CN100429294C - Refined hydrogenation catalyst and its preparation method - Google Patents
Refined hydrogenation catalyst and its preparation method Download PDFInfo
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- CN100429294C CN100429294C CNB2005101166128A CN200510116612A CN100429294C CN 100429294 C CN100429294 C CN 100429294C CN B2005101166128 A CNB2005101166128 A CN B2005101166128A CN 200510116612 A CN200510116612 A CN 200510116612A CN 100429294 C CN100429294 C CN 100429294C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title description 5
- 238000001035 drying Methods 0.000 claims abstract description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000005078 molybdenum compound Substances 0.000 claims description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- -1 phosphorus compound Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003658 tungsten compounds Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 13
- 239000003921 oil Substances 0.000 abstract description 11
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 3
- 238000007654 immersion Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 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
- 238000001816 cooling Methods 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910018104 Ni-P Inorganic materials 0.000 description 4
- 229910018536 Ni—P Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention belongs to a hydrofining catalyst and a preparation method thereof. The catalyst uses aluminum oxide or aluminum oxide containing silicon as a carrier, uses WO3, MoO3 and NiO as active components, and uses oxides of phosphorus as auxiliary agent components. The preparation method of the catalyst comprises: (1) preparing the carriers for the catalyst; (2) dissolving the compounds of W, Mo, Ni and P at room temperature to prepare common immersion liquid; (3) once immersing the carriers prepared in step (1) by the common immersion liquid prepared in step (2); (4) continuously heating, drying and calcining the immersed and dried carriers in the atmosphere of vapor. The catalyst of the present invention has the advantages of uniform distribution of the active components, large pore volume and specific surface area, high desulphurizing activity and denitrifying activity and low cost; therefore, the present invention is especially suitable for hydrofining distillate oil of which the reacting substances have the wide range of molecular weight.
Description
Technical field
The invention belongs to the oil refining field, relate to a kind of liquid towards petroleum product and distillate and carry out Hydrobon Catalyst And Its Preparation Method.
Background technology
Hydrofining technology is comfortable certain temperature and pressure, has under the condition of catalyzer and hydrogen existence, make all kinds of non-hydrocarbon compound generation hydrogenolysis in oil product or the distillate, and then from oil product or distillate, remove, to reach the purpose of refined oil or distillate.Hydrobon catalyst generally is to be carrier with the aluminum oxide, with VIII family and group vib metallic element is active ingredient, also have in order to improve activity of such catalysts and stability, carrier is improved, it for example is carrier with the aluminium oxide-silicon oxide, or the adding auxiliary agent, generally be P, F, B, Si, Ti, Zr etc.And present W-Mo-Ni-P/Al
2O
3Catalyzer is widely used in hydrorefined commercial catalysts with its high reactivity.
Chinese patent application 99113281 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, this catalyzer is to be carrier with aluminum oxide or siliceous aluminum oxide, with W, Mo, Ni is active ingredient, is auxiliary agent with P, the method preparation that employing is repeatedly flooded altogether.This patent application need be heated to the compound that 70～120 ℃ of ability dissolvings contain reactive metal element and auxiliary element when the preparation co-impregnated solution, mainly be to be water-soluble bad molybdic oxide because the molybdenum source selects for use, can make that so just W, Mo mainly are present in the co-impregnated solution with the heteropolyacid anions form, influence the formation of subsequent preparation catalyst active center, make desulfurization, denitrification activity not high.Drying in this catalyst preparation process behind the dipping is that in the W-Mo-Ni-P co-impregnated solution, W, Mo exist with anionic form, and the pH value of co-impregnated solution is at carrier A l at 80～150 ℃ of down dry 2～8h
2O
3Iso-electric point under, in steeping fluid, carrier surface is positively charged, so W, Mo negatively charged ion mainly are adsorbed on the carrier hole wall, can not flow to aperture with capillary penetration.Because absorption is exothermic process, the unfavorable adsorption equilibrium of heat drying, the adsorption-desorption balance is moved to desorption, W, the Mo negatively charged ion of absorption are come back in the solution, the active ingredient of having aggravated to cause owing to capillary penetration is by the transition process of macropore to aperture, make the active ingredient skewness, and cause specific surface area of catalyst and pore volume to descend.The method of dipping is altogether adopted repeatedly in this patent application in addition, and complex technical process is loaded down with trivial details, and production cost is bigger.
