CN102049295B - Super-deep fraction oil hydrodesulphurization catalyst and preparation method thereof - Google Patents
Super-deep fraction oil hydrodesulphurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bulk phase super-deep hydrodesulphurization catalyst and a preparation method thereof. The catalyst comprises composite oxide NixWyOz, MoO3, alumina and SAPO-11 molecular sieve. The method comprises the following steps of: adding a proper amount of water-soluble nitrogen-containing compound in the precipitation process of Ni, W and Al, gelling, adding SAPO-11 molecular sieve liquid, ageing, pulping with the MoO3, and molding and activating to obtain the catalyst. The method improves the pore structure of the catalyst to expose more metal active sites on the surface of the catalyst, improves the utilization rate of active metals, and enables the SAPO-11 molecular sieve and the hydrogenation active metals to uniformly and fully contact and well match so as to achieve the effect of super-deep desulphurization of diesel oil. Moreover, because of the increment of aperture and pore volume of the catalyst, the Ni-W high active center is fully utilized, the complex big structural molecules are easier to contact the active center, and particularly the effect when the fraction oil with high macromolecule content is treated is more obvious.
Description
Technical field
The present invention relates to a kind of catalyst for hydrodesulfurizationfraction fraction oil and preparation method thereof, particularly contain the body phase distillate ultra-deep hydrodesulfuration Catalysts and its preparation method of SAPO-11 molecular sieve.
Background technology
Because the burning of sulfur-containing compound cause serious harm can for world environments and society in the fuel, so in the standard of the clean fuel formulated of countries in the world, improved greatly the wherein restriction of sulfur content.EPA reduces to 15ppm in June, 2006 with the standard of diesel oil sulfur content.In the various desulfur technologies of diesel oil, the most ripe is the hydrodesulfurization technology.The method that realizes deep desulfuration comprises development of new reactor and new catalyst.Dynamics research shows that if the sulfur content of diesel oil is reduced to below the 15ppm from 500ppm, the volume of reactor must increase by three times, and its cost is very high concerning the high-temperature high-voltage reaction device.Therefore, realize that the only method of deep hydrodesulfurizationof of diesel oil is the highly active catalyst of exploitation.
In petroleum distillate, contain the multiple structure sulfur-containing compound different, comprise mercaptan, thioether, thiophenes with molecular weight.These sulfur-containing compounds can carry out hydrogenation and desulphurization reaction and from raw material, remove sulphur atom (for example the sulfide of mercaptan, straight chain and ring-type is converted into saturated hydrocarbons or aromatic compound) under the industrial hydrodesulfurization reaction condition of routine.In deep desulfuration stage (sulfur content is lower than 500 μ g/g) and ultra-deep desulfurization stage (sulfur content is lower than 50 μ g/g), the sulfur-containing compound in the diesel oil distillate is mainly dibenzothiophenes class sulfide.The reactivity of this type sulfide and substituent quantity and position are closely related.4; 6-dimethyl Dibenzothiophene class sulfide is generally the most difficult one type of sulfide that removes; Because and sulphur atom next-door neighbour's methyl make produced between sulphur atom and the activity of such catalysts center sterically hindered, the not accessible reactive activity of sulphur atom center, thereby cause reaction rate to descend significantly.Therefore, realize that deep desulfuration must develop dibenzothiophenes and derivative thereof are had highly active catalyst.
In Hydrobon catalyst, generally adopt Co-Mo and Ni-Mo at present as active component, with Al
2O
3Be carrier, adopt the method for dipping, utilize the process of one or more dryings and roasting to process catalyst then.Also can be with carrier material and VIII family and vib metal composition prepared by co-precipitation hydrogenation catalyst.
Bulk phase catalyst is meant that the loaded catalyst that is dispersed on the carrier with active component is relative, is not carrier with inactive carrier.The catalyst major part is made up of active component, and the content of active constituent is generally unrestricted, also claims body catalyst sometimes.
