CN1067918C - Solid ziegler catalyst for olefins and preparation thereof - Google Patents
Solid ziegler catalyst for olefins and preparation thereof Download PDFInfo
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- CN1067918C CN1067918C CN98107236A CN98107236A CN1067918C CN 1067918 C CN1067918 C CN 1067918C CN 98107236 A CN98107236 A CN 98107236A CN 98107236 A CN98107236 A CN 98107236A CN 1067918 C CN1067918 C CN 1067918C
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- 239000003054 catalyst Substances 0.000 title claims description 69
- 150000001336 alkenes Chemical class 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000007787 solid Substances 0.000 title claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 3
- 241001347978 Major minor Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000015110 jellies Nutrition 0.000 claims description 2
- 239000008274 jelly Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000006384 oligomerization reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- -1 carbon olefin Chemical class 0.000 abstract description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000011949 solid catalyst Substances 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000001294 propane Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 241000080590 Niso Species 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OWWRMMIWAOBBFK-UHFFFAOYSA-N 3,4-dimethylhex-1-ene Chemical class CCC(C)C(C)C=C OWWRMMIWAOBBFK-UHFFFAOYSA-N 0.000 description 1
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical class CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- LMHUKLLZJMVJQZ-UHFFFAOYSA-N but-1-ene;prop-1-ene Chemical compound CC=C.CCC=C LMHUKLLZJMVJQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a solid catalyst for olefine oligomerization in a fixed bed or kettle type reactor, which comprises the two kinds of metallic sulfate of the eighth group transitional metals, gamma alumina carriers and a phosphoric auxiliary agent. The present invention is suitable for producing high carbon olefin of C9<=> and C12<=> by oligomerization of propene, butylenes, the mixture of propane and the propene, the mixture of the propene and the butylene, etc. The solid catalyst has the characteristics of high oligomerization activity and high selectivity of C9<=> and C12<=> +cut fractions at lower reaction temperature.
Description
The present invention relates to a kind of olefin oligomerization catalyst that comprises two kind of the 8th group 4 transition metal sulfate, gama-alumina carrier and phosphorous assistant and preparation method thereof.
The olefin(e) oligomerization method is one of important means of PETROLEUM PROCESSING and petrochemical materials manufacturing, be used to make aviation kerosine, high-knock rating gasoline additive, and, produce significant to the comprehensive utilization and the development fine chemicals of petroleum resources for surfactant, plasticizer, agricultural chemicals and lube oil additive manufacturing provide olefin feedstock.
U.S. Pat P2,794,842 reports, nickelous sulfate supports in silica gel, aluminium oxide, silica-alumina or diatomite, in oxygen-containing atmosphere, heat-treats under 427 ℃～538 ℃ temperature and makes olefin oligomerization catalyst.U.S. Pat P3,959,400 introduce a kind of C
2 =～C
4 =The high activity catalyst for oligomerization of alkene, its preparation method is that nickelous sulfate supports in gama-alumina or η-aluminium oxide, nickeliferous 2～5% (wt) in the catalyst activate in 399 ℃～621 ℃ temperature and inertia, anaerobic and irreducibility atmosphere.U.S. Pat P4,658,788 have improved said method, have proposed the two stage activation method, after handling in higher temperature (399 ℃～621 ℃) and oxygen-containing atmosphere earlier, handle in lower temperature (177 ℃～399 ℃) and inert atmosphere again.In 288 ℃ of helium flows, remove earlier residual attachment during catalyst regeneration, switch to and rise to 510 ℃ behind the air and heat-treat, switch to helium flow under the last same temperature and handle.European patent 0272970A1 introduces 0.1: 1～0.95: 1 the olefin oligomerization catalyst of S/Ni mol ratio that nickel nitrate and ammonium sulfate double decomposition are made that passes through support on aluminium oxide.U.S. Pat P3, the sulfate of 442,964 narration nickel, cobalt, magnesium and chromium and oxide or its salt-mixture support in the catalyst for cracking silica-alumina, and prepared catalyst is good C