Chinese patent application 99113305 discloses a kind of Hydrobon Catalyst And Its Preparation Method.This catalyzer is to be carrier with siliceous aluminum oxide, is active ingredient with W, Mo, Ni, is auxiliary agent with B, adopts once the method for dipping preparation altogether.Water-soluble bad molybdic oxide is still selected in the molybdenum source of this patent application for use, adopt heating means dissolving preparation co-impregnated solution, still the problem that exists W in the co-impregnated solution, Mo mainly to exist with the heteropolyacid anions form, influence the formation of subsequent preparation catalyst active center, make desulfurization, denitrification activity not high.This patent application does not spell out dipping after drying method in claims and specification sheets, only show to spray dry 4h under back 120 ℃ in embodiment 5.Therefore can think that its also is to carry out heat drying after flooding.There is the lower shortcoming of catalyzer pore volume and specific surface so equally.
Chinese patent application 01129503 discloses a kind of catalyst for hydrogen refining of paraffin wax and its production and use.It is co-impregnated solution of W-Mo-Ni-P that this patent application prepares the used steeping fluid of catalyzer, and co-impregnated solution is at room temperature to dissolve W, Mo, Ni, P-compound preparation, behind the dipping at first drying at room temperature spend the night heat drying then.The support of the catalyst of this patent application is for containing TiO
2Al
2O
3, during the preparation co-impregnated solution, the Mo compound of usefulness may be the ammonium paramolybdate of good water solubility under the room temperature, co-impregnated solution is a strongly-acid.This catalyzer is mainly used in hydrorefining paraffin wax, also can be used for hydrofining light, heavy distillate.In the hydrorefining paraffin wax process, big by the reactant molecule amount of hydrogenation, require catalyzer to have more macropore and large pore volume, hydrogenation reaction is carried out in macropore, and macromole can not diffuse into aperture, so aperture is in fact inoperative in the wax hydrofining reaction.Wax hydrofining catalyzer majority is with Al
2O
3Be carrier, the positively effect of Chinese patent application 01129503 is found exactly at Al
2O
3The middle TiO that adds
2Can make catalyzer form more macropore,, be more suitable for paraffin wax hydrofining so mean pore size is big.The distillate molecular weight ranges is wider, by what the reactant molecule of hydrogenation had a macromolecule small molecular weight is arranged also, and this just requires catalyzer that rational pore distribution is arranged, big aperture all will have, and is unimpeded, and so not only pore volume is big, and specific surface is also big, and more reacting environment are provided.The specific surface of this patent application also is not very high.Therefore the drying at room temperature process of this patent application is spent the night and is got final product, and less than 1 day, so Duan drying at room temperature effect also is not fine, neither be very big to the influence of capillary penetration effect.This patent application is if then price is higher for the ammonium paramolybdate that uses in addition, and production cost is bigger.
Summary of the invention
The object of the present invention is to provide a kind of pore volume and specific surface area more greatly, in use liquid towards oil product or distillate have the active Hydrobon Catalyst And Its Preparation Method of higher desulfurization removing nitric.
