CN101280216B - Method for producing ultra-low sulfur diesel - Google Patents
Method for producing ultra-low sulfur diesel Download PDFInfo
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- CN101280216B CN101280216B CN2007101484327A CN200710148432A CN101280216B CN 101280216 B CN101280216 B CN 101280216B CN 2007101484327 A CN2007101484327 A CN 2007101484327A CN 200710148432 A CN200710148432 A CN 200710148432A CN 101280216 B CN101280216 B CN 101280216B
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Abstract
The invention relates to a method of producing ultra-low sulfur diesel. The diesel distillate is used as raw oil; the single stage or a stage of series process flow is adopted; the feed stock is mixed with hydrogen to pass the hydrogenation reaction area; under the operating condition of hydrorefining, the quality of diesel is improved greatly; wherein, at least one of the catalysts in the hydrogenation reaction area is bulk phase catalyst; the bulk phase catalyst is composed of composite oxide NixWyO z and oxide MoO3 with the weight ratio of 1:10-10:1; the composite oxide NixWyO z and oxide MoO3 account for 40%-100% of the total weight of the catalyst combination. Compared with the prior art, the method of producing ultra-low sulfur diesel in the invention can reduce the operation severity of the hydrorefining reaction area effectively, improve the processing load of the device, prolong the service life of the catalyst or produce the ultra-low sulfur diesel directly.
Description
Technical field
The present invention relates to a kind of production ultra-low-sulphur diesel method, select suitable catalyzer for use, the diesel oil sulphur content is reduced to method below the 10ppm.
Background technology
Oil refining enterprise faces strict clean fuel specification and the global challenges of competition of increasingly sharpening.Because the market requirement need be improved the quality of products, and improves product structure; The environmental regulation increasingly stringent, harsh more to the restriction of content of harmful gas such as the NOx in the Motor vehicles discharging waste gas, SOx.Therefore, the low sulfuration of diesel oil is the development trend of countries in the world and regional diesel oil new spec, estimate 2009, European Union's rules will limit the sulphur content of derv fuel oil below 10 μ g/g, and the U.S. also will limit the sulphur content of derv fuel oil below 15 μ g/g in 2007.How economical, reasonably to produce the low-sulfur diesel-oil product will be the problem that present oil refining enterprise needs emphasis to solve.
The hydrofining technology is the main means that oil refining enterprise improves quality product, and along with cleaning of diesel oil, it is more and more important that the hydrofining technology will seem.Although can improve the diesel fuel desulfurization degree of depth by improving modes such as temperature of reaction, reduction reaction velocity, improvement reactor inner member, but most economical and easy method is to adopt more highly active Hydrobon catalyst, and how to adopt to have difference in functionality catalyst combination loading technology particularly important.Though body phase method catalyzer can be reduced to the sulphur content of diesel oil below the 10 μ g/g, because the influence of factors such as the metal content height of catalyzer, metal price rise, the cost of catalyzer is higher.
The diesel oil distillate processing technology generally has hydrofining, hydro-upgrading, mild hydrocracking etc.As described in CN1156752A and CN1289832A etc., though hydro-upgrading can obviously reduce the sulphur content of diesel oil and improve diesel-fuel cetane number, but the yield of comparing diesel product with hydrofining obviously reduces, and be subjected to the restriction of reaction conditions, have only cetane value is had very significantly improve.
Adopting highly active catalyzer that diesel oil distillate is carried out hydrofining is general method commonly used, but this method is limited to the amplitude that improves the product cetane value, and the performance of existing high activated catalyst still needs further to improve.Method for preparing catalyst described in CN99113281.5, CN00122922.2, CN00122919.2, CN200510046347.0 etc. though catalyzer has higher hydrodesulfurization activity, is reduced to the diesel oil sulphur content and is difficult to below the 10ppm realize.