US6299760, US6156695, US6537442, US6440888, US6652738 disclose and have contained VIII family/group vib active metal component and be used for bulk phase catalyst of hydrotreatment and preparation method thereof.Preparation of catalysts can adopt solution route or solid route, and tenor can reach 50wt%-100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Can contain or not contain adhesive component in the catalyst.Adhesive mainly is used for bonding metal, improves the intensity of catalyst.Because the catalyst metal content of this method preparation is high, often lacks enough interactions between metal and aluminium oxide and can cause catalyst strength poor.Active component part is made up of a large amount of metals, in forming Ni-Mo or Ni-Mo-W powder process, has some interior metal components and can not be fully utilized and cause loss of activity, and this problem can not be able to solution through simple bonding.
CN1951561A has proposed a kind of preparation method of hydrotreatment catalyst, comprising: (1) coprecipitation generates Ni
xW
yO
zThe composite oxides precursor; (2) Ni
xW
yO
zComposite oxides precursor and MoO
3Making beating mixes, filters; (3) moulding, activation are final catalyst.The catalyst metal content of this method preparation is high, but pore volume and specific area are less, have influenced the dispersiveness of high-load reactive metal, do not bring into play the activity of high-load metal component fully.Active metallic content is high can to increase the catalyst cost, the less Application of Catalyst scope that influenced of while pore volume, and (like the hydrocracking prerefining) can not show good catalytic activity when being used to handle heavy distillate.
Sulfur content is when 500 μ g/g are following in the diesel oil, and sulfur-containing compound all is to have sterically hindered difficulty to remove sulfur containing species.In the industry; Common Hydrobon catalyst is just because of being difficult to 4-MDBT (4-MDBT), 4; 6-DMDBT (4; The 6-dimethyl Dibenzothiophene) etc. have sterically hindered sulfur-containing compound and transform and can't carry out deep desulfuration, thereby be difficult to obtain in the product sulfur content less than the ultra clean fuel of 50 μ g/g.In ultra-deep desulfurization; Remove 4,6-dimethyl Dibenzothiophene class sulfides can be saturated through hydrogenation, Methyl transporters, methyl removes and four kinds of reaction paths such as C-C bond fission; Make 4; The methyl of next-door neighbour's sulphur atom is distorted, removes and variation such as transfer in the 6-dimethyl Dibenzothiophene class sulfide, has reduced the sterically hindered of sulphur atom, makes sulphur atom be easy to contact with catalyst active center and carries out desulphurization reaction.Methyl transporters, methyl remove the catalyst that uses with three kinds of reaction path requirements such as C-C bond fission and have certain acidity.Catalyst adds a spot of molecular sieve when having the strong hydrogenation activity, make catalyst have certain strong acid center, can significantly improve desulfurization, the denitrification activity of catalyst, reaches the purpose of diesel oil distillate ultra-deep desulfurization.
The SAPO-11 molecular sieve is a kind of siliceous aluminophosphate molecular sieve of the AEL of having type topological structure.US4,440,871 at first disclose the first synthetic method of SAPO-11 molecular sieve, and US 4 thereafter; 701,485, US5,208; 005, US 4,943, and 424, CN 1155519C, CN 1174919C disclose again about the synthetic method of SAPO molecular sieve or improved synthetic method.The type molecular sieve contains one dimension ten-ring straight hole structure, and the duct is oval, and size is 0.39 * 0.63nm, has tradable cation.Not siliceous AEL type aluminophosphate molecular sieve is not because the skeleton charge balance that aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron are formed has acidic site.The SAPO-11 molecular sieve produces acidic site owing to silicon species is introduced framework of molecular sieve; Therefore expanded the purposes of phosphate aluminium molecular sieve, such as being used for the gasoline isomerization process, lubricating oil isomerization dewaxing process; Low-carbon alkene is converted into the gasoline process, and disproportionation is produced in the xylenes process.EP 0,537, and 372 disclose and adopt two-step method to carry out the process of FCC gasoline hydrogenation modifying.The first step of this process utilizes clay to remove the high unsaturates (for example diene alkene) in the FCC gasoline, thereby forms stable FCC gasoline; Second step adopted the SAPO-11 molecular sieve as the gasoline heterogeneous catalyst, carried out isomerization reaction.