Realize that the technical scheme that provides a kind of Hydrobon catalyst to adopt in the object of the invention is: a kind of Hydrobon catalyst, its carrier are aluminum oxide or siliceous aluminum oxide, and active ingredient is WO
3, MoO
3And NiO, adjuvant component is the oxide compound of phosphorus; It is characterized in that: each components contents of mass percent in catalyzer is respectively SiO
2Be 0%～11%, WO
3Be 17%～24%, MoO
3Be 10.5%～14%, NiO is 4.5%～7%, the oxide compound of phosphorus counts 2%～4% with P, all the other are Al
2O
3Wherein, active ingredient MoO
3Raw material be ammonium tetramolybdate.The preparation process of described Hydrobon catalyst comprises: 1. prepare support of the catalyst; 2. dissolve W, Mo, Ni under the room temperature, P-compound prepares co-impregnated solution; The pH value of co-impregnated solution is 3～4; Molybdenum compound wherein is an ammonium tetramolybdate, and ammonium tetramolybdate is by ammonia solvent; 3. the carrier of using the co-impregnated solution single-steeping that 2. makes by step 1. to make under the room temperature by step; 4. soaked carrier is at room temperature dry earlier, puts into rotary roasting furnace then and carries out heat drying and roasting continuously, and wherein heat drying is to carry out under the water vapour atmosphere that produces at self.
The specific surface of described catalyzer is 180～250m
2/ g, pore volume are 0.40～0.60ml/g, and preferred specific surface is 211～250m
2/ g, preferred pore volume is 0.40～0.45ml/g.
The present invention may further comprise the steps for the preparation method of above-mentioned Hydrobon catalyst: 1. prepare support of the catalyst; 2. dissolve W, Mo, Ni under the room temperature, P-compound prepares co-impregnated solution; Molybdenum compound wherein is an ammonium tetramolybdate, and ammonium tetramolybdate is by ammonia solvent; 3. the carrier of using the co-impregnated solution single-steeping that 2. makes by step 1. to make under the room temperature by step; 4. soaked carrier is at room temperature dry earlier, puts into rotary roasting furnace then and carries out heat drying and roasting continuously, and wherein heat drying is to carry out under the water vapour atmosphere that produces at self.
Above-mentioned steps 2. described in tungsten compound be that ammonium metawolframate, nickel compound are that nickelous nitrate, phosphorus compound are ortho-phosphoric acid.By ammonia solvent, nickelous nitrate and ortho-phosphoric acid is by deionized water dissolving when ammonium tetramolybdate is by ammonia solvent for the ammonium metawolframate of step in 2., and is then that two kinds of solution are mixed, stir, and obtains limpid stable co-impregnated solution after the filtration.Ammonium metawolframate is with WO in the co-impregnated solution that step makes in 2.
3The concentration of meter is that 16～30g/100ml, ammonium tetramolybdate are with MoO
3The concentration of meter is that 11～16g/100ml, nickelous nitrate are that 7～10g/100ml, ortho-phosphoric acid are 3.5～5.5g/100ml in the concentration of P in the concentration of NiO.The pH value of the co-impregnated solution that step makes in 2. is 3～4.Above-mentioned steps 4. in the temperature of drying at room temperature be 5～30 ℃, time of drying 1～3d.
The positively effect that the present invention has: the molybdenum compound that (1) is selected for use when the present invention prepares co-impregnated solution is the ammonium tetramolybdate that dissolves in ammoniacal liquor under the room temperature, thereby can prepare under the room temperature, and need be heated to 70～120 ℃ of ability preparations when selecting water-soluble bad molybdenum oxide for use.Room temperature preparation makes that W, Mo mainly exist with the less isopoly-acid anionic form of molecular weight in the co-impregnated solution, rather than exist with phosphato-molybdic heteropolyacid negatively charged ion and phosphorus heteropoly tungstic acid anionic form, help forming more active centre, have higher desulfurization, denitrification activity.(2) price of the ammonium tetramolybdate selected for use of the present invention is lower than ammonium paramolybdate, therefore selects ammonium tetramolybdate for use, can reduce production costs.(3) because ammonia and ortho-phosphoric neutralization of acid with base, the co-impregnated solution pH value that the present invention uses is 3～4, the co-impregnated solution that uses than Chinese patent application 01129503 acid low, avoided the strongly-acid co-impregnated solution to the carrier disadvantageous effect, but its pH value still is lower than the iso-electric point of carrier, carrier is in co-impregnated solution, the surface is positively charged, hydrogen phosphate negatively charged ion in the preferentially adsorbed co-impregnated solution, make these negatively charged ion can not flow the strong interaction of active ingredient and carrier when having weakened roasting to aperture with capillary penetration.(4) the present invention at first carries out drying at room temperature behind dipping, and the time be 1～3 day, this process will help metal active constituent more uniform distribution on carrier.Carry out directly behind the dipping so that heat drying has reduced since the active ingredient that the capillary penetration effect causes by the transporting action of macropore to aperture.Carrying out heat drying under the water vapour atmosphere after the drying at room temperature again, further reduced the capillary penetration effect in addition.So the catalyst activity uniform component distribution of the present invention's preparation, pore volume and specific surface area are bigger.Be particularly suitable for the hydrofining of the distillate of reactant molecule weight range broad.
