CN102952581A - Inferior heavy oil hydrotreatment process - Google Patents
Inferior heavy oil hydrotreatment process Download PDFInfo
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- CN102952581A CN102952581A CN2011102494746A CN201110249474A CN102952581A CN 102952581 A CN102952581 A CN 102952581A CN 2011102494746 A CN2011102494746 A CN 2011102494746A CN 201110249474 A CN201110249474 A CN 201110249474A CN 102952581 A CN102952581 A CN 102952581A
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Abstract
The invention provides an inferior heavy oil hydrotreatment process capable of improving catalyst utilization rate. In the inferior heavy oil hydrotreatment process, two parallelly connected upflow type deferrization and decalcification reactors, an upflow type demetalization reactor, a fixed bed desulfurization reactor and a fixed bed denitrification reactor are used. By adopting simple and flexible hydrotreatment steps and properly selecting effective catalysts, catalyst hydrogenation and impurity removal capability can be improved finally, and the purpose of prolonging running periods of devices to the greatest extent can be achieved. The inferior heavy oil hydrotreatment process is particularly applicable to treating residual oil high in sulfur, metal content and asphaltene and capable of realizing long-term running of the devices.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for hydrofining and the hydrotreatment of heavy distillate and the residual oil of high metal, high-sulfur, high asphalt content.The inventive method has and not only has higher demetalization, desulfurization, denitrogenation and diasphaltene are active, and has the long device cycle of operation.
Background technology
At present, oil product market will be the trend that continues rising to the demand of light, middle matter oil product both at home and abroad, and is then on a declining curve to the demand of fuel wet goods heavy oil product.In addition, because the pressure of environment protection increases day by day, the quality standard requirement of the especially automobile-used petrol and diesel oil product of petroleum products has generally improved in various countries.Under above-mentioned market trend, can realize that heavy oil lighting, the oil Refining Technologies that can make resulting product satisfy constantly harsh petrol and diesel oil product specification have again become one of technology of domestic and international oil Refining Technologies developer's focus development with the rational cost of less expensive.
Shortening is the most effective heavy oil feed preconditioning technique.By hydrogenation, significantly reduce metal, sulphur, nitrogen, asphalt content in these raw materials, improve hydrogen-carbon ratio, and then provide good raw material for devices such as catalytic cracking and delayed cokings.Main hydrogenation technique mainly contains ebullated bed, suspension bed, moving-bed and fixed-bed process at present, and wherein suspension bed and moving bed process are also very immature, and cost is higher.The ebullated bed investment is higher, and operation easier is larger.Fixed bed is low, simple to operate and security is little because of cost, technology maturation, thereby development is very fast.
But in the fixed-bed catalytic hydrotreatment, if the raw material viscosity is large, metallic impurity or bituminous matter are higher, in hydrogenation process, metal and coke can be deposited on the catalyzer gradually, make easily the catalyzer rapid deactivation, and bed stops up, pressure raises, and the device frequent operation is stopped work.
This class raw material of hydrotreatment must guarantee the cyclical operation grown as far as possible to need not arrestment.Many investigators have proposed multiple solution.
But CN1322097C discloses a kind of method that adopts replaceable reactor and short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction.In the first hydrodemetallation (HDM) section, then hydrotreatment in the second hydrodesulfurizationsection section wherein has a protective belt at least before the hydrodemetallation (HDM) section first.Described hydroprocessing process comprises the steps: a) step, wherein uses the protective belt; B) step, this protective belt short circuit during this step, and regeneration and/or change the contained catalyzer of this section; C) step connects during this step again and has regenerated and/or the protective belt of catalyst changeout more; D) step, wherein the reactor of at least one hydrodemetallation (HDM) section and/or hydrodesulfurizationsection section can short circuit, and regeneration and/or change the contained catalyzer of this section.But such method needs higher initial outlay.
CN1349554 discloses a kind of method of the up-flow reactor system hydrotreating heavy feedstocks with the stratiform beds.The heavy feed stock that pollutes with the residual matter of upflow fixed bed reactor hydrotreatment metal, sulphur and the carbon containing of the catalyzer of at least two different hydrogenation activities.But the method cycle of operation is short, generally is no more than 1 year.
CN1144860 discloses a kind of method of residual hydrocracking.First reactor in heavy residual hydrogenation reactive system is set up one or more opening for feeds, change simultaneously original catalyzer grating, when an anticatalyzer bed pressure drop designs 0.4-0.8 times of maximum pressure drop for device, use successively next opening for feed instead, original opening for feed can advance the mixture of turning oil or turning oil and stock oil simultaneously.This technique can effectively prevent bed pressure drop and prolong the work-ing life of residual oil hydrocatalyst, and can increase the processing power of device.