In the catalyst of body phase method preparation, because active metallic content is higher, making full use of of activity of such catalysts metal component is very important.In the prior art; The only cooperation effect between the kind of emphasical metal and content and the different metal; How to let catalyst have the active metal component of rational pore structure and high-load to play one's part to the full; How to let acidic components and reactive metal in the catalyst reasonably combine, how to let when same tenor catalyst have aspects such as better hydrogenation activity and do not relate to.
Summary of the invention
To weak point of the prior art, the invention provides a kind of body phase distillate ultra-deep hydrodesulfuration Catalysts and its preparation method.This method can be improved the catalyst pores structure; Metal disperses more even; Better its metal component of performance is active, and the SAPO-11 molecular sieve can give full play to its acidity, and with the hydrogenation active metals better fit; Reach the effect of Ultra-deep Desulfurization of Diesel Fuels, suit especially in the mink cell focus hydrotreatment, to use.
The bulk phase catalyst major part is made up of active metal component, and the content of active metal component is generally unrestricted, but active metallic content is high, will increase the Preparation of catalysts cost, and influences the pore structure and the intensity of catalyst.And the conventional negative supported catalyst receives the restriction of carrier hole structure, and the reactive metal load capacity can not be too much, and active the raising is restricted.The present invention finds through a large amount of experiments; Become an amount of water-soluble nitrogen-containing compound of introducing in the glue process at bulk phase catalyst; Can regulate the pore structure of catalyst and the distribution of reactive metal; Under the situation that is lower than conventional bulk phase catalyst active metallic content, still can reach the activity of conventional bulk phase catalyst, can also increase the intensity of catalyst simultaneously.And add the β zeolite with suitable way, and it is matched with active metal component better, be beneficial to 4, the desulfurization of sterically hindered big sulfur-containing compound such as 6-dimethyl Dibenzothiophene class, and then reach the purpose of ultra-deep desulfurization.
Body phase ultra-deep hydrodesulfuration catalyst of the present invention contains Mo, W, three kinds of metal components of Ni, and wherein W, Ni exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Weight with catalyst is benchmark, composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 30%～70%, be preferably 35%～55%, the content of aluminium oxide is 10%～65%, is preferably 30%～60%, the content of SAPO-11 molecular sieve is 1%～20%, is preferably 5%～15%; The character of catalyst of the present invention is following: specific area is 150～450m
2/ g; Pore volume is 0.20～0.60ml/g; Pore-size distribution is following: diameter is that the shared pore volume in hole below the 4nm accounts for 10%～35% of total pore volume; Diameter is that the shared pore volume in the hole of 4～15nm accounts for 50%～85% of total pore volume, and what diameter was that the above pore volume of 15nm accounts for total pore volume is 5%～15%, and preferred pore-size distribution is following: diameter is that the shared pore volume in hole below the 4nm accounts for 10%～25% of total pore volume; Shared pore volume accounts for 60%～80% of total pore volume to diameter in the hole of 4～15nm, and what diameter was that the above shared pore volume in hole of 15nm accounts for total pore volume is 8%～15%.
In the catalyst of the present invention, composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 7～7: 1, is preferably 1: 3～3: 1.Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 8～8: 1, be preferably 1: 5～5: 1.
The used SAPO-11 molecular sieve of catalyst of the present invention can adopt conventional method synthetic, and such as hydrothermal crystallization method, the character of used SAPO-11 molecular sieve is following: SiO
2/ Al
2O
3Mol ratio is 0.1～1.3, and meleic acid 0.6～1.3mmol/g, pore volume are 0.10～0.25ml/g, specific area 150～300m
2/ g.
Can also contain in silica, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, the boron oxide compound one or more in the catalyst of the present invention, the weight content in catalyst is 0～30%, is preferably 1%～20%.