US 4880526 discloses a kind of Ni of containing, Mo, W, the Co high reactivity is used for bulk phase catalyst of hydrotreatment and preparation method thereof, and this preparation method adopts metal to mix kneading to be equipped with technology, and the different metal component distributes under the microcosmic in mutually also inhomogeneous at body.US6299760, US6156695, US6537442, US6440888, the disclosed VIII family/group vib active metal component that contains of US6652738 are used for bulk phase catalyst of hydrotreatment and preparation method thereof, adopt and prepare the metal-powder that contains Ni-Mo or Ni-Mo-W earlier, use aluminum oxide bonding again, or the metal-powder of Ni-Mo or Ni-Mo-W is mixed back dehydration, extrusion, drying with alumina gel.Because the catalyst metal content height of this method preparation, often lack enough interactions between metal and aluminum oxide and cause catalyst strength poor.Active ingredient is made up of a large amount of metals, has some interior metal components and can not be fully utilized and cause the active ingredient loss in forming Ni-Mo or Ni-Mo-W powder process, and this problem can not be by simple bonding the solution.CN1342102A discloses a kind of mixed metal catalyst, and concrete grammar is for to obtain three kinds of reactive metal co-precipitation, and its main weak point is not find the cooperation effect between the different activities metal.US6162350, CN1339985A disclose a kind of mixed metal catalyst composition, and it is solid-state keeping at least a metal in preparation process, forms another kind of soild oxide in this solid metal compound surface reaction, finally forms the core-shell type composition.This method can not make different metal obtain good cooperation.The performance of above-mentioned high reactivity bulk phase catalyst still can further improve.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of diesel fraction deep desulfurization method, it can reduce the operating severity in hydrofining reaction district, promptly can reach under processing condition such as suitable working pressure, temperature of reaction and promptly satisfy the purpose that the ultra-low-sulphur diesel production requirement reduces the catalyzer overall expenses again.
The present invention produces the ultra-low-sulphur diesel method and comprises following content: with one or more of diesel oil distillate is raw material, under the hydrofining operational condition, stock oil and hydrogen are by the refining reaction district, the hydrofining that obtains generates the oily gas that obtains in gas-liquid separator separates and recycles after desulfurization, and the liquid fractionation that obtains is a following products: gas, petroleum naphtha, diesel oil etc.At least comprise a kind of bulk phase catalyst bed in the described refining reaction district, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, catalyzer before sulfuration W, Ni with composite oxides Ni
xW
yO
zForm have z=x+3y wherein; Mo is with oxide M oO
3Form exist.Composite oxides Ni
xW
yO
zThe ratio of middle x and y (atomic molar ratio) is 1: 8～8: 1, is preferably 1: 4～4: 1.Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 10～10: 1, be preferably 1: 5～5: 1.Composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%, be preferably 50%～80%.
The stock oil that the inventive method is used can be the straight-run diesel oil that obtains in the petroleum refining process, catalytic cracking turning oil, and coker gas oil, one or more of viscosity breaking diesel oil etc. also can be the diesel oil distillates of coal tar, gelatin liquefaction wet goods.
Hydrofining operating operation condition is generally reaction pressure 2.0～12.0MPa, and hydrogen to oil volume ratio is 200: 1～1000: 1, and the cumulative volume air speed is 0.2～5.0h
-1, 310 ℃～417 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 3.0～10.0MPa, hydrogen to oil volume ratio 200: 1～800: 1, volume space velocity 0.5～4.0h
-1, 320～400 ℃ of temperature of reaction.
