CN1030395C - Heavy oil hydrodenitrogenation catalyst - Google Patents
Heavy oil hydrodenitrogenation catalyst Download PDFInfo
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- CN1030395C CN1030395C CN92112511A CN92112511A CN1030395C CN 1030395 C CN1030395 C CN 1030395C CN 92112511 A CN92112511 A CN 92112511A CN 92112511 A CN92112511 A CN 92112511A CN 1030395 C CN1030395 C CN 1030395C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 239000000295 fuel oil Substances 0.000 title claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 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 description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 238000001125 extrusion Methods 0.000 abstract description 7
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910017318 Mo—Ni Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000772415 Neovison vison Species 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- -1 nitrogenous compound Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
A heavy oil hydrodenitrogenation catalyst and a preparation method thereof are described. The catalyst composition is W-Mo-Ni/SiO2-B2O2-A12O3. The preparation method of the catalyst is characterized in that low-sodium silica sol is added in the carrier extrusion molding process, and the function of the low-sodium silica sol is to increase the pore volume and the average pore diameter of the carrier, so that the pore distribution becomes more concentrated and the acid amount of the carrier is increased.
Description
The present invention relates to Hydrobon Catalyst And Its Preparation Method, particularly mink cell focus hydrodenitrogenation catalyst and preparation method.
The present invention is to be CN1052501A(application number 89109140.8 at publication number) Chinese invention patent on improvement.
Common Hydrobon catalyst is a carrier with aluminum oxide or siliceous aluminum oxide, is the hydrogenation activity component with VIII family and VI B family metallic element.For under the prerequisite that does not make the preparation process condition harshnessization, further improve the activity and the activity stability of Hydrobon catalyst, add various auxiliary agents.Usually the auxiliary agent of usefulness has fluorine, phosphorus, boron, titanium etc.For hydrodenitrification, it is clearly that catalyzer adds the boron effect, and supports that to add boron again after the hydrogenation component better.There are the following problems but pickling process adds boron: the most frequently used boron-containing compound is a boric acid when adding boron, and boric acid solubleness in water is very low under the room temperature, and 100ml water can only dissolve the boric acid about 6g.So when at room temperature using the boric acid aqueous solution impregnated catalyst, the boron loading does not seldom have the effect that improves catalyst activity on the catalyzer.The content of boron trioxide is (2-6) W% on the general requirement catalyzer.
Publication number is that the patent of invention of CN1052501A proposes the compound method that a kind of high density contains the ammoniacal liquor stabilizing solution of molybdenum, boron compound, has solved this problem.But the catalyzer that this patent application proposed, average pore diameter is about 8.0nm, relatively is suitable for the hydrofining of lighter fraction oil.Being used for the hydrorefined catalyzer of mink cell focus should have bigger aperture, is beneficial to the macromolecular internal diffusion in the mink cell focus.
It is bigger to the purpose of this invention is to provide a kind of aperture, and the acid amount is bigger, is applicable to the catalyzer of mink cell focus hydrodenitrification, and a kind of practical easily novel method of row for preparing larger aperture catalyzer or carrier is provided.
The aperture of catalyzer depends primarily on the aperture of used carrier, and the reaming of carrier has various methods.For the reaming of extrusion carrier, method commonly used has: (1) adds various expanding agents in the extrusion process, as carbon black, starch, organic polymer material, tensio-active agent etc.; (2) behind extruded moulding, use water vapor pyroprocessing etc.The shortcoming of first method is that the tap density of gained carrier is low, bad mechanical strength.Second method dies down support acidity, finally makes acidity of catalyst strong inadequately, is not easy to make the carbonnitrogen bond fracture of the nitrogenous compound in the stock oil, thereby does not reach the purpose of hydrodenitrification.
The present invention proposes a kind of method for preparing the larger aperture carrier, its main points are: in aluminium hydroxide extrusion process, add the low silicon sol that contains sodium, silicon sol plays the elimination aperture in drying and roasting, increase the effect of macropore.
Adopt silicon sol as the advantage of expanding agent to be: (A) after the carrier reaming, tap density and physical strength do not descend.(B) after carrier added silicon, the acid amount increased.(C) after carrier added silicon, it is more concentrated that pore distribution becomes.(D) when extrusion, adding silicon sol does not increase the extrusion difficulty, need not increase peptization acid amount yet.