Preparation of catalysts process of the present invention may further comprise the steps:
(1) coprecipitation generates Ni
xW
yO
zThe composite oxides precursor; (2) to Ni
xW
yO
zAdd the SAPO-11 molecular sieve pulp in the composite oxides precursor, aging under stirring condition; (3) to step (2) obtain aging after mixture in add MoO
3Making beating mixes, filters, and is dry then; (4) through roll, moulding, activation be final catalyst; Wherein step (1) process is following: preparation contains the saline mixed solution of Ni, W, Al component; Also flow to add in the retort that water purification is housed simultaneously with the water miscible nitrogen-containing compound aqueous solution, precipitating reagent ammoniacal liquor then and become glue; The pH value of slurries is in 7.0～10.0 scopes in the retort, processes gelatinous precipitate, promptly is composite oxides Ni
xW
yO
zPrecursor; Wherein the addition of water miscible nitrogen-containing compound is with NH
4 +Meter, with the mol ratio of active metal nickel and tungsten total amount be 0.2～2.0, precipitating reagent can working concentration ammoniacal liquor arbitrarily.Described water miscible nitrogen-containing compound can be selected one or more in ammonium citrate, carbonic hydroammonium, ammonium acetate, the ammonium oxalate, is preferably carbonic hydroammonium.
The described preparation of step (1) contains the saline mixed solution of Ni, W, Al component; Wherein contain nickel salt and can be in nickelous sulfate, nickel nitrate, the nickel chloride etc. one or more; Tungstenic salt can be in sodium tungstate, the ammonium metatungstate etc. one or more, contains aluminium ion solution and can be in aluminum nitrate, aluminium chloride, the aluminum sulfate etc. one or more.Becoming the glue temperature is 30～100 ℃, and gelation time was generally 0.5～5.0 hour, was preferably 0.5～3.0 hour.
The described SAPO-11 molecular sieve pulp of step (2) is to be to mix in 1: 1～10: 1 by volume with SAPO-11 molecular sieve and water, through grinding, processes molecular sieve pulp then.The described aging condition of step (2) is under stirring state, and aging temperature is 30～90 ℃, and ageing time 1～5 hour, pH value are 7.0～10.0.
50～150 ℃ of the described baking temperatures of step (3), 0.5～24 hour drying time.
Step (4) is described to roll in the process; Can add extrusion aid; Described extrusion aid is meant the material that helps extrusion modling, and like in sesbania powder, carbon black, graphite powder, the citric acid etc. one or more, the consumption of extrusion aid accounts for the 1wt%～10wt% of total material butt.Can or contain with water purification after the moulding and can decompose salt (like ammonium acetate) solution and wash.
The described activation of step (4) comprises processes such as dry and roasting.Stripe shape thing drying, roasting obtain final catalyst prod after will washing.Wherein dry and roasting can be adopted this area normal condition, as 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour, is preferably 1～8 hour.
In the inventive method, add required catalyst promoter and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprises one or more among P, F, Ti, Si, B, the Zr etc.The interpolation component is generally one or more in silica, zirconia, clay, sial, titanium oxide, the magnesia etc.
Catalyst shape can be sheet, spherical, cylinder bar and special-shaped bar (clover, bunge bedstraw herb), preferably cylinder bar and special-shaped bar (clover, bunge bedstraw herb) as required.The diameter of catalyst can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Catalyst of the present invention has higher hydrodesulfurization activity, can be used in the distillate hydrogenation process, is particularly useful in the heavy distillate hydrogenation process, has widened body phase method Application of Catalyst scope.
The nitrogen-containing compound consumption is wanted suitably when consumption is big, can causes difficulty to the moulding of catalyst, and catalyst strength is caused very big influence in the inventive method.When consumption hour, the pore structure of catalyst is changed little, metal is evenly distributed on catalyst.
