CN1102643C - Catalyst for hydrorefining pertroleum wax and its preparing process - Google Patents
Catalyst for hydrorefining pertroleum wax and its preparing process Download PDFInfo
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- CN1102643C CN1102643C CN98114346A CN98114346A CN1102643C CN 1102643 C CN1102643 C CN 1102643C CN 98114346 A CN98114346 A CN 98114346A CN 98114346 A CN98114346 A CN 98114346A CN 1102643 C CN1102643 C CN 1102643C
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Abstract
The present invention discloses a catalyst for hydrorefining petroleum wax and a preparation method thereof. Gamma Al2O3 is firstly prepared, wherein the chemical monolayer dispersion quantity of metal (such as Mo) on the surface of the gamma Al2O3 is 30 to 50% higher than the chemical monolayer dispersion quantity of the metal on gamma Al2O3 prepared by a common method and the catalyst has appropriate pore structure and mechanical strength. Besides, a Mo-Ni-P solution with high metal concentration and high stability is prepared, the gamma Al2O3 is immersed in the Mo-Ni-P solution at room temperature, and then the mixed solution is filtered, dried, roasted to prepare the Mo-Ni-P or Al2O3 catalyst for hydrorefining petroleum wax.
Description
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, particularly a kind of high reactivity catalyst for hydrorefining pertroleum wax and preparation method thereof.
The oil wax material contains coloured and destabilization component of a small amount of objectionable impurities such as aromatics that some is harmful and some etc. usually.The main purpose of hydrorefining petroleum waxes is to remove contained coloured, destabilization and harmful material in the oil wax material by hydrogenation.Therefore need a kind of catalyzer efficiently.The saturated performance of the existing very high hydrogenation of this catalyzer has the very high ability that removes aromatic organic compounds again.
Catalyst for hydrorefining pertroleum wax is an active ingredient with VIII family (Mo or W) and group vib (Ni) metallic element mainly, with γ-Al
2O
3Or SiO
2-Al
2O
3Be carrier.It is generally acknowledged: oil wax material molecule big (taking from the three-way cut of decompression), therefore, the ideal catalyst for hydrorefining pertroleum wax should have very high hydrofining performance, and promptly reactive metal has high degree of dispersion, big dispersion amount and good dispersion state on catalyst surface.In order to help in the reaction process diffusion of reactant and hydrogenation reaction product molecule, the pore distribution that requires catalyzer bigger aperture to be arranged and concentrate.The acidity of catalyzer (carrier) should be less, to avoid the generation of deleterious heat scission reaction in the process.In addition, the physical strength of catalyzer (carrier) should be enough high.
U.S. Pat P4,186,078 (contain SiO by adding a large amount of silicon in carrier
25～25w%) prepare SiO
2-Al
2O
3Carrier has than large specific surface, larger aperture and concentrated pore distribution to guarantee carrier.In order to reduce the acidity of catalyzer, in the process of preparation carrier, add the basic metal of 0.2～5w%.The weak point of this method is: the chemical individual layer dispersion amount of metal on carrier is not high (has only 12.5～19.1w%, with MoO
3Count), thereby the hydrofining activity is not high.Chinese patent CN 1085594A also adopts high siliceous SiO
2-Al
2O
3(contain SiO
25～10w%) make carrier.With U.S. Pat P4,186,078 differences are: add H in preparation process
3PO
4Reduce the acidity of carrier (catalyzer).This method has and U.S. Pat P4,186,078 same shortcomings.
The present invention is a kind of catalyst for hydrorefining pertroleum wax, and it has much in common with catalyst for hydrorefining pertroleum wax and other petroleum fractions hydrotreatment (making with extra care) catalyzer: be active ingredient with VIII family and group vib metallic element mainly, with γ-Al
2O
3Or SiO
2-Al
2O
3Be carrier.Therefore, guaranteeing that catalyzer has enough big aperture, sufficiently high specific surface area and bigger pore volume to be beneficial under the prerequisite of reactant and product molecular diffusion in the treating process, the hydrofining reaction activity that improves catalyzer is crucial.