CN00110714.3 discloses a kind of residual oil treatment process.By before heavy residual hydrogenation reactive system, adopt one section absorption filter agent bed or one section absorption filter agent bed and one section adsorption filtration beds to use simultaneously, not only can farthest remove the suspended particle that carries in the stock oil, but also can remove Iron sulfuret and the most of easily material of green coke that the iron naphthenate in the crude oil generates, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times that because of fouling cause of device in running period.
Summary of the invention
The purpose of this invention is to provide a kind of inferior heavy oil or process for hydrogenating residual oil, by adopting unique hydrotreatment flow process, and select rightly effective hydrogenation catalyst, and finally reaching and both improved catalyst hydrogenation removing impurities mass-energy power, assurance device has long cycle of operation this purpose again.
A kind of inferior heavy oil hydroprocessing technique, inferior heavy oil is or/and residual oil raw material and hydrogen enter deferrization decalcification reactor successively, fixed bed demetalization reactor, the fixed bed desulphurization reactor, the fixed bed denitrification reactor is processed, it is characterized in that being connected to two arms the material house steward, be equipped with check valve on two arms, link to each other with a upflowing deferrization decalcification reactor respectively behind the valve, the outlet line of two upflowing deferrization decalcification reactors is provided with check valve, after being merged into a pipeline behind the check valve, be connected with upflowing demetalization reactor from the bottom, more successively with the fixed bed desulphurization reactor, the fixed bed denitrification reactor links to each other; Inlet line at upflowing demetalization reactor is connected to 3-way valve, is connected by the outlet line of 3-way valve arm with upflowing demetalization reactor; The processing condition of each reactor are: hydrogen pressure 5.0MPa～20.0MPa, 300 ℃～450 ℃ of temperature, volume space velocity 0.2h during liquid
-1～3h
-1, hydrogen to oil volume ratio 300～2000.
In the present invention, inferior heavy oil is or/and residual oil raw material and hydrogen from bottom to top successively enter 1 or 2 in two upflowing deferrization decalcification reactors, and the in-built hydrogen deferrization decalcification catalyzer of dosing of reactor carries out deferrization decalcification reaction; Its resultant of reaction has two operation scheme afterwards: the one, directly enter upflowing demetalization reactor without separating, in the presence of catalyst for demetalation, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter the fixed bed desulphurization reactor, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter desulphurization reactor, in the presence of desulfurization catalyst, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters the fixed bed denitrification reactor without separation.Upflowing deferrization decalcification reactor bed filling hydrogenation deferrization decalcification catalyzer, preferably from the granules of catalyst center to outside surface, the active metal component concentration gradient of hydrogenation deferrization decalcification catalyzer reduces; Upflowing demetalization reactor bed filling Hydrodemetalation catalyst, preferably from the granules of catalyst center to outside surface, the active metal component concentration gradient of Hydrodemetalation catalyst reduces; Desulphurization reactor bed filling Hydrobon catalyst, preferably the active metal component concentration of Hydrobon catalyst is evenly distributed; Denitrification reactor bed filling hydrodenitrogenation catalyst, preferably from the granules of catalyst center to outside surface, the active metal component step increase of hydrodenitrogenation catalyst.
Wherein two simultaneously chargings of deferrization decalcification reactor also can be opened a standby form with one.
Method the method provided by the present invention can be processed high-sulfur, high metal content, high bitum residual oil, and can effectively slow down the lift velocity of reactor pressure decrease, thus the long-term operation of implement device.
The logistics direction of up-flow reactor of the present invention is to flow from bottom to top, and liquid phase is continuous in the reactor, slightly microdilatancy of the catalyzer in the bed.Mink cell focus, residual oil raw material and hydrogen can mix rear from up-flow reactor ground bottom feed.Make whole beds produce slight expansion, thus the rate of growth of slowing down the Pressure Drop of beds, the running period of extension fixture.Same ebullated bed, moving-bed and suspension bed are compared, and up-flow reactor has the characteristics such as low, simple to operate of investing.
Among the present invention, hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, preferably: the catalyzer aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Can load respectively one or more catalyzer in above-mentioned 4 classification reactors among the present invention, preferably along the logistics direction, the aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, generally take porous inorganic oxide such as aluminum oxide as carrier, group vib metal (such as W or/and Mo) and/or VIII family metal (such as Co or/and Ni) oxide compound is active ingredient, the physical property of catalyzer, forms preferably:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.1～3.0ml/g, is preferably 0.3～1.3ml/g;
3) specific surface is 20～400m
2/ g is preferably 100～240m
2/ g;
4) catalyzer contains 1.0～20.0% in corresponding burning amount (as follows), is preferably 3.0～16% group vib metal (such as MoO
3And/or WO
3), and/or 0.5～8.0%, be preferably 1.0～5.5% VIII family metal (such as CoO and/or NiO).