In diesel oil distillate ultra-deep desulfurization process; Because 4, during the desulfurization of 6-dimethyl Dibenzothiophene class sulfides, Methyl transporters can take place, methyl removes and the C-C cleavage reaction; And the present invention selects SAPO-11 as acidic components; Can carry out above-mentioned reaction effectively, and match, reach the purpose of Ultra-deep Desulfurization of Diesel Fuels with hydrogenation active metals.
The present invention is through becoming an amount of water-soluble nitrogen-containing compound of adding in the glue process at bulk phase catalyst; Make in the glue thing except forming precipitation of hydroxide, also contain an amount of basic salt deposition, make it in roasting process; Emit a certain amount of gas; Under the percussion of gas, not only improved the pore structure of catalyst, but also made more metal active position be exposed to the surface of catalyst; Improved the utilization rate of reactive metal, simultaneously also for more reactive metal and the interactional chance of acidic components molecular sieve are provided.Under the situation of same metal content, activity under the suitable situation of catalyst hydrogenation activity, can reduce conventional bulk phase catalyst reactive metal consumption apparently higher than conventional bulk phase catalyst, reduces the Preparation of Catalyst cost.Simultaneously, because in the inventive method, the SAPO-11 molecular sieve is to join Ni with the slurries form
xW
yO
zIn the composite oxides precursor; So not only make SAPO-11 molecular sieve and hydrogenation active metals evenly, contact fully; Avoided kneading method to add the caused molecular sieve of molecular sieve shortcoming pockety; But also make the SAPO-11 molecular sieve give full play to its acidity, and can with the hydrogenation active metals better fit, reach the effect of Ultra-deep Desulfurization of Diesel Fuels.And the increase of bulk phase catalyst of the present invention aperture and pore volume, Ni-W high activity center is fully utilized, complicated macrostructure molecule contacts the activated centre more easily, and especially effect is more obvious when handling the more distillate of big molecule content.
The specific embodiment
Further specify scheme of the present invention and effect through specific embodiment below.The percentage composition that relates to is a weight percentage.Specific surface area of catalyst adopts the BET method to measure, and pore volume is a determination of nitrogen adsorption, and intensity adopts the side pressure method to measure.
SAPO-11 molecular sieve used in the embodiment of the invention is for synthetic according to patent US 4,440,871 methods, and character is following: SiO
2/ Al
2O
3Mol ratio is 0.8, and meleic acid amount 1.1mmol/g, pore volume are 0.18ml/g, and specific area is 220m
2/ g.
Embodiment 1
In dissolving tank, add 1000mL water, add nickel chloride 26g dissolving, ammonium metatungstate 41.5g dissolving successively, add liquor alumini chloridi 415ml again, evenly stir the back wiring solution-forming.Get 160g carbonic hydroammonium and be made into the aqueous solution that molar concentration is 2.5mol/l.Mixed solution, ammonium bicarbonate aqueous solution, precipitating reagent 10% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed then, and one-tenth glue pH value is 8.0, and one-tenth glue temperature is 50 ℃.After becoming glued bundle, add 8 gram SAPO-11 molecular sieve pulps, aging 2 hours.Filter aging back, and filter cake adds 600ml water purification and 6.3g molybdenum trioxide, and making beating stirs; Filter, the filter cake that obtains is at 80 ℃ of dryings 5 hours, extruded moulding then; With water purification washing 3 times, wet bar is 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours; Obtain final catalyst A, composition and main character are seen table 1, and table 2 is seen in pore size distribution.
Embodiment 2
According to the method for embodiment 1, press the constituent content proportioning of catalyst B in the table 2, in NaOH solution tank NaOH, add aluminium chloride, nickel chloride, sodium tungstate, zirconium oxychloride, evenly stir the back wiring solution-forming.Get 100g carbonic hydroammonium and be made into the solution that molar concentration is 2.0mol/l.Mixed solution, ammonium bicarbonate aqueous solution, precipitating reagent 20% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed then, and one-tenth glue pH value is 7.5, and one-tenth glue temperature is 60 ℃.After becoming glued bundle, add 10 gram SAPO-11 molecular sieve pulps, aging 3 hours, filtered aging back; Filter cake adds 600ml water purification and 8.3g molybdenum trioxide, and making beating stirs, filtration, and the filter cake that obtains was 70 ℃ of dryings 7 hours; Extruded moulding then, with water purification washing 2 times, wet bar is 100 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours; Obtain final catalyst B, composition and main character see Table 1, and pore size distribution sees Table 2.
