CN100590180C - Diesel oil fraction upgrading and pour point reducing process - Google Patents
Diesel oil fraction upgrading and pour point reducing process Download PDFInfo
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Abstract
The diesel oil fraction upgrading and pour point reducing process has the mixture of diesel oil material and hydrogen passing through the hydroupgrading reaction region to result in diesel oil with low solidification point through reaction under certain condition. The catalyst in the hydroupgrading reaction region includes at least one kind of bulk phase catalyst comprising complex oxide NixWyOz and oxide MoO3 in the weight ratio 0.1-10 and accounting for 40-100 wt% of total catalyst, and at least one kind of upgrading catalyst containing beta-zeolite. The present invention can lower the solidification point, 95 vol% point temperature and sulfur content of diesel oil, and raise cetane number and oxidation stability under mild condition.
Description
Technical field
The present invention relates to a kind of diesel oil fraction upgrading and pour point reducing process, particularly use the strong catalyzer of hydrogenation performance, the diesel oil fraction hydrogenating modification isomerization-visbreaking is produced the method for fine-quality diesel oil.
Background technology
Along with the increasingly stringent of environmental regulation, more and more higher to the specification of quality of automotive fuel.In the urban atmospheric pollution source, motor-vehicle tail-gas is an important component part.Therefore, more strict for the specification of quality of urban automobile automotive fuel.
Secondary processing technologies such as catalytic cracking in the oil refining enterprise, coking, viscosity breaking and wax oil hydrogenation processing extensively exist, but the distillate that these technologies obtain can not directly dispatch from the factory as product basically, need carry out aftertreatment.Generally the aftertreatment technology of Cai Yonging is hydrofining, but because common hydrofining technology can only reduce sulphur content, improves oxidation stability, can not increase substantially cetane value, effectively reduces condensation point, more can not reduce the 95v% point.
Adopt highly active Hydrobon catalyst, take off the impurity reaction though can carry out the degree of depth, but still can not improve the comprehensive use properties of product, and the performance of existing high-activity hydrofining catalyst still needs further to improve.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 of containing of US6652738 family/group vib active metal component 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.
CN 1171430A has introduced a kind of employing middle pressure hydrocracking method, though can increase substantially diesel-fuel cetane number, but owing to there is some diesel oil to be converted to naphtha fraction, diesel product yield is reduced, this market requirement with current raising diesel and gasoline ratio contradicts, so it is applied and is subjected to certain limitation.US 6,129, and 835 have introduced the conventional hydrofining technology that adopts, though impurity such as energy effective elimination sulphur, nitrogen obviously improve the color and the stability of diesel product, and keep very high diesel yield, diesel product cetane value amplification is limited.It is to select shape cracked technological process under hydrogen and the middle pressure condition facing that CN 1061679C has introduced the hydrodewaxing technology.It utilizes the pore passage structure of particular molecule sieve catalyst uniqueness and suitable acid sites, and the contour condensation point component of the normal paraffin in the diesel feed is carried out selective splitting, and to reduce the zero pour of diesel product, the while by-product is gasoline and C partly
3, C
4Lighter hydrocarbons.Adopt this technology, the maximum pour point depression amplitude of diesel oil can reach more than 50 ℃, and can be by adjusting the pour point depression amplitude of controlling reaction temperature diesel oil.But because the hydrogenation ability of used Hydrodewaxing catalyst is very weak, do not remove the impurity such as sulphur nitrogen in the oil product substantially, cause therefore that low-coagulation diesel oil product foreign matter content is higher, oxidation stability is relatively poor.CN1257107A has introduced hydrogenation pour point depression technology.This technology adopts hydrofining-hydrodewaxing combination process flow process, by the hydrogenation pre-refining is carried out in charging, not only improved hydrodewaxing section feeding quality, improved adaptability to stock oil, prolonged the running period of device, and alleviated operational condition greatly, and the purpose quality product is greatly improved.Adopt hydrogenation pour point depression technology to produce low-coagulation diesel oil, though can reduce the zero pour of diesel product significantly, but compare still with the requirement of producing clean fuel and to come with some shortcomings, as: can not obviously improve the diesel product cetane value, can not significantly reduce diesel product density and T95, diesel product yield is lower, and by-product naphtha olefins content is higher.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of diesel oil fraction hydrogenating modification isomerization-visbreaking and produce the method for fine-quality diesel oil, it can reduce the operating severity in hydrofining reaction district, promptly can realize reducing working pressure, reduce temperature of reaction, increase the device processing power and prolong in the effect such as catalyzer work-ing life one or more, and improving cetane value, reduce raw material 95v% point temperature when reducing condensation point, reduce foreign matter contents such as sulphur nitrogen.