Hydrobon catalyst can adopt ordinary method of the prior art to prepare.
The preparation process that hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst are recommended is:
With Al
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, VIB and/or VIII compound (such as molybdenum and/or tungsten compound and/or nickel and/or cobalt compound) and deionized water or ammoniacal liquor are mixed and made into dipping solution, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, then lower dry 1～8 hour at 80～150 ℃, then at 300～650 ℃, be preferably in 400～550 ℃ of lower roastings and made catalyzer in 2～6 hours.Resulting catalyzer, requiring catalyst activity metal component distributed density autocatalysis agent particle center to be from high to low Gradient distribution to outside surface, can be that a reactive metal also can be the Gradient distribution that a plurality of active metal component distributed densities are above situation.
The Gradient distribution that catalyst activity metal component distributed density autocatalysis agent particle center is from high to low to outside surface can be by the denseer dipping solution of preparation, spray in the process at carrier, the saturated spray-stain carrier of method that progressively adds deionized water or ammoniacal liquor dilution dipping solution obtains; Or by the preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain at carrier.
The preparation process that hydrodenitrogenation catalyst is recommended is:
With Al
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with VI B and/or VIII family metallic compound, preferred molybdenum and/or tungsten and/or nickel and/or cobalt compound and deionized water or ammoniacal liquor are mixed and made into dipping solution, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, then descended dry 1～8 hour at 80～150 ℃, at 300～650 ℃, be preferably in 400～550 ℃ of lower roastings and made catalyzer in 2～6 hours.Resulting catalyzer requires active metal component distributed density autocatalysis agent particle center to be from low to high Gradient distribution to outside surface, can be that a reactive metal also can be the Gradient distribution that a plurality of reactive metal concentration are above situation.
The Gradient distribution that catalyst activity metal component distributed density autocatalysis agent particle center is from low to high to outside surface can be by preparation rarer VIB and/or VIII family metallic solution or deionized water, spray in the process, progressively adding the saturated sprayed carrier of denseer dipping solution obtains, or the dipping solution by the preparation different concns, spray at carrier from low to high by dipping solution concentration and to obtain.
In hydrogenation deferrization decalcification catalyzer and the Hydrodemetalation catalyst particle, the metal component concentration distribution reduces distribution in gradient from the particle center to outside surface, the granules of catalyst outside surface is 0.05～0.70 with the ratio of center reactive metal mass content, be preferably 0.15～0.45,0.66R (the particle center is point of beginning, R is the granules of catalyst radius) ratio located with center reactive metal mass content is 0.2～0.8, be preferably 0.35～0.6,0.33R the ratio that (R is the granules of catalyst radius) located with center reactive metal mass content is 0.4～0.9, is preferably 0.5～0.8.
In the hydrodenitrogenation catalyst particle, active metal component concentration increases gradually from the particle center to face.The granules of catalyst center is 0.05～0.70 with the ratio of outside surface reactive metal mass content, be preferably 0.15～0.45,0.33R (center is point of beginning, R is the granules of catalyst radius) ratio located with outside surface reactive metal mass content is 0.2～0.8, be preferably 0.3～0.6,0.66R the ratio that (R is the granules of catalyst radius) located with outside surface reactive metal mass content is 0.4～0.9, is preferably 0.5～0.8.
The carrier that uses in the method for preparing catalyst of the present invention can be to drip ball forming, spin granulation, extrusion molding, compression molding etc., to drip ball forming and extrusion molding as best.Catalyst shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.Take spherical and bar shaped as best.
Heavy-oil hydrogenation treatment process of the present invention, each reactor can adopt the hydroprocessing technique condition of any suitable this area, general processing condition are as follows: hydrogen pressure 5.0MPa～20.0MPa, be preferably 8.0MPa～18.0MPa, and that best is 10.0MPa～16.0MPa; 300 ℃～450 ℃ of temperature are preferably 360 ℃～440 ℃, and best is 360 ℃～430 ℃; Volume space velocity 0.2h during liquid
-1～3h
-1, be preferably 0.2h
-1～2h
-1, that best is 0.2h
-1～1h
-1Hydrogen to oil volume ratio 300～2000 is preferably 400～1500, and best is 500～1000.
The present invention has adopted up-flow reactor, and the logistics direction is to flow from bottom to top, and liquid phase is continuous in the reactor, slightly microdilatancy of the catalyzer in the bed.Same ebullated bed, moving-bed and suspension bed are compared, and up-flow reactor has the characteristics such as low, simple to operate of investing.Inferior heavy oil of the present invention, residual oil raw material and hydrogen mix rear bottom feed from up-flow reactor, make whole beds produce slight expansion, thereby slow down the rate of growth of the Pressure Drop of beds, simultaneously in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and denitrification reactor as select special catalyst, be particularly suitable for processing high-sulfur, high metal content, high bitum residual oil, the long-term operation of implement device.