Embodiment
1, preparation carrier.
(example 1)
Get macropore aluminium hydroxide dry powder and (be meant that pore volume is greater than 0.8mlg
-1Aluminium hydroxide dry powder) 2000g, add acetic acid 50g, citric acid 50g, sesbania powder 50g and deionized water 1600ml, mix and pinch the back extruded moulding.110 ℃ of dry 3h, 550 ℃ of roasting 3h make carrier S 1, and main physico-chemical property sees Table 1.
(example 2)
Get macropore aluminium hydroxide dry powder 2000g, add acetic acid 50g, citric acid 50g, sesbania powder 50g, silicon sol 370g and deionized water 1500ml, mix and pinch the back extruded moulding.110 ℃ of dry 3h, 550 ℃ of roasting 3h make carrier S 2, and main physico-chemical property sees Table 1.
2, preparation co-impregnated solution.
(example 1)
Under the room temperature, be that 10% ammoniacal liquor adds deionized water to 46ml, add with MoO toward the 40ml mass percentage concentration
3Meter content is 83.0% ammonium tetramolybdate 18.9g and with WO
3Meter content is 80.0% ammonium metawolframate 35.2g, stirring and dissolving.In the 24ml deionized water, add 28g nickelous nitrate and 10ml ortho-phosphoric acid, after the stirring and dissolving, mix two kinds of solution.After being stirred well to dissolving fully, filter, mend deionized water, obtain limpid stable co-impregnated solution 100ml.Ammonium tetramolybdate is with MoO in this co-impregnated solution
3The concentration of meter is that 15.7g/100ml, ammonium metawolframate are with WO
3Meter concentration is that 28.9g/100ml, nickelous nitrate are that 7.19g/100ml, ortho-phosphoric acid are 4.11g/100ml in the concentration of P in the concentration of NiO, the pH=3.9 of this co-impregnated solution.
(example 2)
The method of this examples preparation single-steeping co-impregnated solution is identical with Chinese patent application 86107828, and molybdenum compound is a molybdenum oxide, preparation single-steeping co-impregnated solution under the condition of heating.
With the 15.7g molybdenum oxide, with WO
3Meter content is that 82.0% ammonium metawolframate 35.2g, 11.3g nickelous carbonate, 10ml ortho-phosphoric acid are put into the 100ml deionized water, in heating time, stir, all after the dissolving, cool off, filter limpid stable co-impregnated solution, be diluted to 100ml with deionized water, in this co-impregnated solution: MoO
3Concentration be that 15.7g/100ml, ammonium metawolframate are with WO
3The concentration of meter is that 28.9g/100ml, nickelous nitrate are that 7.19g/100ml, ortho-phosphoric acid are 4.11g/100ml in the concentration of P in the concentration of NiO.