The method that hydro-upgrading isomerization-visbreaking of the present invention is produced diesel oil comprises following content: be stock oil with the diesel oil distillate, adopt single hop or one-stage serial technical process, under the hydro-upgrading reaction conditions, stock oil and hydrogen order are by hydrofining reaction district and hydro-upgrading reaction zone, the hydro-upgrading that obtains generates oil and uses in the gas circulation that gas-liquid separator separates obtains, and the liquid that obtains obtains various products in the separation column fractionation: one or more in gas, petroleum naphtha, the diesel oil etc.At least comprise a kind of body phase method beds in the described hydrofining reaction district, body phase method catalyzer contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Composite 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 hydro-upgrading reaction zone has a kind of catalyst for hydro-upgrading of the β of containing zeolite at least.
The stock oil that the inventive method is used can be the catalytic cycle oil that obtains in the petroleum refining process, coker gas oil, and one or more of viscosity breaking diesel oil etc. also can be coal tar, gelatin liquefaction wet goods.Described diesel oil distillate stock oil can be diesel oil distillate, also can be the heavy distillate that comprises diesel oil distillate, can be 350～430 ℃ as the final boiling point of stock oil.
The hydrogenation reaction operational condition is generally reaction pressure 2.0～20.0MPa, and hydrogen to oil volume ratio is 200: 1～2500: 1, and the cumulative volume air speed is 0.1～6.0h-1,310 ℃～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 3.0～19.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～4.0h
-1, 320～435 ℃ of temperature of reaction.
The catalyzer in hydrofining reaction of the present invention district can all be a bulk phase catalyst, also can be the combination of 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 catalyst is 90: 10～10: 90, preferred 20: 80～80: 20.During combination loading, preferred feed by common Hydrobon catalyst bed, by bulk phase catalyst bed of the present invention, helps bringing into play the catalyzer overall activity most earlier then.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-98, FH-DS, 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, KF-757, KF-848 or the like.
The catalyzer of hydro-upgrading reaction zone of the present invention is the diesel oil hydrogenation modification catalyzer.Contain in the catalyst for hydro-upgrading of β zeolite and contain β zeolite 0.5～50.0wt%, preferably contain β zeolite 1.0～15.0wt%.β zeolite General N a
2The O weight content is less than 0.15wt%, preferably less than 0.10wt%, and SiO
2/ Al
2O
3Mol ratio 30～300, preferred 70～170, infrared acidity 0.05～0.8mmol/g, preferred 0.1～0.4mmol/g.Other carrier component can be one or more in the various inorganic refractory oxides such as mixture of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white and above several oxide compounds, and commonly used is aluminum oxide and/or amorphous silicon aluminium.The hydrogenation metal component can be selected from one or more in group vib and the group VIII base metal, and one or more that commonly used is among W, Mo, Ni, the Co are generally 15.0～40.0wt% in the oxide compound metal content, preferred 20.0～35.0wt%.Usually contain group vib metal and group VIII metal simultaneously, as contain W and/or Mo 15.0～30.0wt% in oxide compound, preferred 18.0～26.0wt% contains Ni and/or Co3.0～9.0wt% in oxide compound, preferred 5.0～7.0wt%.FC-14 that commercial catalyst for hydro-upgrading such as Fushun Petrochemical Research Institute (FRIPP) develop and FC-20 etc., also can be according to disclosed patented technology preparation, as CN1054153C, CN1108356C, CN1107710C, CN1151238C, CN1147574C, CN1219031C or the like.The catalyst volume ratio of hydrofining reaction district and hydro-upgrading reaction zone is 20: 80～80: 20, is preferably 30: 70～70: 30.
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
2Composite 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 molecule 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 highly active bulk phase catalyst, strengthened the hydrogenation performance of hydrofining reaction district catalyzer, can effectively reduce the content of organonitrogen in the stock oil, 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, thereby reduce the construction investment and the running cost of device.And because the increase of the hydrofining degree of depth, improved the aromatic hydrocarbons degree of saturation greatly, thereby can effectively carry out ring-opening reaction, reduce 95v% point temperature and improved cetane value, and low organonitrogen atmosphere more helps the performance of catalyst for hydro-upgrading isomery performance, and the condensation point of diesel product is lower.
Description of drawings
Fig. 1 is a principle process flow diagram of the present invention.
Fig. 2 is another principle process flow diagram of the present invention.
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, hydrofining reaction district and hydro-upgrading reaction zone need the layering filling according to the temperature distribution situation, cold hydrogen inlet is arranged between each bed, inject cold hydrogen during operation, take away the reaction heat that hydrogenation reaction and cracking reaction are given birth to, make temperature of reaction control within the specific limits, make operation safe, steady.