In order to improve the hydrofining reaction activity of catalyzer, require metal at γ-Al
2O
3Have on the surface than high degree of dispersion and big dispersion amount, thereby require its chemical individual layer dispersion amount should be bigger.And this chemical individual layer dispersion amount is by γ-Al
2O
3Carrier surface properties determined.Therefore, the good γ-Al of processability
2O
3Carrier has conclusive effect to the activity that improves catalyst for hydrorefining pertroleum wax.
The objective of the invention is γ-Al by the preparation advantageous property
2O
3Carrier and the corresponding high density of preparation, high stability dipping solution not only have high metal content but also high metal dispersity is arranged thereby prepare, and also have the high reactivity catalyst for hydrorefining pertroleum wax of good metal dispersion state simultaneously.This catalyzer should have bigger specific surface area and pore volume equally, good pore structure and higher physical strength.
Catalyst for hydrogen refining of paraffin wax of the present invention is with γ-Al
2O
3Be carrier, support the Mo-Ni-P component, wherein MoO
323～28w%, NiO 4.5～6.0w%, P 2.3～3.0w%, the specific surface area of catalyzer is 160～205m
2/ g, pore volume 0.30～0.40ml/g, average pore diameter 7.5～11.0nm, particularly MoO
3Individual layer dispersion amount on alumina supporter is 23.0～27.0w%.
The active ingredient loading is big in order to obtain, MoO
3Individual layer scatter coefficient height, the catalyzer that structure properties is good, the present invention improves the preparation of preparing carriers method and steeping fluid.
The present invention includes three aspects: (1) prepares novel γ-Al
2O
3Metal (as Mo) is at this γ-Al
2O
3Lip-deep chemical individual layer dispersion amount is than the γ-Al that adopts usual way to make
2O
3Exceed 30%～50%, thereby guarantee have more active metal component (Mo and Ni) to be dispersed on the catalyst surface.Can guarantee that also catalyzer has proper pore structure and physical strength.(2) the Mo-Ni-P solution of compounding high concentration, high stability; (3) use above-mentioned solution impregnated catalyst carrier, prepare highly active Mo-Ni-P/Al
2O
3Catalyst for hydrogen refining of paraffin wax.
Carrier γ-Al of the present invention
2O
3The preparation main points are: at roasting γ-Al
2O
3During precursor, adopt " three sections constant temperature calcinings " program with control γ-Al
2O
3Structure and surface properties, thereby improve final γ-Al
2O
3The physico-chemical property of product makes it have bigger metallochemistry individual layer dispersion amount.Simultaneously, this γ-Al
2O
3In the requirement that also should satisfy the preparation catalyst for hydrorefining pertroleum wax aspect specific surface area, aperture, pore volume and the physical strength.
γ-Al of the present invention
2O
3The preparation process of carrier is: a water aluminum oxide, promptly α-AlO (OH) (contains alumina trihydrate＜5w%) and is mixed into plastic shape, extruded moulding on banded extruder, drying with peptization acid.Make γ-Al according to " three sections constant temperature calcinings " of the present invention program then
2O
3Carrier.
γ-Al of the present invention
2O
3The concrete preparation process of carrier is:
(1) takes by weighing and contain Al
2O
3The water aluminum oxide of 65～70w% (contents on dry basis) (contains the dry glue powder 100g～350g of alumina trihydrate＜5w%), adds nitric acid and/or acetic acid solution, fully mix and pinch until becoming plastic shape.(2) on banded extruder, be extruded into bar shaped (or trifolium, Herba Galii Bungei type, its shape is determined by orifice plate).(3) the wet bar after the moulding is following dry 2～4 hours at 105～130 ℃.(4) then, place High Temperature Furnaces Heating Apparatus, be warming up to 150～270 ℃ with 3～5 ℃ of/minute speed, and under this temperature constant temperature calcining 0.5～3.0 hour.Then be warming up to 300～495 ℃ with 4～6 ℃ of/minute speed, and under this temperature constant temperature calcining 2.0～5.0 hours.Be warming up to 520～700 ℃ with 4～6 ℃ of/minute speed at last, and under this temperature constant temperature calcining 1.0～3.0 hours.