Description of drawings
Fig. 1 inferior heavy oil of the present invention, residual hydrocracking process flow diagram.
Inferior heavy oil in Fig. 2 Comparative Examples 3, residual hydrocracking process flow diagram.
Fig. 3 in the present invention operable hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst particle center to the reactive metal concentration profile of outside surface.
Fig. 4 in the present invention operable hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst particle center to the reactive metal concentration distribution of outside surface.
Fig. 5 in the present invention operable Hydrobon catalyst particle center to the reactive metal concentration distribution of outside surface.
Fig. 6 in the present invention operable hydrodenitrogenation catalyst particle center to the reactive metal concentration distribution of outside surface.
Fig. 7 in the present invention operable hydrodenitrogenation catalyst particle center to the reactive metal concentration distribution of outside surface.
Embodiment
Below in conjunction with accompanying drawing the method that the present invention improves is further described, but does not therefore limit the present invention.
Fig. 1 is the hydroprocessing process synoptic diagram of inferior heavy oil or residual oil.
Divide together up-flow reactor R-1A that two-way enters hydrotreater and the bottom of R-1B with heavy oil or residual oil, contact with the up-flow reactor catalyzer and to carry out deferrization decalcification reaction, its resultant of reaction has two operation scheme afterwards: the one, directly enter upflowing demetalization reactor R-2 without separating, in the presence of catalyst for demetalation, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters fixed bed denitrification reactor R-4 without separation.In operational process, when upflowing demetalization reactor catalyst inactivation, feed switched flows to, and the residual oil material out directly enters desulphurization reactor R-3 from deferrization decalcification reactor.
It is worth mentioning that R-1 and R-2 reactor can be opened simultaneously, also can one open one standby.
The Active components distribution of the catalyzer of upflowing deferrization decalcification reactor provided by the invention and upflowing demetalization reactor as shown in Figures 2 and 3.Wherein, from deferrization decalcification catalyzer and catalyst for demetalation particle center to outside surface, active metal component concentration can be with Fig. 2 formal distribution, also can be with Fig. 3 formal distribution.Can find from Fig. 3: from the granules of catalyst center to outside surface, a platform has appearred in concentration distribution, two steps.Here need to prove that concentration distribution can exist with one or more stepped form.But total trend is: autocatalysis agent particle center is to outside surface, and active metal component concentration in gradient reduces distribution.
The active metal component concentration that outside surface is arrived at the used desulfurization catalyst particle center of desulphurization reaction distributes as shown in Figure 4.Wherein, from the surface of desulfurization catalyst particle to the center, the active metal component concentration form that substantially is evenly distributed.
The used denitrification catalyst particle center of denitrification reactor to the reactive metal concentration distribution of outside surface as shown in Figure 5 and Figure 6.Wherein, to outside surface, in the denitrification catalyst particle, active metal component concentration can be with Fig. 5 formal distribution, also can be with Fig. 6 formal distribution by the center of denitrification catalyst particle; Can find from Fig. 6: from the granules of catalyst center to outside surface, three platforms have appearred in concentration distribution, two steps.Here need to prove that concentration distribution can exist with one or more stepped form.But total trend is: to outside surface, active metal component concentration in gradient increases distribution from denitrogenation granules of catalyst center.
Embodiment 1 (described concentration % is quality %)
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflowing deferrization decalcification reactor charge decalcifying agent is numbered DFC-1#, and the preparation method of catalyzer is as follows:
Present embodiment is with five jiaos of circular Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is Mo.
Take by weighing 150g, water-intake rate is the Al of 1.10ml/g
2O
3Carrier sprays 50ml and contains the 8.6g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) dipping solution at the uniform velocity splashes into the 115ml aqueous solution in dipping solution and stirs in the spray-stain process, spray while splashing into, and sprays in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer DFC-1#.Its physical data is as follows: MoO
3Content is 4.3%, specific surface area 98m
2/ g, pore volume 0.92ml/g, bulk density 0.40g/ml, porosity is 50%, catalyst particle size is 10mm.
Upflowing demetalization reactor loads 2 kinds of Hydrodemetalation catalysts from top to bottom successively, and numbering is respectively DM-1# and DM-2#.Method for preparing catalyst is as follows:
To contain 2.0%ZrO
2Two kinds of trifolium Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer DM-1# that active metal component is Mo.