Poor-quality diesel-oil by cut fraction hydrogenation modification method particular content of the present invention is as follows: with one or more of poor-quality diesel-oil by cut fraction is stock oil, adopt single hop or one-stage serial technical process, under the hydro-upgrading operation condition, stock oil and hydrogen order are by hydrofining reaction district and hydro-upgrading reaction zone, the hydro-upgrading that obtains generates oil and uses in the gas circulation that gas-liquid separator separates obtains, and the liquid fractionation that obtains obtains following products: one or more in gas, petroleum naphtha, the diesel oil.
Specifically technical process as shown in Figure 1: stock oil and hydrogen are mixed into the hydrofining reaction district of all or part of high reactivity bulk phase catalyst of filling, generate oil and be mixed into the hydro-upgrading reaction zone, the generation oil fractionation separation column that obtains from the hydro-upgrading reaction zone obtains gas, products such as petroleum naphtha, diesel oil.
Fig. 2 is that with the difference of Fig. 1 hydrofining reaction district and hydrocracking reaction district are in different reactors.
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.
Catalyzer 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 percentage composition of wherein not pointing out benchmark is a 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 |
| Al 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 1.5wt%, 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 hydrofining activity, 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 Hydrobon catalyst has more intense hydrogenation performance, in hydrodenitrification, make the aromatic hydrocarbons degree of depth saturated, thereby promoted the quality of hydro-upgrading product relatively simultaneously.
Table 2 stock oil character
| The stock oil title | Stock oil-1 | Stock oil-2 |
| Density (20 ℃)/gcm -3 | 0.9130 | 0.8873 |
| The boiling range scope/℃ | 178～385 | 160～405 |
| T95/℃ | 376 | 390 |
| Sulphur content, wt% | 1.40 | 0.10 |
| Nitrogen content, wt% | 0.08 | 0.04 |
| Cetane value | 29.0 | 45.1 |
| Condensation point/℃ | 3 | 20 |
The main composition and the character of table 3-1. Hydrobon catalyst
Table 3-2 catalyst for hydro-upgrading is formed
| Catalyzer | HI-1 | HI-2 | HI-3 | HI-4 |
| The source | CN1107710 C embodiment 3 | CN1147574C embodiment 7 | CN1107710 C embodiment 5 | CN1147574 C embodiment 8 |
| Chemical constitution/wt% | ||||
| WO 3 | 20 | 22.5 | 22 | 22.5 |
| NiO | 5.5 | 7.5 | 7 | 7.5 |
| The β zeolite | 10 | 3 | 40 | 10 |
| Other carrier | Surplus | Surplus | Surplus | Surplus |
Table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 1 | Reference scheme 1 | Process program 2 | Reference scheme 2 |
| Catalyzer | A/HI-1 | FH-98/HI-1 | B/HI-2 | E/HI-2 |
| Stock oil | Raw material 1 | Raw material 1 | Raw material 2 | Raw material 2 |
| The catalyst loading volume ratio | 60∶40 | 60∶40 | 50∶50 | 50∶50 |
| Pressure/MPa | 8.0 | 8.0 | 56.0 | 6.0 |
| The inlet hydrogen to oil volume ratio | 600∶1 | 600∶1 | 700∶1 | 700∶1 |
| Air speed/h -1 | 1.2/1.8 | 1.2/1.8 | 1.6/1.6 | 1.6/1.6 |
| Temperature/℃ | 370/390 | 370/390 | 380/395 | 380/395 |
| Diesel yield, wt% | 98.1 | 96.2 | 98.8 | 98.1 |
| Diesel oil sulphur content/μ gg -1 | 3.6 | 30.5 | 2.8 | 10.4 |
| Diesel oil nitrogen content/μ gg -1 | 2.1 | 19.5 | 5.3 | 8.6 |
| Condensation point of diesel oil/℃ | -29 | -20 | -32 | -27 |
| T95/℃ | 348 | 356 | 354 | 365 |
| Diesel cetane-number | 50.0 | 39.0 | 46.37 | 41.1 |
Continuous table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 3 | Process program 4 |
| Stock oil | Raw material 2 | Raw material 1 |
| Catalyzer | FH-98/C/HI-3 | D/HI-4 |
| The catalyst loading volume ratio | 35∶35∶30 | 40∶60 |
| Pressure/MPa | 10.0 | 5.0 |
| Temperature/℃ | 360/370/390 | 380/410 |
| Air speed/h -1 | 2.4/2.4/2.0 | 3.0/2.0 |
| The inlet hydrogen to oil volume ratio | 500∶1 | 1000∶1 |
| Diesel yield, wt% | 98.2 | 97.1 |
| Diesel oil sulphur content/μ gg -1 | 1.7 | 2.5 |
| Diesel oil nitrogen content/μ gg -1 | 1.9 | 3.6 |
| Condensation point of diesel oil/℃ | -25 | -36 |
| T95/℃ | 349 | 358 |
| Diesel cetane-number | 55.1 | 46.4 |
Claims (10)
1, a kind of diesel oil fraction upgrading and pour point reducing process, comprise following content: be stock oil with the diesel oil distillate, under the hydro-upgrading reaction conditions, stock oil and hydrogen order are by hydrofining reaction district and hydro-upgrading reaction zone, the hydro-upgrading that obtains generates oil and uses in the gas circulation that gas-liquid separator separates obtains, and the liquid that obtains is in the separation column fractionation; It is characterized in that described hydro-upgrading reaction zone has a kind of catalyst for hydro-upgrading of the β of containing zeolite at least; At least comprise a kind of bulk phase catalyst bed in the described hydrofining reaction district, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, catalyzer before sulfuration W, Ni with Ni
xW
yO
z, the composite oxides form of z=x+3y exists, and Mo is with MoO
3Oxide form exists; 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 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 catalyst for hydro-upgrading contains β zeolite 0.5wt%～50.0wt%, β zeolite SiO
2/ Al
2O
3Mol ratio 30～300, infrared acidity 0.05～0.8mmol/g.