The catalyzer in refining reaction of the present invention district can all be a bulk phase catalyst, the combination of preferably conventional Hydrobon catalyst and bulk phase catalyst.During combination loading, bulk phase catalyst can be seated in the top of reaction zone, also can be seated in the bottom of reaction zone, and perhaps two types catalyzer loads at interval, the volume ratio of bulk phase catalyst and conventional Hydrobon catalyst is 90: 10～10: 90, preferred 20: 80～80: 20.During combination loading, preferred feed by common pre-refining beds, by bulk phase catalyst bed of the present invention, helps bringing into play the catalyzer overall activity most earlier then.Conventional Hydrobon catalyst has following character: pore volume 0.25～0.55ml/g, specific surface area is 100～400m
2/ g is 15%～45% in oxide weight hydrogenation active metals content in the catalyzer, and hydrogenation active metals comprises W, Mo, Ni or Co.Conventional Hydrobon catalyst specific surface area is preferably 150～300m
2/ g is preferably 25%～40% in oxide weight hydrogenation active metals content in the catalyzer.
Wherein conventional Hydrobon catalyst can be various commercial catalysts, as Fushun Petrochemical Research Institute (FRIPP) develop 3936,3996, Hydrobon catalysts such as FF-16, FF-26, FH-5, FH-5A, FH-40A, FH-40B, FH-40C, FH-98, FH-98A, FH-DS, FH-UDS, the HC-K of Uop Inc., HC-P, S-120, the TK-557 of Topsor company, TK-915 catalyzer, the KF-756 of AKZO company, KF757, KF-848 etc.
Can contain in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve one or more in the bulk phase catalyst of the present invention as required, the weight content of these components in catalyzer is 0～60%, is preferably 20%～50%.The specific surface area of bulk phase catalyst is 120～400m
2/ g, pore volume are 0.10～0.50ml/g.
The preparation process of bulk phase catalyst of the present invention comprises following content: (1) coprecipitation method 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 catalyzer.
Wherein (1) described coprecipitation method generates Ni
xW
yO
zThe process of composite oxides precursor can adopt following method: with the salts solution of tungstenic, nickel, form required ratio in catalyzer and add in the glue jar, add precipitation agent and make gelatinous mixture.Precipitation agent can be inorganic or organic alkaline ammoniac compounds, is preferably ammonia, can working concentration ammoniacal liquor arbitrarily.
Add required catalyst adjuvant and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprise P, F, Ti, Si, B, Zr etc. one or more.Add component and be generally refractory porous mass and precursor thereof, as aluminum oxide and precursor (aluminium hydroxide, aluminum salt solution etc.), clay, sial, titanium oxide-magnesium oxide, molecular sieve etc.The method that adds auxiliary agent and interpolation component adopts this area ordinary method.
Though W, Mo, Ni are activity of hydrocatalyst component commonly used, find that through a large amount of The effects the performance of different fit system catalyzer has very big-difference.Particularly in the bigger bulk phase catalyst of total metal content, the different fit systems of these metals are bigger to the performance impact of catalyzer.The present invention finds by a large amount of experiments, is used for the body phase hydrogenation catalyst that the hydrocarbon material degree of depth is taken off impurity, earlier with W and Ni co-precipitation, makes Ni
xW
yO
zThe precursor of composite oxides, this composite oxides precursor again with MoO
3Making beating mixes, and adopts conventional means to prepare preformed catalyst then, and this preparation process organically cooperates element W and Ni, forms a kind of composite oxides, then with MoO
3Combination finally forms Ni
xW
yO
zThe composition of composite oxides and Mo oxide compound.The result shows when the catalyzer of this microtexture of the present invention is used for hydrocarbons hydrogenation, to have the outstanding impurity activity of taking off, and during especially for deep impurity removal process, significantly improves than the activity of such catalysts of similar chemical constitution.The mechanism that the composition of Ni-W composite oxides of the present invention and Mo oxide compound can improve catalyst activity is very not clear and definite as yet, and, in bulk phase catalyst, the content of reactive metal is higher, reactive metal exist form different fully with traditional loaded catalyst, therefore, can not be suitable for the metal cooperation theory of conventional negative supported catalyst.For example, it is generally acknowledged that Ni can promote the activity of Mo to improve, wishing has a stronger interaction between Ni and the Mo, and the present invention finds in experiment, for bulk phase catalyst, Mo and Ni is fully combined then take off impurity in the degree of depth and do not show perfect performance.The composition catalyzer of Ni-W composite oxides of the present invention and Mo oxide compound, the