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2Al
2O
3Carrier sprays 82.5ml and contains the 10.33g ammonium molybdate and (contain MoO
382%) the aqueous solution at the uniform velocity splashes into 82.5ml and contains the 2.33g ammonium molybdate and (contain MoO in the spray-stain process
382%) ammonia soln also stirs in mentioned solution, sprays while splashing into, and sprays in 10 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DM-1#.The physical data of DM-1# is as follows: MoO
3Content is 6.51%, specific surface area 108m
2/ g, pore volume 0.82ml/g, bulk density 0.48g/m, porosity is 45%, particle diameter is 3.5mm.
To contain 1.5%TiO
2Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer DM-2# that active metal component is Mo, Co.
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 1.5%TiO
2A l
2O
3Carrier sprays 50ml and contains the 18.6g ammonium molybdate and (contain MoO
382%) and the 8.75g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (contain CoO 25.2%, Beijing chemical reagents corporation) ammonia soln, spray-stain process moderate at the uniform velocity splash into 115ml concentration be 15% ammonia soln in soaking solution and stir, spray while splashing into, sprayed in 15 minutes.Homogenizing is after 10 minutes in spraying equipment, 120 ℃ lower dry 5 hours, again roasting 4 hours in 500 ℃ of air makes catalyzer.Be numbered DM-2#.The physical data of DM-2# is as follows: MoO
3Content is that 8.5%, CoO mass content is 1.3%, specific surface area 128m
2/ g, pore volume 0.76ml/g, bulk density 0.51g/ml, porosity is 43%, particle diameter is 2.5mm.
The catalyzer that the fixed bed desulphurization reactor loads from top to bottom successively is numbered DS-1# and DS-2#.
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 5%ZrO
2Al
2O
3Carrier sprays 165ml by the saturated absorption amount of solution and contains the 22.6g ammonium molybdate and (contain MoO
382%) and the ammonia soln of 21g nickelous nitrate (containing NiO 25.2%).Homogenizing is after 5 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DS-1#.The physical data of DS-1# is as follows: MoO
3Content is that 10.81%, NiO mass content is 2.8%, specific surface area 165m
2/ g, pore volume 0.62ml/g, bulk density 0.64g/ml, porosity is 42%, particle diameter is 1.5mm.
Take by weighing 150g, water-intake rate is the Al of 1.10ml/g
2O
3Carrier sprays 165ml by the saturated absorption amount of solution and contains the 29.8g ammonium molybdate and (contain MoO
382% quality) and the ammonia soln of 22.0g nickelous nitrate (containing NiO 25.2%).Homogenizing is after 5 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DS-2#.The physical data of DS-2# is as follows: MoO
3Content is that 13.5%, NiO mass content is 3.3%, specific surface area 182m
2/ g, pore volume 0.53ml/g, bulk density 0.68g/ml, porosity is 41%, particle diameter is 1.3mm.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, method for preparing catalyst is as follows:
The hydrodenitrogenation catalyst preparation method is as follows:
To contain 2.0%ZrO
2Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is W, Ni.
Take by weighing 150g, water-intake rate is that 1.10ml/g is to contain 2.0%ZrO
2Al
2O
3Carrier sprays 100ml concentration and is 5% ammonia soln, at the uniform velocity splashes into 65ml and contain the 63g ammonium metawolframate and (contain WO in the spray-stain process
388%) and the phosphate aqueous solution of 33.7g nickelous nitrate (containing NiO 25.2%) in mentioned solution and stir, spray while splashing into, sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DN-1#.Wherein, WO
3Content is that 25.8%, NiO content is 4.45%, and specific surface area is 182m
2/ g, pore volume are 0.42ml/g, and bulk density is 0.82g/ml, and porosity is 40%, and particle diameter is 1.1mm.
Be the device operating scheme below, adopt technique shown in Figure 1:
Divide together up-flow reactor R-1A that two-way enters hydrotreater and the bottom of R-1B with heavy oil or residual oil, contact with the up-flow reactor catalyzer and to carry out deferrization decalcification reaction, its resultant of reaction has two operation scheme afterwards: the one, directly enter upflowing demetalization reactor R-2 without separating, in the presence of catalyst for demetalation, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters fixed bed denitrification reactor R-4 without separation.In operational process, when upflowing demetalization reactor catalyst inactivation, feed switched flows to, and the residual oil material out directly enters desulphurization reactor R-3 from deferrization decalcification reactor.
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer is numbered DFC-2#, and the preparation method is as follows:
Select spherical Al
2O
3Make carrier, take by weighing the Al that the 150g water-intake rate is 1.10ml/g
2O
3Carrier sprays 50ml and contains the 8.6g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) the aqueous solution at the uniform velocity splashes into 115ml concentration and is 15% ammonia soln in mentioned solution and stirs in the spray-stain process, spray while splashing into, and sprays in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.The physical data of DFC-2# is as follows: MoO
3Content is 4.12%, and specific surface area is 107m
2/ g, pore volume are 0.86ml/g, and bulk density is 0.43g/ml, and porosity is 50%, and catalyst particle size is 9mm.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent from top to bottom successively, and numbering is respectively DM-1# and DM-2#.The Hydrodemetalation catalyst preparation method is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogen desulfurization agents from top to bottom successively, and numbering is respectively DS-1# and DS-2#.The desulfurization catalyst preparation method is with embodiment 1.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalysts from top to bottom successively, numbering DN-1# and DN-2#.Wherein the DN-1# method for preparing catalyst is with embodiment 1.