γ-the Al that makes according to the inventive method
2O
3Has following character: (1) MoO
3Chemical individual layer dispersion amount in its surface is than the γ-Al that adopts usual way to make
2O
3Exceed 30～50% or more.(2) specific surface area is 300～400m
2/ g; Average pore diameter is 7.0～10.0nm; Pore volume is 0.65～0.75ml/g; Physical strength 〉=130N/cm (to little of φ=1.0mm).
The preparation main points of high density Mo-Ni-P solution of the present invention are: by the strength of solution requirement required phosphoric acid is added in the entry, make phosphate aqueous solution.Above-mentioned phosphate aqueous solution is joined in the molybdenum oxide of aequum.This system under agitation is warming up to little boiling, and is heated to the most of dissolving of molybdenum oxide.System temperature is reduced to 60～70 ℃, add the basic nickel carbonate of requirement.Heat up once more be heated to little boil and be heated to basic nickel carbonate all dissolve.Last slowly heating evaporation is removed redundant moisture and is made solution concentration, makes the Mo-Ni-P solution of high density, high stability.
The step that the present invention prepares Mo-Ni-P solution is as follows:
(1) molybdenum oxide is added in the phosphate aqueous solution.Stir.Slowly heat temperature raising boils and is heated to molybdenum oxide all or most of dissolving to little.
(2) after above-mentioned solution is cooled to 60～70 ℃, slowly add basic nickel carbonate.Place be warming up to again after 15 minutes little boil and be heated to basic nickel carbonate all dissolve.Reduce to the room temperature after-filtration to remove insoluble impurities.
(3) above-mentioned solution heating is concentrated into needed concentration.
The prepared Mo-Ni-P solution according to the present invention has following character:
(1) every 100ml solution contains MoO
350～55g, NiO 8～10g.P/MoO
3Weight ratio is 0.08～0.18.
(2) if desired, this solution can continue to heat and is concentrated into higher concentration.
(3) this solution at room temperature can be stablized more than 3 years.
The preparation main points of catalyst for hydrorefining pertroleum wax of the present invention are as follows: with the γ-Al of method for preparing
2O
3(or SiO
2-Al
2O
3) for the Mo-Ni-P solution of carrier and method for preparing is steeping fluid, with a step immersion process for preparing Mo-Ni-P/Al
2O
3Catalyst precursor.Adopt " three section roastings " preparation catalyzer then, promptly behind dipping and dry (110～130 ℃), catalyst precursor respectively at 160～205 ℃, is carried out roasting under 282～371 ℃ and 388～499 ℃, make catalyst for hydrorefining pertroleum wax.
In the above-mentioned roasting process, initially the heat-up rate between intensification and per two the constant temperature calcining sections is 3～5 ℃/minute.The first constant temperature zone roasting time is 0.5～2.0 hour, and the second constant temperature zone roasting time is 0.5～2.0 hour, and the 3rd constant temperature zone is 2.0～5.0 hours.
Prepared hydrotreating catalyst has following character according to the present invention:
(1) metal content is MoO
323～28w%, NiO 4.5～6.0w%, P 2.3～3.0w%.
(2) specific surface area is 160～200m
2/ g; Pore volume is 0.30～0.40ml/g; Average pore diameter is 7.5～11.0nm; Physical strength 〉=160N/cm (little of φ=1.0mm).
(3) active ingredient Mo-Ni-P not only has bigger dispersion amount and higher dispersity on catalyst surface, and preferable dispersion state is arranged, thereby the hydrofining activity is higher.
Advantage of the present invention is:
(1) the present invention is simple and easy to do.Control carrier γ-Al by control calcination steps and maturing temperature
2O
3Surface properties and improve reactive metal at Mo-Ni-P/Al
2O
3Dispersion state on the catalyst surface improves Mo-Ni-P/Al thereby reach
2O
3The active purpose of the hydrorefining petroleum waxes of catalyzer.