possible cause that takes off the unexpected raising of performance in the impurity in the degree of depth is, in the very high bulk phase catalyst of metal content, reactive metal exist form different with loaded catalyst, take off in the impurity process in the hydrocarbon raw material degree of depth, the Ni-W composite oxides have stronger hydrogenation activity after sulfuration, make to have the effective hydrogenation of complex construction macromole, eliminate and take off the sterically hindered of impurity reaction.Has the stronger impurity activity of taking off after the Mo sulfuration in the bulk phase catalyst, simple in structure, the sterically hindered little heteroatoms hydrocarbon that contains is easy to react, reduced of the interference of this part heteroatoms hydro carbons, helped the hydrogenation that Ni-W high reactivity center is used for the complex construction molecule the Ni-W hydrogenation activity.After containing the effective hydrogenation in heteroatomic complex construction macromole process Ni-W high reactivity center, take off the sterically hindered of impurity and reduce greatly, can in taking off impurity activity, remove easily in the heart.Therefore, the active centre of Ni-W composite oxides of the present invention and Mo oxide compound obtains cooperation, and combination catalyst takes off in the impurity reaction in the degree of depth and has outstanding activity.Bulk phase catalyst preparation method of the present invention does not use the salts solution of Mo, because the reaction product of Mo salts solution and precipitation agent generally has certain solubleness, has therefore avoided the loss of Mo.
Compared with prior art, characteristics of the present invention are: because the present invention has used some or all of highly active bulk phase catalyst, strengthened the hydrogenation performance of hydrofining reaction district catalyzer, can effectively reduce the content and the aromaticity content of sulphur in the stock oil, nitrogen, promptly under the identical operations condition, can reduce reaction pressure, reduce service temperature etc., perhaps under same reaction pressure, service temperature, increase the treatment capacity of device, perhaps reduce the usage quantity of catalyzer, reduced the construction investment and the running cost of device.Think ratio with the hydrofining reaction of routine, owing to improved the hydrorefined degree of depth, the aromatic hydrocarbons saturation depth also increases, thereby can improve diesel-fuel cetane number by a relatively large margin, and can carry out ultra-deep desulfurization.
Embodiment
According to the scale of device, the inventive method can adopt a reactor or two (or a plurality of) reactors, adopts a reactor to be commonly referred to single hop technology, adopts two (or a plurality of) reactors to be commonly referred to one-stage serial technology.Adopt one way pass-through mode those skilled in the art to know, the hydrofining reaction district needs the layering filling according to the temperature distribution situation, cold hydrogen inlet is arranged between each bed, inject cold hydrogen during operation, take away hydrogenation reaction institute liberated heat, make temperature of reaction control within the specific limits, make operation safe, steady.
The present invention produces the specific as follows of ultra-low-sulphur diesel method: with one or more of diesel oil distillate oil is stock oil, adopt single hop or one-stage serial technical process, under the hydrofining operational condition, stock oil and hydrogen order are by the refining reaction district, the hydrofining that obtains generates the oily gas that obtains in gas-liquid separator separates and recycles after desulfurization, and the liquid that obtains obtains following products in the separation column fractionation: one or more in gas, petroleum naphtha, the diesel oil.
Bulk phase catalyst of the present invention can make as follows.
1, Ni
xW
yO
zComposite oxides precursor and MoO
3The preparation of mixture
In retort, add the saline solution that contains reactive metal Ni, W component by catalyst component content proportioning.Contain nickel salt and can be single nickel salt, nickelous nitrate, nickelous chloride etc.Tungstenic salt can be sodium wolframate, ammonium metawolframate etc.Mix the back, precipitation agent is added under stirring state in the said mixture, until forming collosol intermixture.Becoming the glue temperature is 30-100 ℃, and becoming the glue pH value is 7.0-10.0.Can become under the glue temperature to wear out 1-5 hour after becoming glue.Becoming in the glue thing promptly is Ni
xW
yO
zThe precursor of composite oxides.Can filter or not filter before and after becoming glue, add the solid molybdic oxide, making beating mixes, and filters then and obtains filter cake, and filter cake can wash or not wash, and filter cake dehydrates under 50-150 ℃ of condition, 0.5～24 hour time of drying, obtains Ni
xW
yO
zComposite oxides precursor and MoO
3Mixture.