The DN-2# method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2Al
2O
3Carrier sprays 82.5ml and contains the 21.35g ammonium molybdate and (contain MoO
382%) and the aqueous solution of 39.7g nickelous nitrate (containing NiO 25.2%), at the uniform velocity splashing into 82.5ml in the spray-stain process contains the 21.35g ammonium molybdate and (contains MoO
382%) the aqueous solution also stirs in solution, sprays while splashing into, and sprays in 10 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DN-2#.The physical data of DN-2# is as follows: MoO
3Content is that 17.91%, NiO mass content is 5.12%, specific surface area 191m
2/ g, pore volume 0.43ml/g, bulk density 0.78g/ml, porosity is 40%, particle diameter is 1.1mm.
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-1#, catalyzer is with embodiment 1.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-2#, catalyzer is with embodiment 1.
1 kind of hydrogen desulfurization agent of desulphurization reactor filling, numbering is respectively DS-2#.Catalyzer is with embodiment 1.
1 kind of hydrodenitrogenation catalyst DN-2# of fixed bed denitrification reactor filling, catalyzer is with embodiment 2.
Estimating raw materials used oily C is residual oil raw material, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-1#, catalyzer is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogen desulfurization agents from top to bottom successively, and numbering is respectively DS-1# and DS-2#.Catalyzer is with embodiment 1 and embodiment 2.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, catalyzer is with embodiment 1.
Estimating raw materials used oily D is residual oil raw material, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and the preparation method is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogen desulfurization agents from top to bottom successively, and numbering is respectively DS-1# and DS-2#.Catalyzer is with embodiment 1 and embodiment 2.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-1# from top to bottom successively, and catalyzer is with embodiment 1.
Estimating raw materials used oily E is vacuum residuum, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 6
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-1#, the preparation method is with embodiment 1.
1 kind of hydrogen desulfurization agent of desulphurization reactor filling, numbering is respectively DS-1#.Catalyzer is with embodiment 1.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, catalyzer is with embodiment 1.
Estimating raw materials used oily F is vacuum residuum, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 7
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and the preparation method is with embodiment 1.
The fixed bed desulphurization reactor loads 2 kinds of hydrogen desulfurization agents from top to bottom successively, and numbering is respectively DS-1# and DS-2#.Catalyzer is with embodiment 1 and embodiment 2.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-1# and DN-2# from top to bottom successively, and catalyzer is with embodiment 1 and embodiment 2.
Estimating raw materials used oily G is vacuum residuum, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 8
Use hydrogenation technique combination shown in Figure 1, comprise 5 fixed-bed reactor, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer is numbered DFC-3#, and the preparation method of catalyzer is as follows:
With five jiaos of circular Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is Mo.
Take by weighing 150g, water-intake rate is the Al of 1.10ml/g
2O
3Carrier sprays 165ml and contains the 8.6g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) the aqueous solution sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer DFC-3#.Its physical data is as follows: MoO
3Content is 4.28%, NiO mass content 0.47%, specific surface area 101m
2/ g, pore volume 0.88ml/g, bulk density 0.41g/ml, porosity is 50%, catalyst particle size is 10mm.
1 kind of Hydrodemetalation catalyst of upflowing demetalization reactor charge is numbered DM-3#.Method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 2%m TiO
2Al
2O
3Carrier sprays 165ml and contains the 18.6g ammonium molybdate and (contain MoO
382%) and the ammonia soln of 8.75g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (containing CoO 25.2m%, Beijing chemical reagents corporation), sprayed in 15 minutes.Homogenizing is after 10 minutes in spraying equipment, 120 ℃ lower dry 5 hours, again roasting 4 hours in 500 ℃ of air makes catalyzer.Be numbered DM-3#.The physical data of DM-3# is as follows: MoO
3Content is that 8.91%, CoO mass content is 1.28%, specific surface area 125m
2/ g, pore volume 0.78ml/g, bulk density 0.5g/ml, porosity is 45%, particle diameter is 2.5mm.
The catalyzer of fixed bed desulphurization reactor filling is selected DS-2#, and the preparation method is together with embodiment 1.
1 kind of hydrodenitrogenation catalyst of fixed bed denitrification reactor filling is numbered DN-3#.