(2) the made γ-Al of the present invention
2O
3Carrier has higher metallochemistry individual layer dispersion amount, than the γ-Al that makes with usual way
2O
3Exceed 30～50% or more.
(3) the made γ-Al of the present invention
2O
3Specific surface area, the pore volume of carrier are bigger, and average pore diameter can (7.0～10.0nm) change, thereby can satisfy the requirement of preparation catalyst for hydrorefining pertroleum wax to the aperture in a big way.
(4) the made Mo-Ni-P solution of the present invention is formed rationally, and concentration is high and can be steady in a long-term.Therefore, reactive metal is at made Mo-Ni-P/Al
2O
3High level is not only arranged on the catalyst surface, and higher dispersity and good dispersion state are arranged, help improving the hydrofining activity of this catalyzer.
(5) Mo-Ni-P/Al of the present invention
2O
3Catalyst for hydrorefining pertroleum wax, the catalyzer that its hydrofining reaction specific activity makes with usual way wants high.
For further specifying all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1 (1) γ-Al
2O
3The preparation of carrier
Take by weighing a water aluminum oxide dry glue powder (containing the 2w% alumina trihydrate) 200g, add the 2.0ml Glacial acetic acid, the 5.0g silicon sol (contains SiO
230w%), 160ml HNO
3(3%) and an amount of H
2O.Thorough mixing, be kneaded into and be extruded into trifolium strip (φ=1.2mm) behind the plastic shape.After air drying spends the night, be that 110 ℃ dried 2 hours down.
Dry sample is placed High Temperature Furnaces Heating Apparatus, is warming up to 200 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then with 4 ℃ of speed of per minute be warming up to 468 ℃ and under this temperature constant temperature calcining 3.0 hours, again with 4 ℃ of speed of per minute be warming up to 600 ℃ and under this temperature constant temperature calcining 2.0 hours.(2) preparation of Mo-Ni-P solution
20ml phosphoric acid (85%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 60～70 ℃, under agitation slowly add basic nickel carbonate 60g, be warming up to again and littlely boil and heated 3 hours, dissolve substantially to throw out, filter.Filtrate is concentrated into 260ml.(3) Mo-Ni-P/Al
2O
3Preparation of Catalyst
Take by weighing γ-Al
2O
3100g adds the Mo-Ni-P solution of 150ml according to embodiment 1 (2) preparation.After at room temperature flooding 4 hours, leach redundant solution.Moist catalysis was dried 2 hours down at 120 ℃ after air drying spends the night.Dried sample is warming up to 190 ℃ with 5 ℃ of/minute speed, constant temperature calcining 1 hour.Be warming up to 368 ℃ with 5 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 490 ℃ with 5 ℃ of/minute speed at last, constant temperature calcining 4 hours.
Embodiment 2 (1) γ-Al
2O
3The preparation of carrier
Take by weighing a water aluminum oxide dry glue powder (containing the 2w% alumina trihydrate) 200g, add the 2.0ml Glacial acetic acid, the 10.0g silicon sol (contains SiO
230w%), 160ml HNO
3(3%) and an amount of H
2O.Thorough mixing, be kneaded into and be extruded into trifolium strip (φ=1.2mm) behind the plastic shape.After air drying spends the night, be that 110 ℃ dried 2 hours down.
Dry sample is placed High Temperature Furnaces Heating Apparatus, is warming up to 250 ℃ with 5 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then with 5 ℃ of speed of per minute be warming up to 380 ℃ and under this temperature constant temperature calcining 4.0 hours, again with 6 ℃ of speed of per minute be warming up to 680 ℃ and under this temperature constant temperature calcining 1.0 hours.(2) preparation of Mo-Ni-P solution
With embodiment 1 (2).But the last simmer down to 240ml of filtrate.(3) Mo-Ni-P/Al
2O
3Preparation of Catalyst
Take by weighing γ-Al
2O
3100g adds the Mo-Ni-P solution of 150ml according to (2) preparation.After at room temperature flooding 4 hours, leach redundant solution.Moist catalysis was dried 2 hours down at 120 ℃ after air drying spends the night.Dried sample is warming up to 200 ℃ with 4 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 350 ℃ with 4 ℃ of/minute speed again, constant temperature 1 hour.Be warming up to 470 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 4 hours.