5 =～C
8 =Dimerization catalyst.Catalyst needs 350 ℃～850 ℃ activation down, and for sulfate catalyst, activation is for good in air, and oxide catalyst is then different, as nickel oxide catalyst, after 550 ℃ of following heat treatment, is cooled to reaction temperature and is advisable in helium flow in air.U.S. Pat P3,692,697 reports contain F
-Support in the cobaltous sulfate catalyst of aluminium oxide alkene is had polymerization, but be unfavorable for producing the purpose of oligomerization product because of the degree of polymerization is higher.U.S. Pat P4,423,267 reports, support in the ferric sulfate of aluminium oxide, silica-alumina and support cobaltous sulfate in aluminium oxide under temperate condition to C
3 =～C
18 =Alkene have high activity and to two, the high selectivity of trimerization.The dimerization selectivity is lower when being raw material with the propylene, and three, four poly-selectivity are obviously high, and 3,4 dimethylbutanes account for more than 90% in the hydrogenation products of dimer.Butylene is mainly based on dimerization, and 3,4 dimethyl hexenes account for more than 90% in the hydrogenation products of dimer.Chinese patent CN1073124A has reported a kind of alumina silicate catalyst that is applicable to propylene oligomerization.In preparation catalyst process, add a certain amount of ferric sulfate, Al in last component
2O
38～30%, SiO
270～92%, Fe
2O
32.5～5% and Na
2O 0～0.15%.At 80 ℃～100 ℃ of reaction temperatures, pressure 2.2MPa, liquid air speed 1.5h
-1Propylene conversion 85% and three, four poly-selectivity are greater than 62% under the condition.
The objective of the invention is by with the gama-alumina of macropore as carrier, seek two kinds of complex vitriolates as active component, and by metal molar than the kind of, auxiliary agent to improve oligomerisation activity and selectivity, develop the low-carbon alkene catalyst for oligomerization that a kind of activity is high, the higher olefins selectivity is good, particularly use this Catalyst Production C
9 =And C
12 =+ cut, as producing petrochemical materials and diesel oil distillate.
Catalyst carrier of the present invention contains 50～80% macropore gama-alumina, active component content 10～30%, and active component is selected from two kinds of compound sulfate, and wherein ferric sulfate is major constituent, and cobaltous sulfate or nickelous sulfate are accessory constituent.The atomic fraction of the metallic element of major constituent in two kinds of component metals elements of major-minor is between 0.5～0.8.Phosphate builder derives from two kinds of phosphorus-containing compounds, and a kind of is phosphoric acid, and another kind is an ammonium dihydrogen phosphate (ADP), and phosphorous assistant content is with P
2O
5The P elements ratio of counting 1～8%, two kinds of compounds is 1: 2～1: 6.
Catalyst carrier preparation method of the present invention is:
1. with the dried glue of macropore gama-alumina, pore volume 0.8～1.1ml/g, specific area 200～300m
2/ g, aperture＞50nm accounts for 80～95% for main component.
2. in the SB-alumina dry glue, add rare nitric acid and form jelly, make adhesive.
3. will be 1., 2. mixed-forming, 80～120 ℃ of dryings 4～10 hours 500～500 ℃ of roastings 4～10 hours, are made the macropore gamma-aluminium oxide carrier then.
The used macropore gamma-aluminium oxide carrier of catalyst of the present invention has following characteristic:
Bulk density, g/ml 0.5-0.8 pore-size distribution %
Diameter, nm 3-8 2.0-5.0nm 0-3
Pore volume, cm
3/ g 0.55-0.85 5.0-8.0nm 25-35
Specific area, m
2/ g 200-250 8.0-10.0nm 35-45
Average pore size, nm 10-15 10.0-15.0nm 20-25
Crushing strength (radially), N/mm 10-20 15.0-20.0nm 1-3
20.0-100nm 0-1
Catalyst adopts immersion process for preparing.Take by weighing stoichiometric metal sulfate and phosphorus-containing compound and be added in the deionized water, form Fe
2(SO
4)
3-NiSO
4-P maceration extract adds the γ-Al that measures then
2O
3The saturated dipping of carrier, 80～120 ℃ of dryings 4～10 hours, 450 ℃～500 ℃ activation 2～6 hours, and make catalyst.