The DN-3# method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 2.0%Z rO
2Al
2O
3Carrier sprays 165ml and contains the 42.7g ammonium molybdate and (contain MoO
382%) and the aqueous solution of 39.7g nickelous nitrate (containing NiO 25.2%), sprayed in 10 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DN-3#.The physical data of DN-3# is as follows: MoO
3Content is that 17.85%, NiO mass content is 5.2%, specific surface area 195m
2/ g, pore volume 0.42ml/g, bulk density 0.78g/ml, porosity is 40%, particle diameter is 1.1mm.
Estimating raw materials used oily C is residual oil raw material, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 9
Use hydrogenation technique combination shown in Figure 1, comprise 5 fixed-bed reactor, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Feedstream is to embodiment 5.
Hydrogenation deferrization decalcification catalyzer is selected DFC-3#; Hydrodemetalation catalyst is selected DM-4#; Hydrobon catalyst is selected DS-1# and DS-2#; And hydrodenitrogenation catalyst is selected DN-1#.
To contain 2.0%ZrO
2Trifolium Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer DM-4# that active metal component is Mo.
Take by weighing 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2Al
2O
3Carrier sprays 165ml and contains the 12.66g ammonium molybdate and (contain MoO
382%) the aqueous solution sprayed in 10 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DM-4#.The physical data of DM-4# is as follows: MoO
3Content is 6.50%, specific surface area 110m
2/ g, pore volume 0.79ml/g, bulk density 0.47g/ml, porosity is 45%, particle diameter is 3.5mm.
Estimating raw materials used oily E is vacuum residuum, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 10
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-3#, the preparation method is with embodiment 8.
1 kind of hydrogen desulfurization agent of desulphurization reactor filling, numbering is respectively DS-1#.Catalyzer is with embodiment 1.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, catalyzer is with embodiment 1.
Estimating raw materials used oily F is vacuum residuum, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Embodiment 11
Use hydrogenation technique combination shown in Figure 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and the preparation method is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogen desulfurization agents from top to bottom successively, and numbering is respectively DS-1# and DS-2#.Catalyzer is with embodiment 1 and embodiment 2.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-3# and DN-4# from top to bottom successively.
The DN-4# method for preparing catalyst is as follows:
To contain 2.0%ZrO
2Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is W, Ni.
Take by weighing 150g, water-intake rate is that 1.10ml/g is to contain 2.0%ZrO
2Al
2O
3Carrier sprays 165ml and contains the 63g ammonium metawolframate and (contain WO
388%) and the phosphate aqueous solution of 33.7g nickelous nitrate (containing NiO 25.2%), sprayed in 5 minutes.Homogenizing is after 10 minutes in spraying equipment, 60 ℃ lower dry 2 hours, take out rear 120 ℃ lower dry 3 hours, again roasting 3 hours in 500 ℃ of air makes catalyzer.Be numbered DN-4#.Wherein, WO
3Content is that 26.1%, NiO content is 4.72%, and specific surface area is 188m
2/ g, pore volume are 0.55ml/g, and bulk density is 0.745g/ml, and porosity is 40%, and particle diameter is 1.1mm.
Estimating raw materials used oily G is residual oil raw material, and its character is as shown in table 3.The device operating scheme is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Comparative Examples 1
Hydrogenation technique combination in the Comparative Examples 1 comprises 5 fixed-bed reactor, and comprising 2 deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor, feed stream all passes through reactor from top to bottom.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load respectively hydrogen desulfurization agent and hydrodenitrification agent.Catalyzer is with embodiment 1.
Comparative Examples 1 raw materials used oily A is vacuum residuum, and its character is as shown in table 1.The device operating scheme is with embodiment 1.Its reaction conditions and reaction product character are as shown in table 4, and as can be seen from Table 4, in the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 1 all are higher than Comparative Examples.And the operational cycle of Comparative Examples also is starkly lower than embodiment 1.
Comparative Examples 2
Hydrogenation technique combination in the Comparative Examples 2 comprises 5 fixed-bed reactor, and comprising 2 deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor, feed stream all passes through reactor from top to bottom.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load respectively hydrogen desulfurization agent and hydrodenitrification agent.Catalyzer is with embodiment 2.
Comparative Examples 2 raw materials used oily B are vacuum residuum, and its character is as shown in table 3.The device operation is with embodiment 2.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.As can be seen from Table 4, in the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 2 all are higher than Comparative Examples.And the operational cycle of Comparative Examples 2 also is starkly lower than embodiment 2.
Comparative Examples 3
Hydrogenation technique combination in the Comparative Examples 3 comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.But technical process as shown in Figure 2, and processing condition, catalyzer are all identical with embodiment 3, and its its reaction conditions of reaction conditions and reaction result are as shown in table 4.As shown in Table 4, in the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 3 all are higher than Comparative Examples 3.In satisfying the qualified standard of product, its operational cycle is starkly lower than embodiment 3.