Embodiment 3 (1) γ-Al
2O
3The preparation of carrier
With embodiment 1 (2).(2) preparation of Mo-Ni-P solution
With embodiment 1 (1).But the last simmer down to 220ml of filtrate.(3) Mo-Ni-P/Al
2O
3Preparation of Catalyst
With embodiment 2 (3).The preparation of comparative example 1 (according to CN 1085594A method) (1) carrier
To contain Al
2O
3The AlCl of 5g/100ml
3Solution 10L with contain SiO
2The acidified sodium silicate 0.5L of 5g/100ml mixes, and pH value is transferred to 2.8, keeps 15 ℃, leaves standstill 2 hours.Be 15 ℃ with temperature then, concentration is in 9% the ammoniacal liquor and above-mentioned solution.Control ammoniacal liquor flow, making reaction contact time is 10 minutes, and total reaction time is 90 minutes, and material PH is 7.8.Filtration under diminished pressure.Filter cake distilled water wash 3 times.Wash temperature is 25 ℃, and washing time is 40 minutes.Corresponding to 1kg Al
2O
3The wet gel amount of butt, the H of adding 81g 53%
3PO
4Solution and 190ml 33%HNO
3, stirred 2 hours under the room temperature, make colloidal sol.Colloidal sol is dripped by water dropper, by oil ammonia column (room temperature).The wet bulb of making soaked 3 hours in 5% ammoniacal liquor.Then wet bulb was dried 3 hours down at 90 ℃, 620 ℃ of following roastings 4 hours.(2) Preparation of Catalyst
Take by weighing by (1) prepared γ-Al
2O
3Bead 200g added after bleeding in filter flask 1 hour and contains MoO
325g/100ml, the ammonium molybdate of NiO 6.0g/100ml and nickelous nitrate ammonia soln 400ml flood 1 hour after-filtration.Catalyst precursor was dried 3 hours down at 120 ℃, 530 ℃ of following roastings 3 hours.Comparative example 2
Step is identical with comparative example 1.53% H
3PO
4Solution usage changes 120g into, i.e. the cost example.
More than the physico-chemical property of each routine carrier and catalyzer list in table 1 and the table 2 respectively.Each routine catalyst activity evaluation result is as shown in table 3.Evaluation of catalyst activity is raw materials used to be No. 60 wax materials (Shenyang).Reaction process condition is: LHSV 0.8h
-1, pressure (hydrogen pressure) 6.0MPa, 270 ℃ of temperature of reaction, hydrogen/wax is 300 than (body).Evaluate catalysts was vulcanized respectively under 230 ℃ and 300 ℃ 8 hours with the grand celebration aviation kerosene cut that contains dithiocarbonic anhydride 2V%.Sulfuration finishes, and the swap-in paraffin is stablized after 8 hours and begun to test.
By table 1 as seen: with the carrier γ-Al of comparative example
2O
3Compare carrier γ-Al of the present invention
2O
3Have suitable aperture and pore distribution, and specific surface and pore volume are bigger.The more important thing is carrier γ-Al of the present invention
2O
3Have much bigger chemical individual layer dispersion amount, help more active ingredient (Mo, Ni) and disperse in its surface.
By table 2 as seen: (1) is compared with comparative example, and the content of catalyst activity metal of the present invention (Mo, Ni) is higher, helps improving the hydrofining activity of catalyzer.(2) catalyzer of the present invention has bigger aperture and concentrated characteristics such as pore distribution equally.