Preferably 30～80 ℃ of described one-tenth glue temperature, gelation time was generally 0.5～5 hour, was preferably 0.5～3 hour, slurries pH value 7.0-9.0 preferably during cemented into bundles.Preferably 50～100 ℃ of described drying temperatures are preferably 1～8 hour time of drying.
Can add aluminum salt solution in the saline solution of Ni, W component, make the precursor that contains aluminum oxide in the throw out, aluminum salt solution can be aluminum nitrate, Tai-Ace S 150, aluminum chloride or aluminum acetate etc.Directly add aluminium hydroxide after also can becoming glue.The purpose of introducing aluminium in the catalyzer mainly is the intensity that increases catalyzer, and improves pore structure etc.In the preparation process of this mixture, can add auxiliary agent and additive etc. as required.
2, Preparation of Catalyst
The filter cake that above-mentioned drying is good rolls extruded moulding.Can or contain with water purification after the moulding and can decompose salt (as ammonium acetate) solution and wash.The activation of catalyzer comprises processes such as dry and roasting.To wash back stripe shape thing drying, roasting obtains final catalyst prod.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.Also can introduce auxiliary agent and additive as required in the catalyst preparation process.
Catalyst shape can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei) as required.The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Bulk phase catalyst of the present invention has higher hydrodenitrification, hydrogenating desulfurization, the saturated isoreactivity energy of aromatic hydrocarbons.
Further specify Preparation of catalysts method of the present invention and use properties below by embodiment.The per-cent that wherein relates to is weight percentage.
Embodiment 1
In retort, add 1000mL water, add nickelous chloride 40g dissolving then, add ammonium metawolframate 52g dissolving again, add zirconium oxychloride 5g dissolving again, add 10% ammoniacal liquor then and become glue, until pH value is 8, becoming the glue temperature is 50 ℃, wears out 1 hour behind the one-tenth glue, filters then, filter cake adds 600ml water purification and 16g molybdic oxide and 32g aluminium hydroxide, making beating stirs, and filters, and filter cake was 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 see Table 1.
Embodiment 2
Method according to embodiment 1, press the component concentration proportioning of catalyst B in the table 1, adding aluminum chloride, nickelous chloride, sodium wolframate in retort, add 16% ammoniacal liquor then and become glue, is 9 until pH value, becoming the glue temperature is 80 ℃, wore out 3 hours after becoming glue, filter then, filter cake washs 2 times with the 500mL water purification, add water purification and molybdic oxide, making beating stirs, and filters, and filter cake 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.
Embodiment 3
Method according to embodiment 1, press the component concentration proportioning of catalyzer C in the table 1, in retort, add nickelous nitrate, ammonium metawolframate, aluminium hydroxide, silicon sol, add 12% ammoniacal liquor then and become glue, until pH value is 10, and becoming the glue temperature is 60 ℃, wears out 2 hours behind the one-tenth glue, filter then, filter cake adds molybdic oxide, and making beating stirs, and filters, filter cake was 120 ℃ of dryings 1 hour, extruded moulding then, wet bar is 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyzer C, composition and main character see Table 1.