Embodiment 3
According to the method for embodiment 1, press the constituent content proportioning of catalyst C in the table 1, in retort, add nickel nitrate, ammonium metatungstate, aluminium chloride, phosphoric acid, waterglass, evenly stir the back wiring solution-forming.Get the 120g ammonium oxalate and be made into the solution that molar concentration is 1.8mol/l.Mixed solution, the ammonium oxalate aqueous solution, precipitating reagent 12% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed then, and one-tenth glue pH value is 8.0, and one-tenth glue temperature is 65 ℃.After becoming glued bundle, add 12 gram SAPO-11 molecular sieve pulps, aging 2 hours, filtered aging back; Filter cake adds 600ml water purification and 8.3g molybdenum trioxide, and making beating stirs, filtration, and the filter cake that obtains was 120 ℃ of dryings 1 hour; Extruded moulding then, wet bar is 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours; Obtain final catalyst C, composition and main character are seen table 1, and table 2 is seen in pore size distribution.
Embodiment 4
Method according to embodiment 1; Press the constituent content proportioning of catalyst D in the table 2; In retort, add 1000mL water, add nickel chloride 33g dissolving, ammonium metatungstate 40g dissolving, 348 milliliters of liquor alumini chloridis, 8.5 milliliters of waterglass successively, evenly stir the back wiring solution-forming.Get the 140g ammonium citrate and be made into the solution that molar concentration is 2.5mol/l.Mixed solution, the ammonium oxalate aqueous solution, precipitating reagent 12% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed then, and one-tenth glue pH value is 9.0, and one-tenth glue temperature is 60 ℃.Becoming the glue temperature is 60 ℃, behind the glued bundle of one-tenth,, add 8 gram SAPO-11 molecular sieve pulps, wore out 2 hours; Filter aging back, and filter cake adds 600ml water purification and 7.2g molybdenum trioxide, and making beating stirs, and filters; Filter cake is 80 ℃ of dryings 5 hours, extruded moulding then, and with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours; 500 ℃ of roastings 4 hours, obtain final catalyst D, composition and main character are seen table 1, table 2 is seen in pore size distribution.
Comparative example 1
According to the method for embodiment 1, wherein do not add ammonium bicarbonate aqueous solution, preparation reference agent E.Catalyst property is seen table 1, and table 2 is seen in pore size distribution.
Comparative example 2
According to the method for embodiment 1, wherein do not add the SAPO-11 molecular sieve, preparation reference agent F.Catalyst property is seen table 1, and table 2 is seen in pore size distribution.
Table 1 catalyst is formed and character
| Catalyst | A | B | C | D | E | F |
| Catalyst is formed, % | ||||||
| WO 3 | 34 | 36 | 32 | 33 | 34 | 34 |
| NiO | 8 | 6 | 8 | 10 | 8 | 8 |
| MoO 3 | 6 | 8 | 8 | 7 | 6 | 6 |
| SAPO-11 | 8 | 10 | 12 | 10 | 8 | 0 |
| Al 2O 3 | 44 | 38 | 37 | 38 | 44 | 52 |
| Other | Do not have | ZrO 2/2.0 | SiO 2/2.0 P/1.0 | SiO 2/2.0 | Do not have | Do not have |
| Physico-chemical property: | ||||||
| Pore volume, cm 3/g | 0.225 | 0.233 | 0.231 | 0.235 | 0.191 | 0.229 |
| Specific area, m 2/g | 239 | 245 | 250 | 241 | 186 | 241 |
| Bulk density, g/100cm 3 | 92.54 | 93.78 | 93.28 | 91.89 | 109.5 | 92.31 |
Table 2 catalyst pores distributes
Embodiment 5
Present embodiment is a catalyst hydrogenation desulphurization reaction performance evaluation.