The preparation method of catalyzer used carrier of the present invention: take by weighing the aluminum hydroxide solid elastomer of calculated amount, low sodium silicon sol, preferably Na
+Content is less than 0.10% silicon sol, with mineral acid or organic acid (as nitric acid, hydrochloric acid, citric acid, oxalic acid, formic acid, acetate etc.) and mixed paste of pinching into of water mixing (or adding extrusion aid such as sesbania powder in case of necessity in right amount) as peptizing agent, extruded moulding on banded extruder, the shape of carrier can be regulated with the mode of changing the banded extruder orifice plate, can be cylindrical, also can be special-shaped bar.Carrier after the shaping then at (500-650) ℃ following roasting (2-6) h, obtains siliceous alumina supporter at (90-130) ℃ following oven dry (2-6) h at last, and carrier contains SiO
2(14-19) W%.Carrier pore volume (0.55-0.65) ml/g, specific surface (200-240) m
2/ g, average pore diameter is (10.5-12.5) nm, tap density, (0.56-0.68) g/ml.
Catalyzer of the present invention is a carrier with siliceous aluminum oxide, is the hydrogenation activity component with tungsten, molybdenum, nickel, adds boron as auxiliary agent.
The present invention prepares the siliceous alumina supporter of larger aperture with a kind of easy novel method, adopts the mode load hydrogenation component and the auxiliary agent of dipping.
Catalyst preparation step of the present invention is: take by weighing a certain amount of aforesaid siliceous alumina supporter, water-intake rate according to carrier, measure the aqueous solution of a certain amount of tungstenic, nickel compound, carrier is flooded, can be that saturated dipping also can be the supersaturation dipping, then at (100-130 ℃) down dry (2-6) h, again at (350-550) ℃ following roasting (2-6) h; get the catalyzer work in-process after the roasting; according to its water-intake rate; measure a certain amount of ammonia soln that contains molybdenum, boron compound and flood, dipping can be that saturated dipping also can be the supersaturation dipping.At (100-130) ℃ down dry (2-6) h,, make finished catalyst then at (400-550) ℃ following roasting (2-6) h.
Catalyzer of the present invention has following feature, and in vehicle weight, the silica content of siliceous alumina supporter is (14-19) %, the pore volume of catalyzer (0.30-0.45) ml/g, specific surface (110-160) m
2/ g, mean pore size (10.5-12.5) nm.In catalyst weight, contain WO
3(13-20) %, MoO
3(7-10) %, NiO(3-5) %, B
2O
3(3-5) %, catalyst buildup density is (0.90-0.98) g/ml.
Utilize catalyzer of the present invention, for being the unifining process of raw material with the mink cell focus, at hydrogen dividing potential drop (5.0-16.0) MPa, temperature of reaction (360-410) ℃, volume space velocity (0.5-2.0) h
-1, under the condition of hydrogen to oil volume ratio (600-1500), handle high nitrogenous mink cell focus such as VGO, can obtain good refining effect.
VGO is a raw material with triumph, at hydrogen dividing potential drop 6.37MPa, and 378 ℃ of temperature of reaction, volume space velocity 1.0h
-1, under the condition of hydrogen to oil volume ratio 1000, denitrification percent can reach more than 95%, has good hydrodenitrogenationactivity activity, and continuous operation 2000h, and average temperature raising speed only is 0.048 ℃/day.
Compared with prior art, catalyzer of the present invention has good hydrodenitrogenationactivity activity and satisfactory stability.Adopt new easy expanding method to enlarge the aperture of catalyzer, and make pore distribution become concentrated, improved the acid matter of carrier simultaneously, and reaming can not cause the physical strength of carrier and catalyzer and tap density to descend.
Embodiment 1
Take by weighing eight parts of 200g aluminum hydroxide solid elastomers respectively and (contain Al
2O
370W%), and respectively add and contain SiO
240%, Na
+0.08% silicon sol 0g, 10.8g, 30.5g, 52.2g, 61.8g, 71.8g, 82.0g and 93.0g.Following operation steps is identical to these eight parts of materials.Mix and to pinch evenly, add the 4.7W% salpeter solution 148g that has dissolved the 4.0g citric acid again, mix again and pinch evenly, being extruded into equivalent diameter on banded extruder is the trifolium bar of 1.3mm, then at 120 ℃ of dry 4h down, 550 ℃ of following roasting 4h.The gained carrier is called after A, B, C, D, E, F, G and H respectively, and its chemical constitution and physico-chemical property are listed in table 1.