Catalytic component content of the present invention:
The suitableeest gamut
Fe％(wt) 5～7
Ni％(wt) 1～3
P is (with P
2O
5Meter, % (wt)) 1～5
γ-Al
2O
3All the other (deduction stoichiometry SO
4 =Outward)
Catalyst of the present invention is used for fixing bed or tank reactor, but more is applicable to fixed bed system.Reaction system will pressurize, and is in a liquid state at conversion zone to keep raw material.Reactant is from the reactor lower part charging, and the top discharging after the pressure regulator decompression, by gas-liquid separator, is collected product liquid, and unreacted raw material is with gaseous state emptying or collection and treatment.
Raw material of the present invention can be propylene, butylene, propane-propylene mixtures, propene-1-butene mixture etc.Raw material does not preferably contain ethene, and needs drying to handle, and water content is not more than 20ppm.
The present invention is specially adapted to oligomerization of propene and produces C
9 =And C
12 =+ higher olefins.C
9 =And C
12 =+ all be to produce surfactant primary raw material, C
12 =Can make fine-quality diesel oil behind the+hydrogenation.Typical reaction condition is as follows:
Pressure (MPa) 〉=3.0
Temperature (℃) 40～80
Liquid volume air speed (h
-1) 0.5～3.0
Raw material water content (ppm) 0～20
Now, industrial normally used solid olefin oligomerization catalyst only just can reach high conversion and C under higher reaction temperatures
9 =, C
12 =+ high selectivity, but, under the reaction temperature condition more much lower, just can reach high conversion and C than common industrial catalyst with the catalyst that the present invention prepares
9 =, C
12 =+ high selectivity.
Advance-go on foot to describe the present invention below by example:
Embodiment 1
Take by weighing Fe
2(SO
4)
39H
2O 37.6g, NiSO
47H
2O 14.5g, 85%H
3PO
42.8g, NH
4H
2PO
411.2g be added in the deionized water, make saturated maceration extract, take by weighing 106.7g γ-Al again
2O
3Carrier carries out saturated dipping, 100 ± 10 ℃ of dryings 4～10 hours, and 450～500 ℃ of roastings 4 hours, catalyst A gets product.Catalyst contains Fe 5%, Ni 2%, P 2.5%.
Embodiment 2
Take by weighing 37.6g Fe
2(SO
4)
39H
2O is added to and makes saturated maceration extract in the deionized water.Take by weighing 123.2g γ-Al again
2O
3Carrier carries out saturated dipping.By the condition drying of catalyst A, activate reference catalyst B.Catalyst contains Fe 5%.
Embodiment 3
Take by weighing 57.9g NiSO
47H
2O is added to and makes saturated maceration extract in the deionized water.Take by weighing 118.2g γ-Al again
2O
3Carrier carries out saturated dipping.By the condition drying of catalyst A, activate reference catalyst C, catalyst contains Ni 8%.
Embodiment 4
Adopt CoSO
47H
2O replaces NiSO
47H
2The O component, the catalyst method for making is with embodiment 1.CoSO
47H
2O measures 14.4g, gets catalyst D and contains Fe 5%, Co 2%, P 2.5%.
Embodiment 5
Take by weighing Fe
2(SO
4)
39H
2O 37.6g, NiSO
47H
2O 14.5g is added in the deionized water, makes saturated maceration extract, takes by weighing 115.3g γ-Al again
2O
3Carrier carries out saturated dipping, and 100 ± 10 ℃ of dryings 4～10 hours, 450～500 ℃ of roastings 4 hours promptly got reference catalyst E, and catalyst contains Fe 5%, Ni 2%.
Embodiment 6
Adopt H
3PO
4Replace H
3PO
4And NH
4H
2PO
4Compounding ingredients, Preparation of Catalyst is with embodiment 1.Get reference catalyst F and contain Fe 5%, Ni 2%, P 2.5%.