Embodiment 4
Method according to embodiment 1, press the component concentration proportioning of catalyzer D in the table 1, in retort, add 1000mL water, add nickelous chloride 48g dissolving then, add ammonium metawolframate 40g dissolving again, adding 10% ammoniacal liquor then and become glue, is 8 until pH value, and becoming the glue temperature is 40 ℃, wore out 3 hours after becoming glue, filter then, filter cake adds 600ml water purification and 28g molybdic oxide and 17g aluminium hydroxide, and making beating stirs, filter, filter cake is 80 ℃ of dryings 5 hours, and extruded moulding then is with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyzer D, composition and main character see Table 2.
Comparative example
Catalyzer according to embodiment 1 is formed, and presses the disclosed method for preparing catalyst of Chinese patent CN1342102A, preparation reference agent E.
In retort, add 1000mL water, add Ammonium Heptamolybdate 25g dissolving then, add ammonium metawolframate 52g dissolving again, add 25% ammoniacal liquor then and become glue, until pH value is 10.0, and being heated to temperature is 90 ℃, drips the solution that contains the 40g nickelous chloride simultaneously in retort.The suspension liquid that forms is continued to stir 90 ℃ of temperature 30 minutes.Filter then, the filter cake hot wash, 100 ℃ of dryings 5 hours add 32g aluminium hydroxide extruded moulding then, and wet bar 500 ℃ of roastings 4 hours, obtains final reference catalyst E 100 ℃ of dryings 8 hours, and composition and main character see Table 2.Prepare catalyzer by this kind method, the molybdic oxide yield can only reach 80%, and in order to guarantee metal content and proportioning in the catalyzer, Ammonium Heptamolybdate adds 20% when feeding intake.
The catalyzer and the character of the preparation of table 1 the inventive method
| The catalyzer numbering | A | B | C | D | E |
| NiO，wt％ | 18.1 | 17.1 | 12.5 | 22.1 | 17.9 |
| WO 3，wt％ | 42.3 | 21.3 | 28.4 | 32.2 | 41.8 |
| MoO 3，wt％ | 16.5 | 57.6 | 18.6 | 28.1 | 17.0 |
| A1 2O 3，wt％ | Surplus | Surplus | Surplus | Surplus | Surplus |
| Other, wt% | ZrO 2/2.0 | Do not have | SiO 2/4.0 | TiO 2/3.0 | Do not have |
| Specific surface/m 2·g -1 | 143 | 258 | 202 | 135 | 105 |
| Pore volume/mlg -1 | 0.216 | 0.40 | 0.258 | 0.12 | 0.132 |
| Intensity/Nmm -1 | 11.5 | 11.0 | 16.7 | 18.2 | 8.6 |
Embodiment 5
Stock oil character sees Table 2, catalyst property sees Table 3, and processing condition and test-results see Table 4.Oxidized catalyst is carried out conventional sulfidizing before use.As under the 8MPa condition, vulcanize with the diesel oil that contains dithiocarbonic anhydride 2wt%, 230 ℃ of constant temperature 8 hours, 330 ℃ of constant temperature 10 hours, volume space velocity was 1.0h during liquid
-1, hydrogen to oil volume ratio is 500: 1.
From table 4 test-results as can be seen, adopt technology of the present invention can effectively improve the activity of Hydrobon catalyst, can reduce working pressure, reduce service temperature, perhaps improve treatment capacity, also can reduce the usage quantity of catalyzer, saved facility investment and process cost.Because the more intense hydrogenation performance of body phase method catalyzer improves the aromatic hydrocarbons saturation depth in hydrogenating desulfurization, denitrogenation, be beneficial to selective opening more, thereby the cetane value increase rate is bigger simultaneously.