(table 1 is seen the literary composition back)
By table 1 as seen, add an amount of low sodium silicon sol when the carrier extruded moulding, following effect is arranged: (1) increases the pore volume of carrier and mean pore size; (2) carrier hole is distributed and become more concentrated; (3) carrier TPD acid amount is increased; (4) in reaming, physical strength is obviously descended.Therefore, the present invention adds low sodium silicon sol when the preparation carrier, make final carrier contain SiO
2(14-19) W%(is benchmark with the vehicle weight).
Embodiment 2
(1) carrier that to select the siliceous alumina supporter F among the embodiment 1 be this routine catalyzer.
(2) preparation of tungstenic, nickel compound solution.
Measure 60ml distilled water, add 31g six water nickelous nitrates and 35g ammonium metawolframate, stirring and dissolving, again with distilled water diluting to 100ml, the gained strength of solution is that every 100ml contains WO
328.7g, NiO7.8g.
(3) contain the preparation of molybdenum, boron compound solution
Measure and contain NH
3The ammoniacal liquor 85ml of 12W% adds 28g Ammonium Heptamolybdate and 18g boric acid, heats 4h down at 70 ℃, and naturally cooling is standby.Final solution concentration is that every 100ml contains MoO
323.0g, H
2O
310.1g.
(4) take by weighing by (1) described drying support 100g, place rotary drum, get by (2) gained solution 81ml, spray, dipping time is 20min.After dipping finishes, take out material, dry 4h under 120 ℃ is then at 400 ℃ of following roasting 4h.
(5) get by (4) gained catalyzer work in-process 100g, place rotary drum, measure by (3) gained solution 58ml, spray, the time of spraying is 15min.Sprayed the back and taken out, dry 4h under 120 ℃ then at 480 ℃ of following roasting 4h, makes finished catalyst.
Embodiment 3
(1) carrier that to select the siliceous alumina supporter E among the embodiment 1 be this routine catalyzer.
(2) preparation of tungstenic nickel compound solution
Measure 60ml distilled water, add 31g six water nickelous nitrates and 41g ammonium metawolframate, stirring and dissolving, again with distilled water diluting to 100ml.The gained strength of solution is that every 100ml contains WO
333.4g, NiO7.8g.
Following preparation process is with embodiment 2.
Comparative example 1
(1) preparing carriers
Be mixed with acidic solution with aluminum chloride and acidified sodium silicate, the SiO of solution
2/ (SiO
2+ Al
2O
3) than for 7.5W%, this solution and the ammonia soln that contains ammonia 10W% are 8 in pH value, temperature is to become glue continuously under 30 ℃ the condition, controls 10min duration of contact, assembly glue time 90min.Separate behind the aging 0.5h of colloid, colloid is kneaded into false colloidal sol with mineral acid after water purification washing 4 times, and through the oil column balling-up, the ammonia post solidifies, and wet rubber ball is through 110 ℃ of dry 4h of steam baking oven, 600 ℃ of following roasting 3h in retort furnace and make support of the catalyst.
(2) tungstenic, the preparation of nickel compound solution
Take by weighing 54.9g ammonium metawolframate and 46.9g six water nickelous nitrates, add water 78.0ml, stirring and dissolving, last strength of solution is that every 100ml contains WO
345.0g, NiO12.0g.
(3) contain molybdenum, the preparation of boron compound solution
Measure the ammonia soln 81.0ml that contains ammonia 9W%, add 23.5g Ammonium Heptamolybdate and 16.0g boric acid, after mixture placed 50 ℃ of water-bath heating 4h, naturally cooling, final solution concentration were that every 100ml contains MoO
319.0g, B
2O
39.0g.
(4) get the drying support 100g that made by (1) in rotary drum, get the solution 70.0ml that is made by (2), carrier is sprayed, the time of spraying is 24min, has sprayed the back and has taken out nature and dry, then at 400 ℃ of following roasting 3h.