In order to further specify the ultra-deep hydrodesulfuration ability of catalyst of the present invention, adopt catalyst A of the present invention, C and Comparative Examples catalyst E, F, on the 200ml small hydrogenation device, carry out comparative evaluation's test, test raw material is Maoming mixed diesel.The raw material main character sees Table 3, and catalyst activity is estimated process conditions and evaluation result sees Table 4.Adopt gas-chromatography-atomic emission spectrum detector (GC-AED) to detect sulfur compound in the hydrofined oil, the result sees table 5.
Can find out from the evaluation test result; Adopt the catalyst of method preparation of the present invention; Have higher hydrogenation performance, especially shown more tangible removal effect, have excellent hydrogenation and desulphurizing ability having sterically hindered sulfide; Can be used in the hydrodesulfurization reaction, be particularly useful for producing in the ultra-deep desulfurization reaction of ultra clean diesel.
Table 3 feedstock oil main character
| Project | Analysis result |
| Density (20 ℃), g/cm 3 | 0.8614 |
| The boiling range scope, ℃ | 178-374 |
| ?S，μg/g | 12200 |
| ?N，μg/g | 288 |
| Cetane number | 46.5 |
Table 4 catalyst hydrogenation desulphurization reaction process conditions and evaluation result
The content of different sulfide in table 5 hydrofined oil
| Catalyst | A | C | E | F |
| Sulfur content in the hydrofined oil, μ g/g | 7 | 9 | 63 | 56 |
| ?C 1-DBT，μg/g | 0 | 0 | 0 | 0 |
| ?4-BMDBT，μg/g | 0 | 0 | 7.5 | 6.6 |
| ?6-BMDBT，μg/g | 0 | 0 | 12.8 | 9.1 |
| ?4，6-BMDBT，μg/g | 1.1 | 1.4 | 30.8 | 29.6 |
| ?2，4，6-BMDBT，μg/g | 5.9 | 7.6 | 11.9 | 10.7 |
Claims (16)
1. a body phase ultra-deep hydrodesulfuration catalyst contains Mo, W, three kinds of metal components of Ni, and wherein W, Ni exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Weight with catalyst is benchmark, and catalyst is formed and comprised: composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 30%～70%, the content of aluminium oxide is 10%～65%, the content of SAPO-11 molecular sieve is 1%～20%; The character of said catalyst is following: specific area is 150～450m
2/ g; Pore volume is 0.20～0.60mL/g; Pore-size distribution is following: diameter accounts for 10%～35% of total pore volume less than the shared pore volume in the hole of 4nm; Diameter is that the shared pore volume in the hole of 4～15nm accounts for 50%～85% of total pore volume, and what diameter accounted for total pore volume greater than the shared pore volume in the hole of 15nm is 5%～15%.
2. according to the described catalyst of claim 1, it is characterized in that, is benchmark with the weight of catalyst, composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 35%～55%, the content of aluminium oxide is 30%～60%, the content of SAPO-11 molecular sieve is 5%～15%.
3. according to the described catalyst of claim 1, it is characterized in that described composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 7～7: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 8～8: 1.
4. according to the described catalyst of claim 1; The pore-size distribution that it is characterized in that said catalyst is following: diameter accounts for 10%～25% of total pore volume less than the shared pore volume in the hole of 4nm; Shared pore volume accounts for 60%～80% of total pore volume to diameter in the hole of 4～15nm, and what diameter accounted for total pore volume greater than the shared pore volume in the hole of 15nm is 8%～15%.
5. according to the described catalyst of claim 1, it is characterized in that the character of described SAPO-11 molecular sieve is following: SiO
2/ Al
2O
3Mol ratio is 0.1～1.3, and meleic acid 0.6～1.3mmol/g, pore volume are 0.01～0.10mL/g, specific area 100～200m
2/ g.