4, in accordance with the method for claim 1, it is characterized in that described catalyst for hydro-upgrading contains β zeolite 1.0wt%～15.0wt%, β zeolite SiO
2/ Al
2O
3Mol ratio 70～170, infrared acidity 0.1～0.4mmol/g.
5, according to claim 1,3 or 4 described methods, it is characterized in that in the mixture that described catalyst for hydro-upgrading carrier component is aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white and above several oxide compounds one or more, the hydrogenation metal component is selected from one or more in group vib and the group VIII base metal, is 15.0～40.0wt% in the oxide compound metal content.
6, in accordance with the method for claim 1, the final boiling point that it is characterized in that described stock oil diesel oil distillate is 350～430 ℃.
7, in accordance with the method for claim 1, it is characterized in that described hydro-upgrading reaction conditions is: reaction pressure 2.0～20.0MPa, hydrogen to oil volume ratio are 200: 1～2500: 1, and the cumulative volume air speed is 0.1～6.0h
-1, 310 ℃～455 ℃ of temperature of reaction.
8, in accordance with the method for claim 1, it is characterized in that described hydro-upgrading reaction conditions is: reaction pressure 3.0～19.0MPa, hydrogen to oil volume ratio 300: 1～2000: 1, volume space velocity 0.2～4.0h
-1, 320～435 ℃ of temperature of reaction.
9, in accordance with the method for claim 1, the catalyzer that it is characterized in that described hydrofining reaction district all is a bulk phase catalyst, 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 catalyst for refining is 90: 10～10: 90; The catalyst volume ratio of hydrofining reaction district and hydro-upgrading reaction zone is 20: 80～80: 20.
10, in accordance with the method for claim 9, when it is characterized in that described being used in combination, the volume ratio of bulk phase catalyst and conventional catalyst for refining is 20: 80～80: 20; The catalyst volume ratio of hydrofining reaction district and hydro-upgrading reaction zone is 30: 70～70: 30.
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| CN102049288B (en) * | 2009-10-27 | 2012-11-21 | 中国石油化工股份有限公司 | Beta zeolite-containing ultradeep hydrodesulfurization catalyst and preparation method thereof |
| CN103102916B (en) * | 2011-11-10 | 2015-06-17 | 中国石油化工股份有限公司 | Two-stage hydrogenation method for producing low freezing point motor fuel |
| CN103102918B (en) * | 2011-11-10 | 2015-07-22 | 中国石油化工股份有限公司 | Two-stage hydrogenation method for producing solvent oil |
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| CN103102921B (en) * | 2011-11-10 | 2015-07-22 | 中国石油化工股份有限公司 | Two-stage hydrogenation method for producing high quality low freezing point motor fuel |
| CN103805257B (en) * | 2012-11-07 | 2016-02-10 | 中国石油化工股份有限公司 | Catalyzer grating technology is utilized to produce the method for low-coagulation diesel oil |
| CN103805263B (en) * | 2012-11-07 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of method of producing high-grade low-freezing diesel oil |
| CN103805244B (en) * | 2012-11-07 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of production method of clean low-coagulation diesel oil |
| CN103805239B (en) * | 2012-11-07 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil |
| CN113061461B (en) * | 2021-03-25 | 2023-02-03 | 南京延长反应技术研究院有限公司 | Device and method for improving diesel oil quality |
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