(5) get the catalyzer work in-process 100.0g that is made by (4), place rotary drum, use the solution 50.0ml of (3) gained to spray, the time of spraying is 18min, has sprayed the back and has taken out oven dry 3h under 120 ℃, then at 480 ℃ of following roasting 3h.
Embodiment 4
This example is the chemical constitution and the main physico-chemical property (seeing literary composition back table 2) of above each routine catalyzer.
By table 2 as seen, catalyzer total metal contents in soil of the present invention is lower, and mean pore size is bigger, and tap density is moderate.
Embodiment 5
VGO is a raw material with triumph, estimates the hydrodenitrogenationactivity activity of each routine catalyzer.The raw material oil properties sees Table 3.
The main character of table 3 stock oil
Raw material type triumph VGO
Density, d
20 40.8759
Boiling range (ASTM)
IBP/10% 298/367
30%/50% 397/418
70%/90% 436/464
95%/EP 485/503
Nitrogen, ppm 1153
Sulphur, ppm 4700
Condensation point, ℃ 35
The par device is the 200ml small hydrogenation device, and catalyzer is before use with containing CS
2Kerosene carry out prevulcanized.Reaction conditions is: hydrogen pressure 6.37MPa, volume space velocity 1.0h
-1, 378 ℃ of temperature, hydrogen-oil ratio 1000(V).
It is generally acknowledged that VGO hydrodenitrification reaction is one-level, its apparent reaction velocity constant K
nBe defined as:
K
n＝（LHSV）×ln（Co/C）
LHSV is a volume space velocity in the formula, and CO and C are respectively stock oil and give birth to olefiant nitrogen content.Corresponding intrinsic reaction velocity constant K
aBe defined as:
K
n＝K
n/（S·D）
S and D are respectively the specific surface and the tap density of catalyzer in the formula.We are with intrinsic reaction velocity constant K
nCharacterize activity of such catalysts.Evaluating catalyst the results are shown in Table 4.
The HDN specific activity of each routine catalyzer of table 4
Catalyzer K, 10
-6Cmh
-1
Embodiment 2 2.70
Embodiment 3 2.69
Comparative example 1 1.88
By table 4 as seen, catalyzer of the present invention is specially adapted to the deep hydrogenation denitrogenation of VGO.
The chemical constitution of table 1 carrier and main physico-chemical property
Carrier S iO
2The pore distribution of W% pore volume specific surface mean pore size TPD strength of acid, %(nm)
Numbering ml/g m
2/ g nm mM/g N/em＜4.0 4.0-15.0＞15.0
A 0 0.534 218 9.8 0.407 192 4.1 87.1 8.8
B 3 0.579 218 10.6 0.412 184 3.1 90.7 6.2
C 8 0.594 216 11.0 0.417 160 3.4 92.0 4.6
D 13 0.604 213 11.3 0.430 173 3.3 92.8 3.9
E 15 0.614 217 11.3 0.459 157 2.1 94.0 3.9
F 17 0.624 219 11.4 0.462 172 2.3 94.2 3.5
G 19 0.598 214 10.9 0.465 179 2.6 94.0 3.4
H 21 0.569 218 10.4 0.440 168 3.3 92.0 4.7
The composition of each routine catalyzer of table 2 and character
Catalyzer embodiment 2 embodiment 3 comparative examples 1
Chemical constitution W%
WO
315.5 17.8 19.8
MoO
39.0 8.8 7.8
NlO 4.2 4.0 5.0
B
2O
34.0 3.9 3.5
SiO
2/（SiO
2+Al
2O
3） 17.0 15.0 7.5
Character
Pore volume, ml/g 0.374 0.367 0.30
Specific surface, m
2/ g 132 130 150
Average pore diameter, nm 11.3 11.3 8.00
Tap density, g/ml 0.94 0.95 1.15
Claims (4)
1, a kind of heavy-oil hydrogenation denitrification catalyst, with tungsten, molybdenum, three kinds of elements of nickel is the hydrogenation activity component, siliceous aluminum oxide is a carrier, add boron and make auxiliary agent, it is characterized in that in vehicle weight, the silica content of carrier is in the 14-19% scope, and the pore volume of catalyzer is 0.30-0.45ml/g, and specific surface is 110-160m
2/ g average pore diameter is 10.5-12.5nm, and tap density is 0.90-0.98g/ml, in catalyst weight trioxygen-containing tungsten 13-19%, molybdic oxide 7-10%, nickel oxide 3-5%, boron trioxide 3-5%.