6. according to the described catalyst of claim 1; It is characterized in that containing in the described catalyst in silica, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, the boron oxide compound one or more, the weight content in catalyst is 1%～20%.
7. the arbitrary said Preparation of catalysts method of claim 1～5 may further comprise the steps: (1) coprecipitation generation Ni
xW
yO
zThe composite oxides precursor; (2) to Ni
xW
yO
zAdd the SAPO-11 molecular sieve pulp in the composite oxides precursor, aging under stirring condition; (3) to step (2) obtain aging after mixture in add MoO
3Making beating mixes, filters, and is dry then; (4) through roll, moulding, activation be final catalyst; Wherein step (1) process is following: preparation contains the saline mixed solution of Ni, W, Al component; Also flow to add in the retort that water purification is housed simultaneously with the water miscible nitrogen-containing compound aqueous solution, precipitating reagent ammoniacal liquor then and become glue; The pH value of slurries is in 7.0～10.0 scopes in the retort, processes gelatinous precipitate, promptly is composite oxides Ni
xW
yO
zPrecursor; Wherein the addition of water miscible nitrogen-containing compound is with NH
4 +Meter, with the mol ratio of active metal nickel and tungsten total amount be 0.2～2.0.
8. according to the described method of claim 7, it is characterized in that described water miscible nitrogen-containing compound is one or more in ammonium citrate, carbonic hydroammonium, ammonium acetate and the ammonium oxalate.
9. according to the described method of claim 7, it is characterized in that described water miscible nitrogen-containing compound is a carbonic hydroammonium.
10. according to the described method of claim 7; It is characterized in that the described preparation of step (1) contains the saline mixed solution of Ni, W, Al component; Wherein contain nickel salt and be in nickelous sulfate, nickel nitrate, the nickel chloride one or more; Tungstenic salt is one or both in sodium tungstate, the ammonium metatungstate, contains aluminium salt and be in aluminum nitrate, aluminium chloride, the aluminum sulfate one or more; Becoming the glue temperature is 30～100 ℃, and gelation time is 0.5～5.0 hour.
11., it is characterized in that the described SAPO-11 molecular sieve pulp of step (2) is is to mix in 1: 1～10: 1 with SAPO-11 molecular sieve and water by volume, through grinding, processes molecular sieve pulp then according to the described method of claim 7.
12. according to the described method of claim 7, it is characterized in that the described aging condition of step (2) under stirring state, aging temperature is 30～90 ℃, ageing time 1～5 hour, pH value are 7.0～10.0.
13., it is characterized in that 50～150 ℃ of the described baking temperatures of step (3), 0.5～24 hour drying time according to the described method of claim 7.
14. according to the described method of claim 7, it is characterized in that described in the step (4) after the moulding, wash with the water purification or the aqueous solution that contains ammonium acetate.
15. according to the described method of claim 7, it is characterized in that the described activation of step (4) comprises drying and roasting, condition is following: 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour.
16., it is characterized in that in above-mentioned steps goes on foot or the required catalyst promoter and interpolation component of adding in a few step according to the described method of claim 7; Auxiliary agent comprises one or more among P, F, Ti, Si, B, the Zr; The interpolation component is one or more in silica, zirconia, clay, sial, titanium oxide, the magnesia.
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|---|---|---|---|---|
| US6156695A (en) * | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| CN1884446A (en) * | 2006-05-23 | 2006-12-27 | 中国科学院山西煤炭化学研究所 | Hydrocracking catalyst for Tscher-Topsch synthesis of heavy wax, its preparation method and application thereof |
| CN1951561A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A catalyst composition and preparation method thereof |
| CN101089131A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction hydroupgrading process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156695A (en) * | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| CN1951561A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | A catalyst composition and preparation method thereof |
| CN1884446A (en) * | 2006-05-23 | 2006-12-27 | 中国科学院山西煤炭化学研究所 | Hydrocracking catalyst for Tscher-Topsch synthesis of heavy wax, its preparation method and application thereof |
| CN101089131A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction hydroupgrading process |
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