Table 2 stock oil character
| The stock oil title | Stock oil-1 | Stock oil-2 |
| Density (20 ℃)/gcm -3 | 0.8614 | 0.9129 |
| The boiling range scope/℃ | 178～371 | 162～373 |
| Sulphur content, wt% | 1.22 | 1.49 |
| Nitrogen content, wt% | 0.03 | 0.08 |
| Cetane value | 46.5 | 24.5 |
The main composition and the character of table 3. hydrogenation catalyst
Table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 1 | Reference scheme 1 | Process program 2 | Reference scheme 2 |
| Catalyzer | FH-UDS/A | FH-UDS/FH-98 | FH-98/B | FH-98/E |
| Stock oil | Raw material 1 | Raw material 1 | Raw material 1 | Raw material 1 |
| The catalyst loading volume ratio | 50∶50 | 50∶50 | 60∶40 | 60∶40 |
| Pressure/MPa | 8.0 | 8.0 | 7.0 | 7.0 |
| The inlet hydrogen to oil volume ratio | 500∶1 | 500∶1 | 700∶1 | 700∶1 |
| Air speed/h -1 | 2.0/2.0 | 2.0/2.0 | 2.0/2.6 | 2.0/2.6 |
| Temperature/℃ | 360/365 | 360/365 | 365/365 | 365/365 |
| Diesel oil sulphur content/μ gg -1 | 9.8 | 49 | 8.6 | 22.8 |
| Diesel oil nitrogen content/μ gg -1 | 3.0 | 15.2 | 2.3 | 9.6 |
| Diesel cetane-number | 52.0 | 49.0 | 51.8 | 49.2 |
Continuous table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 3 | Process program 4 | Process program 5 |
| Stock oil | Raw material 2 | Raw material 2 | Raw material 2 |
| Catalyzer | A | FH-UDS/C | D/FH-UDS |
| The catalyst loading volume ratio | 100 | 30∶70 | 50∶50 |
| Pressure/MPa | 8.0 | 10.0 | 8.0 |
| Temperature/℃ | 350 | 360/370 | 370/370 |
| Air speed/h -1 | 1.2 | 2.6/2.6 | 2.0/2.0 |
| The inlet hydrogen to oil volume ratio | 500∶1 | 500∶1 | 800∶1 |
| Diesel oil sulphur content/μ gg -1 | 9.0 | 8.7 | 9.5 |
| Diesel oil nitrogen content/μ gg -1 | 1.0 | 1.6 | 1.8 |
| Diesel cetane-number | 34.5 | 34.7 | 33.5 |
Claims (10)
1. method of producing ultra-low-sulphur diesel comprises following content:
(a) diesel oil distillate adopts single hop or one-stage serial technical process as the stock oil of hydro-refining unit, comprises a kind of bulk phase catalyst bed in the reaction zone at least, and stock oil mixes with hydrogen by the hydrofining reaction district;
(b) under the hydrofining operational condition, obtain the oily gas that obtains in gas-liquid separator separates of hydrofining generation and after desulfurization, recycle;
(c) the isolating liquid phase of hydrofining effluent enters separation column;
(d) fractionation obtains all gases, petroleum naphtha, diesel product in separation column;
It is characterized in that comprising at least in the described refining reaction district a kind of bulk phase catalyst bed, bulk phase catalyst contains Mo, W, three kinds of metallic elements of Ni, catalyzer before sulfuration W, Ni with composite oxides Ni
xW
yO
zForm have z=x+3y wherein; Mo is with oxide M oO
3Form exist; Composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 8～8: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 10～10: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%.
2. in accordance with the method for claim 1, it is characterized in that composite oxides Ni in the described bulk phase catalyst
xW
yO
zThe ratio of middle x and y is 1: 4～4: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 5～5: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 50%～80%.
3. in accordance with the method for claim 1, it is characterized in that described hydrofining operational condition is: reaction pressure 2.0～12.0MPa, hydrogen to oil volume ratio are 200: 1～1000: 1, and the cumulative volume air speed is 0.2～5.0h
-1, 310 ℃～417 ℃ of temperature of reaction.
4. in accordance with the method for claim 1, it is characterized in that described hydrofining operational condition is: reaction pressure 3.0～10.0MPa, hydrogen to oil volume ratio 200: 1～800: 1, cumulative volume air speed 0.5～4.0h
-1, 320～400 ℃ of temperature of reaction.