By table 3 as seen: (1) catalyzer of the present invention has excellent results to the petroleum wax hydrogenation.Compare the light stability low at least (being better than) number (embodiment 1) of refining wax with the comparative example catalyzer.Refining wax (embodiment 1) is at the ultraviolet absorption value (characterizing the height of aromatic hydrocarbon content in the wax) at 280～289nm and 290～299nm place, and is all much lower than comparative example.Illustrate catalyzer of the present invention have very high to aromatic hydrocarbon saturated performance and to the refining performance of petroleum wax.(2) further improve active metallic content (embodiment 2,3), the hydrofining of catalyzer is active further to improve, and light stability can lower than comparative example (being better than) two numbers, and ultraviolet absorption value then further reduces.
Each routine carrier γ-Al of table 1
2O
3Physico-chemical property
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Chemical constitution, w% | SiO 2 P Al 2O 3 | 1.9---surplus | 3.8---surplus | 3.8---surplus | 7.4 2.0 surpluses | 7.3 2.7 surpluses |
| Chemistry individual layer dispersion amount, MoO 3w％ | 24.0 | 24.6 | 26.0 | 17.6 | 18.3 | |
| Specific surface, m 2The total pore volume of/g, the pore distribution of ml/g physical strength, v%＜4.0nm 4.0～15.0nm＞15.0nm | 346 0.71 138N/cm (φ=1.0mm bar) 6.3 87.7 6.0 | 350 0.73 136N/cm (φ=1.0mm bar) 6.6 87.0 6.4 | 352 0.72 140N/cm (φ=1.0mm bar) 6.6 87.1 6.3 | 240 0.56 112N/ grains 4.6 92.3 3.1 | 248 0.60 111N/ grains 7.0 90.6 2.4 |
| PVI, %[annotates] | 90.0 | 90.2 | 90.4 | 91.2 | 90.0 |
The physico-chemical property of each routine catalyzer of table 2 relatively
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Chemical constitution, w% MoO 3 NiO P SiO 2 | 23.6 4.6 2.4 1.5 | 24.7 4.8 2.5 2.9 | 25.7 5.1 2.5 2.9 | 19.0 4.6 1.3 5.2 | 20.2 4.6 1.9 5.1 |
| Specific surface, m 2The total pore volume of/g, the pore distribution of ml/g physical strength, v%＜4.0nm 4.0～15.0nm＞15.0nm | 180 0.34 180N/cm (φ=1.0mm bar) 6.1 87.7 6.2 | 171 0.33 180N/cm (φ=1.0mm bar) 6.5 86.9 6.6 | 163 0.32 180N/cm (φ=1.0mm bar) 6.3 87.1 6.6 | 240 0.53 63N/ grains 4.1 92.3 3.6 | 248 0.58 62N/ grains 6.6 90.6 2.8 |
| PVI, %[annotates] | 90.2 | 89.9 | 90.4 | 91.8 | 90.0 |
Each routine activity rating of catalyst result of table 3
| Paraffin | Refining wax product character | |||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Fusing point, ℃ | 60.3 | 60.3 | 60.4 | 60.3 | 60.2 | 60.2 |
| Oleaginousness, w% | 0.14 | 0.14 | 0.13 | 0.14 | 0.14 | 0.15 |
| Color (Saybolt) number | +19 | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ＞+30 |
| Light stability, number | 5 | 3 | 2～3 | 2 | 4 | 4 |
| Readily carbonizable substance | Defective | Qualified | Qualified | Qualified | Qualified | Qualified |
| Ultraviolet extinction value (simple and easy FDA) 280～289nm, 290～299nm | 0.250 0.189 | 0.030 0.020 | 0.026 0.016 | 0.019 0.010 | 0.050 0.028 | 0.047 0.026 |
[notes]: PVI=(6～15nm/0～15nm) * 100
Claims (5)
1. catalyst for hydrogen refining of paraffin wax is with γ-Al
2O
3Be carrier, support the Mo-Ni-P component, the specific surface area of catalyzer is 160～205m
2/ g, pore volume 0.30～0.40ml/g, average pore diameter 7.5～11.0nm is characterized in that this catalyzer contains MoO
323～28w%, NiO 4.5～6.0w%, P 2.3～3.0w%, MoO
3Individual layer dispersion amount on alumina supporter is 23.0～27.0w%.