(example 3)
This example is for to prepare the W-Mo-Ni-P co-impregnated solution with ammonium paramolybdate.Will be with MoO
3The content of meter is 80.0% ammonium paramolybdate 19.7g, with WO
3The content of meter is that 82.0% ammonium metawolframate 35.2g, nickelous nitrate 28g, ortho-phosphoric acid 10ml join in the 70ml deionized water, stirs, the moisturizing of dissolving after-filtration deionization gets the 100ml co-impregnated solution.In this co-impregnated solution: ammonium paramolybdate is with MoO
3The concentration of meter is that 15.7g/100ml, ammonium metawolframate are with WO
3The concentration of meter is that 28.9g/100ml, nickelous nitrate are that 7.19g/100ml, ortho-phosphoric acid are 4.11g/100ml in the concentration of P in the concentration of NiO.
3, preparation catalyzer.
(embodiment 1)
The carrier S 1 of preparation in the preparation carrier example 1 is dried 2h down at 150 ℃, get 90g after the cooling, its co-impregnated solution 100ml with preparation in the preparation co-impregnated solution example 1 (is not meant the temperature of system is carried out special control in room temperature, for example be under 5～35 ℃ the envrionment temperature and get final product, down together) saturated dipping (is pressed the carrier water-intake rate and is calculated the steeping fluid consumption down, down together), soaked carrier is dry 1d under 20 ℃, put into rotary roasting furnace then and carry out heat drying and roasting continuously, wherein heat drying is to carry out under the water vapour atmosphere that water vapor produced that produces at self, the exsiccant temperature is 110 ℃, time is 2h, and maturing temperature is 500 ℃, roasting time is 3h.The catalyzer that makes is designated as C1, and main physico-chemical property sees Table 2.
(embodiment 2)
The carrier S 2 of preparation in the preparation carrier example 2 is dried 2h down at 150 ℃, get 90g after the cooling, to its at room temperature saturated dipping of co-impregnated solution 100ml with preparation in the preparation co-impregnated solution example 1, soaked carrier is at 25 ℃ of dry 1d, put into rotary roasting furnace then and carry out heat drying and roasting continuously, wherein heat drying is to carry out under the water vapour atmosphere that water vapor produced that produces at self, the exsiccant temperature is that 110 ℃, time of drying are 2h, and maturing temperature is that 500 ℃, roasting time are 3h.Make catalyzer and be designated as C2, main physico-chemical property sees Table 2.
(embodiment 3)
All the other are identical with embodiment 1 for present embodiment, and difference is: soaked carrier is at 20 ℃ of dry 3d.Make catalyzer and be designated as C3, main physico-chemical property sees Table 2.
(embodiment 4)
All the other are identical with embodiment 2 for present embodiment, and difference is: soaked carrier is at 25 ℃ of dry 3d.Make catalyzer and be designated as C4, main physico-chemical property sees Table 2.
(Comparative Examples 1)
The carrier S 2 of preparation in the preparation carrier example 2 is dried 2h down at 150 ℃, get 90g after the cooling, to its at room temperature saturated dipping of co-impregnated solution 100ml with preparation in the preparation co-impregnated solution example 2, soaked carrier is dry 3d under 25 ℃, put into rotary roasting furnace then and carry out heat drying and roasting continuously, wherein heat drying is to carry out under the water vapour atmosphere that water vapor produced that produces at self, the exsiccant temperature is 110 ℃, be 2h time of drying, maturing temperature is 500 ℃, roasting time is 3h, make catalyzer and be designated as C5, main physico-chemical property sees Table 2.
(Comparative Examples 2)
The carrier S 2 of preparation in the preparation carrier example 2 is dried 2h down at 150 ℃, get 90g after the cooling, to its at room temperature saturated dipping of co-impregnated solution 100ml with preparation in the preparation co-impregnated solution example 3, soaked carrier is dry 3d under 25 ℃, put into rotary roasting furnace then and carry out heat drying and roasting continuously, wherein heat drying is to carry out under the water vapour atmosphere that water vapor produced that produces at self, the exsiccant temperature is 110 ℃, be 2h time of drying, maturing temperature is 500 ℃ in rotary roasting furnace, roasting time is 3h, make catalyzer and be designated as C6, main physico-chemical property sees Table 2.