2, a kind of preparation method of heavy-oil hydrogenation denitrification catalyst, it is characterized in that with the aluminum hydroxide solid elastomer powder with contain low sodium silicon sol and peptizing agent, water mixes, the mixed paste of pinching into, extruded moulding, forming composition at 500-650 ℃ of following roasting 2-6 hour, obtains containing Sio again 90-130 ℃ of oven dry
2The carrier of 14-19W%, average pore diameter 10.5-12.5nm, with the aqueous solution dipping of above-mentioned carrier with tungstenic, nickel compound, descended dry 2-6 hour at 100-130 ℃, 350-550 ℃ roasting 2-6 hour, again with the ammonia soln dipping that contains molybdenum, boron, descended dry 2-6 hour at 100-130 ℃ then,, make finished catalyst at 400-550 ℃ of roasting 2-6 hour.
3,, it is characterized in that used silicon sol Na according to the method for claim 2
+Content is less than 0.10W%.
4, according to the method for claim 2, it is characterized in that siliceous alumina supporter pore volume is 0.55-0.65ml/g, specific surface area is 200-24m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112511A CN1030395C (en) | 1992-11-05 | 1992-11-05 | Heavy oil hydrodenitrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92112511A CN1030395C (en) | 1992-11-05 | 1992-11-05 | Heavy oil hydrodenitrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1086534A CN1086534A (en) | 1994-05-11 |
| CN1030395C true CN1030395C (en) | 1995-11-29 |
Family
ID=4945978
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92112511A Expired - Fee Related CN1030395C (en) | 1992-11-05 | 1992-11-05 | Heavy oil hydrodenitrogenation catalyst |
Country Status (1)
| Country | Link |
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| CN (1) | CN1030395C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055877C (en) * | 1996-03-26 | 2000-08-30 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
| CN1075546C (en) * | 1998-11-18 | 2001-11-28 | 中国石油化工集团公司 | Mixed solution containing silicon and boron and its preparation |
| CN1088090C (en) * | 1999-05-18 | 2002-07-24 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN1088087C (en) * | 1999-09-17 | 2002-07-24 | 中国石油化工集团公司 | Preparation of hydrogenation catalyst |
| CN1091137C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Mixed solution and its preparing process |
| CA2501973C (en) | 2002-10-10 | 2010-10-26 | China Petroleum & Chemical Corporation | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| US20060058174A1 (en) * | 2004-09-10 | 2006-03-16 | Chevron U.S.A. Inc. | Highly active slurry catalyst composition |
| CN100371077C (en) * | 2004-10-29 | 2008-02-27 | 中国石油化工股份有限公司 | A kind of macroporous alumina carrier and preparation method thereof |
| CN1840618B (en) * | 2005-03-31 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst with silicon oxide-alumina as carrier and its preparation |
| CN100421784C (en) * | 2005-04-27 | 2008-10-01 | 中国石油化工股份有限公司 | A kind of alumina dry glue containing silicon and boron and preparation method thereof |
| CN101347735B (en) * | 2007-07-19 | 2013-02-06 | 中国石油化工股份有限公司 | Methanation catalyst for removing trace amounts of oxycarbide |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
| CN106040283B (en) * | 2016-05-30 | 2018-07-24 | 沈阳三聚凯特催化剂有限公司 | A kind of catalyst for demetalation carrier and preparation method thereof |
| CN106622309B (en) * | 2016-09-27 | 2019-06-11 | 西安元创化工科技股份有限公司 | A kind of n-hydroxyethyl pyrrolidone dehydration catalyst and preparation method thereof |
| CN119608181B (en) * | 2024-11-13 | 2025-12-09 | 浙江皇马科技股份有限公司 | Preparation method of supported nickel-based catalyst and polyether amine prepared by using preparation method |
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1992
- 1992-11-05 CN CN92112511A patent/CN1030395C/en not_active Expired - Fee Related
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| CN1086534A (en) | 1994-05-11 |
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