Embodiment 7
Activity of such catalysts of the present invention, selective evaluation, and with the contrast of other catalyst be what to carry out with following method.
Evaluation of catalyst activity on the liquid-solid fixed-bed reactor of 50ml small pressurized.Raw materials used is propylene, propylene content 99.6%.Raw material needs preliminary treatment to remove alkaline organic, and carries out drying, requires water content less than 20ppm.Appreciation condition: pressure 3.0MPa, air speed 2.0h
-1, 60 ℃ of temperature.It the results are shown in Table 1.
Table 1 catalyst activity, selective evaluation
| Catalyst | A | B | C | D | E | F | |
| Conversion ratio % | 92.89 | 66.25 | 95.60 | 84.97 | 79.01 | 81.02 | |
| Selectivity % | C 6 =C 7-8 =C 9 =C 10-11 =C 12 =C 13-14 =C 15 =C 18 =C 12 =+ | 5.45 0.163 42.39 0.165 30.54 0.182 15.76 5.35 51.83 | 9.87 0.238 49.73 0.210 26.12 0.264 10.92 2.66 39.95 | 44.63 - 21.2 - 18.61 - 13.33 2.23 34.17 | 6.00 0.276 41.10 0.235 29.49 0.339 16.43 6.13 52.39 | 9.38 0.286 46.73 0.254 26.91 0.285 12.76 0.34 43.35 | 8.84 0.289 46.30 0.219 28.02 0.273 12.60 3.46 44.35 |
The active selectivity of catalyst A of the present invention is higher than reference catalyst B, though reference catalyst C conversion ratio height, C
9 =, C
12 =+ poor selectivity mainly is a dimerisation products.So catalyst A activity, selectivity the best.Catalyst A activity, selectivity ratios reference catalyst E, F are good, illustrate that compound phosphate builder improves catalyst activity, selectivity.Catalyst A of the present invention is compared with D, and A catalyst activity, selectivity are best.
Claims (5)
1. one kind is used for solid ziegler catalyst for olefins, it is characterized in that this catalyst comprises two kind of the 8th group 4 transition metal sulfate, gama-alumina carrier and phosphorous assistant, and the composition of catalyst and weight percentage thereof are:
Fe 5～7％
Ni or Co 1～3%
P
2O
5 1～5％
Deduction stoichiometry SO
4 =Outward, all the other are γ-Al
2O
3
2. according to the described catalyst of claim 1, it is characterized in that the 8th group 4 transition metal sulfate in the catalyst is ferric sulfate, cobaltous sulfate or nickelous sulfate, adopt the complex salt of two kinds of sulfate wherein to make active component, its total percentage composition is 10～30%, ferric sulfate is major constituent, cobaltous sulfate or nickelous sulfate are accessory constituent, the metallic element element of major constituent at the mole fraction of two kinds of component metals elements of major-minor between 0.5～0.8.
3. according to the described catalyst of claim 1, it is characterized in that the carrier in the catalyst adopts the gama-alumina component, it has following character:
Bulk density 0.5～0.8g/ml
Diameter 3～8mm
Pore volume 0.55～0.85ml/g
Specific area 200～250m
2/ g
Aperture 5～15nm accounts for 80～90%
Radial compression intensity 10～20N/mm
4. according to the described catalyst of claim 1, be characterised in that the phosphate builder that adopts in the catalyst altogether, a kind of is phosphoric acid, and another kind is an ammonium dihydrogen phosphate (ADP), and content is with P
2O
5Counting 1～5%, two kinds of compound phosphorus content ratios is 1.2～1.6.