(Comparative Examples 3)
The carrier S 2 of preparation in the preparation carrier example 2 is dried 2h down at 150 ℃, get 90g after the cooling, to its at room temperature saturated dipping of co-impregnated solution 100ml with preparation in the preparation co-impregnated solution example 1, soaked carrier is dried 3h down at 140 ℃, at 500 ℃ of following roasting 3h, make catalyzer and be designated as C7, main physico-chemical property sees Table 2.
(Comparative Examples 4)
The carrier S 2 of preparation in the preparation carrier example 2 is dried 2h down at 150 ℃, get 90g after the cooling, the co-impregnated solution 100ml of preparation in the preparation co-impregnated solution example 2 is diluted to 200ml, by dipping, oven dry and the roasting method in the Comparative Examples 3, prepare catalyzer by the secondary co-impregnation, make catalyzer and be designated as C8, main physico-chemical property sees Table 2.
(evaluation Example)
This evaluation Example is for investigating the fraction oil hydrogenation refining activity of C1, C2, C3, C4, C5, C6, C7 and C8 catalyzer.Used stock oil is the mixing oil of a kind of straight-run spirit and coker gasoline, and ratio of mixture is V (a straight vapour): V (burnt vapour)=3: 1, wherein sulphur content is 536 μ gg
-1, nitrogen content is 38 μ gg
-1, appreciation condition with the results are shown in Table 3, activity of such catalysts is represented with the temperature of reaction under identical desulfurization, the denitrification percent condition.As can be seen from Table 3, when reaching same desulfurization, denitrification effect, the temperature of reaction the when temperature of reaction when carrying out hydrofining with catalyzer of the present invention will be lower than with other catalyzer.The desulfurization of this catalyzer, the catalyzer that denitrification activity will be higher than other are described.
The main physico-chemical property of table 1 carrier
The main physico-chemical property of table 2 catalyzer
Table 3 evaluating catalyst condition and result
| Catalyzer | Reaction pressure/MPa | Temperature of reaction/℃ | Volume space velocity/h -1 | Hydrogen to oil volume ratio | Sulphur content/μ gg -1 | Nitrogen content/μ gg -1 |
| C1 | 2.5 | 296 | 3.0 | 150 | 47 | 1.0 |
| C2 | 2.5 | 298 | 3.0 | 150 | 47 | 1.0 |
| C3 | 2.5 | 298 | 3.0 | 150 | 47 | 1.0 |
| C4 | 2.5 | 295 | 3.0 | 150 | 47 | 1.0 |
| C5 | 2.5 | 302 | 3.0 | 150 | 47 | 1.0 |
| C6 | 2.5 | 300 | 3.0 | 150 | 47 | 1.0 |
| C7 | 2.5 | 310 | 3.0 | 150 | 47 | 1.0 |
| C8 | 2.5 | 314 | 3.0 | 150 | 47 | 1.0 |
Claims (10)
1, a kind of Hydrobon catalyst, its carrier are aluminum oxide or siliceous aluminum oxide, and active ingredient is WO
3, MoO
3And NiO, adjuvant component is the oxide compound of phosphorus; It is characterized in that: each components contents of mass percent in catalyzer is respectively SiO
2Be 0%～11%, WO
3Be 17%～24%, MoO
3Be 10.5%～14%, NiO is 4.5%～7%, the oxide compound of phosphorus counts 2%～4% with P, all the other are Al
2O
3Wherein, active ingredient MoO
3Raw material be ammonium tetramolybdate;
The preparation process of described Hydrobon catalyst comprises: 1. prepare support of the catalyst; 2. dissolve W, Mo, Ni under the room temperature, P-compound prepares co-impregnated solution; The pH value of co-impregnated solution is 3～4; Molybdenum compound wherein is an ammonium tetramolybdate, and ammonium tetramolybdate is by ammonia solvent; 3. the carrier of using the co-impregnated solution single-steeping that 2. makes by step 1. to make under the room temperature by step; 4. soaked carrier is at room temperature dry earlier, puts into rotary roasting furnace then and carries out heat drying and roasting continuously, and wherein heat drying is to carry out under the water vapour atmosphere that produces at self.