2. the preparation method of a catalyst for hydrogen refining of paraffin wax is flooded γ-Al with the mixing solutions that contains Mo-Ni-P
2O
3Carrier, and then drying and roasting is characterized in that γ-Al
2O
3The preparation method of carrier is: with the α-AlO (OH) of sour peptization pinch through mixing, extruded moulding, oven dry and roasting make carrier, said roasting be will oven dry strip 150～270 ℃ of following roastings 0.5～3.0 hour, 300～495 ℃ of following roastings 2.0～5.0 hours, at last 520～700 ℃ of following roastings 1.0～3.0 hours.
3. according to the method for claim 2, it is characterized in that the concentration of the mixing solutions of the said Mo-Ni-P of containing is: every 100ml solution contains MoO
350～55g, NiO 9～10g, P/MoO
3Weight ratio is 0.08～0.18.
4. according to the method for claim 2, after it is characterized in that the support of the catalyst dipping contains the mixing solutions and drying of Mo-Ni-P, 160～205 ℃ of following roastings 0.5～2.0 hour, 282～371 ℃ of following roastings 0.5～2.0 hour, at last 388～499 ℃ of following roastings 2.0～5.0 hours.
5. according to the method for claim 2, it is characterized in that the mixing solutions of the said Mo-Ni-P of containing is prepared as follows: a. adds phosphate aqueous solution in the molybdenum oxide, be warming up to little boil and heat make its most of dissolving after, be cooled to 60 ℃～70 ℃; B. in a solution, add basic nickel carbonate, be heated to little boil and continue heating make its dissolving; C. heating evaporation concentrates b solution to needed concentration.
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| CN1331995C (en) * | 2004-10-29 | 2007-08-15 | 中国石油化工股份有限公司 | Paraffin hydrogenation refining catalyst and its preparation method |
| CN101260317B (en) * | 2007-03-08 | 2013-05-08 | 北京三聚环保新材料股份有限公司 | Hydrorefining catalyst and its preparation method |
| CN102600913B (en) * | 2011-01-20 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for preparing molybdenum, nickel and phosphorus dipping aqueous solution |
| CN103962164B (en) * | 2013-02-05 | 2016-03-30 | 神华集团有限责任公司 | Fischer-Tropsch oil hydrofining catalyst and preparation method thereof |
| CN106994362A (en) * | 2017-04-10 | 2017-08-01 | 武汉凯迪工程技术研究总院有限公司 | The preparation method of high-nitrogen raw oil Hydrobon catalyst and preparation method thereof and its carrier |
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| US4186078A (en) * | 1977-09-12 | 1980-01-29 | Toa Nenryo Kogyo Kabushiki Kaisha | Catalyst and process for hydrofining petroleum wax |
| JPS58153539A (en) * | 1982-03-09 | 1983-09-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for hydrodesulfurization |
| US5246569A (en) * | 1990-08-03 | 1993-09-21 | Akzo N.V. | Process for the hydrodesulfurization of light hydrocarbon feeds |
| CN1085594A (en) * | 1992-10-14 | 1994-04-20 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Wax hydrofining catalyst |
-
1998
- 1998-09-28 CN CN98114346A patent/CN1102643C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4186078A (en) * | 1977-09-12 | 1980-01-29 | Toa Nenryo Kogyo Kabushiki Kaisha | Catalyst and process for hydrofining petroleum wax |
| JPS58153539A (en) * | 1982-03-09 | 1983-09-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for hydrodesulfurization |
| US5246569A (en) * | 1990-08-03 | 1993-09-21 | Akzo N.V. | Process for the hydrodesulfurization of light hydrocarbon feeds |
| CN1085594A (en) * | 1992-10-14 | 1994-04-20 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Wax hydrofining catalyst |
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| Publication number | Publication date |
|---|---|
| CN1249329A (en) | 2000-04-05 |
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