5. in accordance with the method for claim 1, the catalyzer that it is characterized in that described refining reaction district is to be bulk phase catalyst all, or the combination of conventional Hydrobon catalyst and bulk phase catalyst; When being used in combination, the volume ratio of bulk phase catalyst and conventional Hydrobon catalyst is 90: 10～10: 90.
6. in accordance with the method for claim 5, when it is characterized in that being used in combination of described conventional Hydrobon catalyst and bulk phase catalyst, the volume ratio of bulk phase catalyst and conventional Hydrobon catalyst is 20: 80～80: 20.
7. in accordance with the method for claim 1, the specific surface area that it is characterized in that described bulk phase catalyst is 120～400m
2/ g, pore volume are 0.10～0.50ml/g.
8. in accordance with the method for claim 5, it is characterized in that described conventional Hydrobon catalyst has following character: pore volume 0.25～0.55ml/g, specific surface area is 100～400m
2/ g is 15%～45% in oxide weight hydrogenation active metals content in the catalyzer, and hydrogenation active metals comprises W, Mo, Ni or Co.
9. in accordance with the method for claim 8, it is characterized in that described conventional Hydrobon catalyst specific surface area is 150～300m
2/ g is 25%～40% in oxide weight hydrogenation active metals content in the catalyzer.
10. in accordance with the method for claim 1, it is characterized in that described stock oil is straight-run diesel oil, the catalytic cracking turning oil that obtains in the petroleum refining process, one or more of coker gas oil and viscosity breaking diesel oil, or the diesel oil distillate in coal tar or the liquefied coal coil.
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| CN102051216B (en) * | 2009-10-27 | 2014-01-01 | 中国石油化工股份有限公司 | Deep hydrodesulphurization and dearomatization method for fraction oil |
| CN102051217B (en) * | 2009-10-30 | 2014-07-30 | 中国石油化工股份有限公司 | Hydrogenation method for producing ultra-low sulfur clean diesel |
| CN102311759B (en) * | 2010-07-07 | 2015-02-18 | 中国石油化工股份有限公司 | Method for hydrodesulfurization of diesel |
| CN103074105B (en) * | 2011-10-25 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of Ultra-deep Desulfurization of Diesel Fuels method of no hydrogen circulation |
| CN103934019B (en) * | 2014-04-21 | 2015-11-11 | 四川省中明环境治理有限公司 | A kind of preparations and applicatio method of producing ultra-clean low-coagulation diesel oil catalyst |
| CN105038843B (en) * | 2015-06-12 | 2017-06-23 | 中国石油大学(华东) | A kind of diesel oil vapor-phase hydrodesulfurization process |
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| CN1171430A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Middle-pressure hydrocracking process for heavy fractional oil |
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| CN1342102A (en) * | 1999-01-15 | 2002-03-27 | 阿克佐诺贝尔公司 | Novel mixed metal catalyst, its preparation by co-precipitation, and its use |
| US6537442B1 (en) * | 1998-06-29 | 2003-03-25 | Akzo Nobel N.V. | Cogel containing oxidic compounds of tetravalent, trivalent, and divalent metallic elements |
| US6635599B1 (en) * | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
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| CN1171430A (en) * | 1996-07-22 | 1998-01-28 | 中国石油化工总公司 | Middle-pressure hydrocracking process for heavy fractional oil |
| US6635599B1 (en) * | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
| US6537442B1 (en) * | 1998-06-29 | 2003-03-25 | Akzo Nobel N.V. | Cogel containing oxidic compounds of tetravalent, trivalent, and divalent metallic elements |
| CN1339985A (en) * | 1999-01-15 | 2002-03-13 | 阿克佐诺贝尔公司 | A mixed metal catalyst composition, its preparation and use |
| CN1342102A (en) * | 1999-01-15 | 2002-03-27 | 阿克佐诺贝尔公司 | Novel mixed metal catalyst, its preparation by co-precipitation, and its use |
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