2, Hydrobon catalyst according to claim 1 is characterized in that: the specific surface of described catalyzer is 180～250m
2/ g, pore volume are 0.40～0.60ml/g.
3, Hydrobon catalyst according to claim 2 is characterized in that: the specific surface of described catalyzer is 211～250m
2/ g.
4, Hydrobon catalyst according to claim 3 is characterized in that: the pore volume of described catalyzer is 0.40～0.45ml/g.
5, by the preparation method of the described Hydrobon catalyst of claim 1, may further comprise the steps: 1. prepare support of the catalyst; 2. dissolve W, Mo, Ni under the room temperature, P-compound prepares co-impregnated solution; Molybdenum compound wherein is an ammonium tetramolybdate, and ammonium tetramolybdate is by ammonia solvent; 3. the carrier of using the co-impregnated solution single-steeping that 2. makes by step 1. to make under the room temperature by step; 4. soaked carrier is at room temperature dry earlier, puts into rotary roasting furnace then and carries out heat drying and roasting continuously, and wherein heat drying is to carry out under the water vapour atmosphere that produces at self.
6, preparation method according to claim 5 is characterized in that: step 2. described in tungsten compound be that ammonium metawolframate, nickel compound are that nickelous nitrate, phosphorus compound are ortho-phosphoric acid.
7, preparation method according to claim 6, it is characterized in that: the ammonium metawolframate of step in 2. when ammonium tetramolybdate is by ammonia solvent by ammonia solvent, nickelous nitrate and ortho-phosphoric acid are by deionized water dissolving, then that two kinds of solution are mixed, stirring obtain limpid stable co-impregnated solution after the filtration.
8, preparation method according to claim 7 is characterized in that: ammonium metawolframate is with WO in the co-impregnated solution that step makes in 2.
3The concentration of meter is that 16～30g/100ml, ammonium tetramolybdate are with MoO
3The concentration of meter is that 11～16g/100ml, nickelous nitrate are that 7～10g/100ml, ortho-phosphoric acid are 3.5～5.5g/100ml in the concentration of P in the concentration of NiO.
9, preparation method according to claim 8 is characterized in that: the pH value of the co-impregnated solution that step makes in 2. is 3～4.
10, preparation method according to claim 5 is characterized in that: the step 4. temperature of middle drying at room temperature is 5～30 ℃, and be 1～3d time of drying.
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| CN100998952B (en) * | 2007-01-04 | 2011-07-20 | 长春惠工净化工业有限公司 | Coking gasoline hydrogenation refining catalyst and its preparation method |
| CN101462078B (en) * | 2007-12-18 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
| CN101507929B (en) * | 2009-03-20 | 2012-09-12 | 抚顺新瑞催化剂有限公司 | Catalyst for coal tar hydrogenation modification and its preparation method and use |
| CN102319577B (en) * | 2011-07-08 | 2013-02-13 | 中国石油天然气股份有限公司 | Hydrotreating catalyst and preparation method thereof |
| CN102806088A (en) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of reformer feed hydrogenation pre-refining catalyst |
| CN105080556B (en) * | 2014-05-14 | 2018-02-13 | 中国石油化工股份有限公司 | Hydrobon catalyst and catalytic cracking light cycle oil process for purification |
| CN106552655A (en) * | 2016-11-26 | 2017-04-05 | 新疆佳宇恒能源科技有限公司 | A kind of preparation method of co-impregnated solution and wax oil hydrogenation catalyst for refining |
| CN114762825B (en) * | 2021-01-13 | 2024-04-26 | 中国科学院大连化学物理研究所 | A composite carrier-supported Pt-based catalyst and its application |
| CN115475622B (en) * | 2022-08-24 | 2023-08-25 | 宁波中金石化有限公司 | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier |
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