7 | 73.3 | 26.7 |
| 240 | 90.9 | 43. | 57 | |
| D | 220 | 37.6 | 88.3 | 11.7 |
| 230 | 58.2 | 79.4 | 20.6 | |
| 240 | 77.4 | 70.2 | 29.8 | |
Claims (9)
1, a kind of catalyst for normal paraffin isomerization, comprise the VIII family metal of 0.01-2.0 quality %, phosphorus and the complex carrier of 0.2～1.0 quality %, described complex carrier comprises the modenite of 10～80 quality %, the Beta zeolite of 10～80 quality % and the aluminium oxide of 10～50 quality %.
2, according to the described catalyst of claim 1, the content that it is characterized in that aluminium oxide in the described complex carrier is 15.0～40.0 quality %, and the Beta zeolite content is 30.0～75.0 quality %.
3,, it is characterized in that the silica of modenite and Beta zeolite is 5～80 according to claim 1 or 2 described catalyst.
4,, it is characterized in that the silica of described modenite and Beta zeolite is 10～60 according to the described catalyst of claim 3.
5, according to claim 1 or 2 described catalyst, it is characterized in that described VIII family tenor is 0.05-0.8 quality %, phosphorus content is 0.2～0.6 quality %.
6,, it is characterized in that described VIII family metal is selected from platinum or palladium according to claim 1 or 2 described catalyst.
7, the described Preparation of catalysts method of a kind of claim 1, comprise h-mordenite, Hydrogen Beta zeolite and aluminium hydroxide mixing aftershaping, make complex carrier after drying, the roasting, with phosphorus-containing compound solution impregnation complex carrier, VIII family metal is introduced in dry, roasting again.
8, in accordance with the method for claim 7, it is characterized in that described phosphorus-containing compound is selected from phosphoric acid, hydrophosphate or dihydric phosphate.
9, in accordance with the method for claim 8, it is characterized in that described hydrophosphate or dihydric phosphate are its sodium salt or sylvite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410029870 CN1286562C (en) | 2004-03-31 | 2004-03-31 | Normal paraffin isomerization catalyst and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410029870 CN1286562C (en) | 2004-03-31 | 2004-03-31 | Normal paraffin isomerization catalyst and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1676217A CN1676217A (en) | 2005-10-05 |
| CN1286562C true CN1286562C (en) | 2006-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410029870 Expired - Lifetime CN1286562C (en) | 2004-03-31 | 2004-03-31 | Normal paraffin isomerization catalyst and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622354A (en) * | 2016-12-30 | 2017-05-10 | 山西潞安纳克碳化工有限公司 | N-alkane isomerization catalyst and catalysis method thereof |
| CN108187735B (en) * | 2017-12-30 | 2020-07-31 | 西安元创化工科技股份有限公司 | Catalyst and method for preparing high-octane gasoline by using coal-based light oil |
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2004
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| CN1676217A (en) | 2005-10-05 |
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