One kind require 1 as profit as described in the Preparation of catalysts method, it is characterized in that this catalyst at first is to form the jelly mixed-forming with the dried glue of gama-alumina and rare nitric acid, 80～120 ℃ of dryings 4～10 hours, and fused 4～10 hours at 500～550 ℃, make the macropore gamma-aluminium oxide carrier, then it is immersed in Fe
2(SO
4)
3-NiSO
4Or CoSO
4In the deionized water of-phosphorus compound,, in 450～500 ℃ of activation 2～6 hours, make catalyst again 80～120 ℃ of dryings 4～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98107236A CN1067918C (en) | 1998-04-13 | 1998-04-13 | Solid ziegler catalyst for olefins and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98107236A CN1067918C (en) | 1998-04-13 | 1998-04-13 | Solid ziegler catalyst for olefins and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1193552A CN1193552A (en) | 1998-09-23 |
| CN1067918C true CN1067918C (en) | 2001-07-04 |
Family
ID=5219294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98107236A Expired - Fee Related CN1067918C (en) | 1998-04-13 | 1998-04-13 | Solid ziegler catalyst for olefins and preparation thereof |
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| CN (1) | CN1067918C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100461758B1 (en) * | 2002-09-16 | 2004-12-14 | 한국화학연구원 | Catalyst for decomposition of perfluoro-compound in waste-gas and method of decomposition with thereof |
| CN101402725B (en) * | 2008-11-12 | 2011-03-30 | 中国科学院长春应用化学研究所 | Supported rare earth ternary catalyst for combined polymerization of carbonic anhydride and epoxide and preparing method therefor |
| CN102240563B (en) * | 2010-05-12 | 2013-04-24 | 中国石油天然气股份有限公司 | Alpha-olefin oligomerization immobilized catalyst and preparation and application thereof |
| CN107185560B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of olefin oligomerization catalyst and preparation method |
| CN107159278A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of method of olefin(e) oligomerization |
| CN110721734B (en) * | 2019-11-12 | 2023-02-03 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil and co-producing gasoline by olefin oligomerization, preparation method and application |
| CN112657482B (en) * | 2020-11-24 | 2023-06-13 | 大连理工大学 | Solid acid catalyst and propylene oligomer obtained by using same |
| CN112657483B (en) * | 2020-11-24 | 2023-08-04 | 大连理工大学 | Catalyst and preparation method thereof |
| CN112452330B (en) * | 2020-11-24 | 2023-10-20 | 广东新华粤石化集团股份公司 | Process for producing propylene oligomer and propylene oligomer prepared by same |
| CN115178267A (en) * | 2022-07-19 | 2022-10-14 | 山东京博石油化工有限公司 | Catalyst for selective oligomerization of mixed butylene and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959400A (en) * | 1973-10-01 | 1976-05-25 | Mobil Oil Corporation | Olefin dimerization |
| US4423267A (en) * | 1982-06-01 | 1983-12-27 | Conoco Inc. | Supported ferric sulfate and cobalt sulfate catalysts for the oligomerization of olefins |
| EP0272970A1 (en) * | 1986-12-17 | 1988-06-29 | Institut Français du Pétrole | Process for the preparation of a catalyst comprising a nickel compound deposited on alumina, and use of the prepared catalyst for the dimerization of olefines |
| CN1073124A (en) * | 1991-12-08 | 1993-06-16 | 兰州大学 | Propene oligomer catalyst and preparation method thereof |
| CN1078663A (en) * | 1992-05-15 | 1993-11-24 | 中国石油化工总公司 | The solid phosphate catalyst that is used for olefin(e) oligomerization |
-
1998
- 1998-04-13 CN CN98107236A patent/CN1067918C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959400A (en) * | 1973-10-01 | 1976-05-25 | Mobil Oil Corporation | Olefin dimerization |
| US4423267A (en) * | 1982-06-01 | 1983-12-27 | Conoco Inc. | Supported ferric sulfate and cobalt sulfate catalysts for the oligomerization of olefins |
| EP0272970A1 (en) * | 1986-12-17 | 1988-06-29 | Institut Français du Pétrole | Process for the preparation of a catalyst comprising a nickel compound deposited on alumina, and use of the prepared catalyst for the dimerization of olefines |
| CN1073124A (en) * | 1991-12-08 | 1993-06-16 | 兰州大学 | Propene oligomer catalyst and preparation method thereof |
| CN1078663A (en) * | 1992-05-15 | 1993-11-24 | 中国石油化工总公司 | The solid phosphate catalyst that is used for olefin(e) oligomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1193552A (en) | 1998-09-23 |
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