Comparative Examples 4
Hydrogenation technique combination in the Comparative Examples 4 comprises 5 fixed-bed reactor, comprising 2 deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Feed stream all passes through reactor from top to bottom.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst are all with embodiment 4.
The raw materials used oily D of Comparative Examples is residual oil raw material, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.As can be seen from Table 4, in the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 4 all are higher than Comparative Examples 4.And the operational cycle of Comparative Examples also is starkly lower than embodiment 4.
Adopt the EDX characterization method that catalyzer DFC-1, DFC-2, DM-1, DM-2, DS-1, DS-2, DN-1, DN-2 are characterized, describe the distribution situation of active ingredient on granules of catalyst, the result is referring to table 1 and table 2.
As can be seen from Table 1, catalyzer DFC-1, DFC-2, DM-1, DM-2 particle from interior to outside, the downtrending of single or multiple reactive metal concentration in gradient; Catalyzer DN-1 and DN-2 particle from interior to outside, single or multiple reactive metal concentration in gradient increase trend; Catalyzer DS-1, DS-2, DFC-3, DN-3 and DN-4 particle from interior to outside, reactive metal substep is comparatively even.
Reactive metal concentration distribution on table 1 granules of catalyst
| Numbering | DFC-1 | DFC-2 | DFC-3 | DM-1 | DM-2 | DM-3 | DM-4 | DS-1 | DS-2 |
| W (outside surface)/W (center) | |||||||||
| Mo (outside surface)/Mo (center) | 0.26 | 0.29 | 0.96 | 0.33 | 0.31 | 0.92 | 0.94 | 0.92 | 1.06 |
| Co (outside surface)/Co (center) | 0.27 | 0.96 | |||||||
| Ni (outside surface)/Ni (center) | 1.03 | 1.10 | |||||||
| W (2/3R)/W (center) | |||||||||
| Mo (2/3R)/Mo (center) | 0.51 | 0.39 | 1.08 | 0.60 | 0.42 | 1.03 | 0.99 | 1.05 | 1.02 |
| Co (2/3R)/Co (center) | 0.38 | 0.95 | |||||||
| Ni (2/3R)/Ni (center) | 0.98 | 0.99 | |||||||
| W (1/3R)/W (center) | |||||||||
| Mo (1/3R)/Mo (center) | 0.78 | 0.81 | 0.96 | 0.98 | 0.76 | 1.06 | 1.03 | 1.03 | 0.96 |
| Co (1/3R)/Co (center) | 0.66 | 1.02 | |||||||
| Ni (1/3R)/Ni (center) | 1.01 | 1.01 |
Annotate: take the particle center as starting point, R is the granules of catalyst radius.
Reactive metal concentration distribution on table 2 granules of catalyst
| Numbering | DN-1 | DN-2 | DN-3 | DN-4 |
| The reactive metal concentration distribution | ||||
| W (center)/W (outside surface) | 0.32 | 0.95 | ||
| Mo (center)/Mo (outside surface) | 0.96 | 1.06 | ||
| Co (center)/Co (outside surface) | ||||
| Ni (center)/Ni (outside surface) | 0.28 | 0.32 | 0.95 | 1.01 |
| W (1/3R)/W (outside surface) | 0.53 | 0.98 | ||
| Mo (1/3R)/Mo (outside surface) | 0.98 | 1.02 | ||
| Co (1/3R)/Co (outside surface) | ||||
| Ni (1/3R)/Ni (outside surface) | 0.49 | 0.56 | 1.02 | 0.99 |
| W (2/3R)/W (outside surface) | 0.81 | 1.02 | ||
| Mo (2/3R)/Mo (outside surface) | 1.01 | 0.96 | ||
| Co (2/3R)/Co (outside surface) | ||||
| Ni (2/3R)/Ni (outside surface) | 0.85 | 0.81 | 1.02 | 0.98 |
Annotate: take the particle center as starting point, R is the granules of catalyst radius.
Table 3 test raw material oil main character
| Material name | A | B | C | D | E | F | G |
| Density (20 ℃), kg/m 3 | 968.1 | 956.2 | 962.2 | 971.3 | 976.2 | 982.3 | 955.2 |
| Fe，μg/g | 25 | 7.8 | 10 | 15 | 2 | 3 | 8 |
| Ca，μg/g | 2.2 | 40 | 30.25 | 10 | 3 | 5 | 15 |
| (Ni+V)，μg/g | 90.6 | 50.2 | 42 | 60 | 110.1 | 105.2 | 60 |
| Sulphur, % | 3.01 | 2.32 | 2.6 | 1.9 | 3.8 | 3.5 | 4.2 |
| Nitrogen, % | 0.19 | 0.39 | 0.16 | 0.3 | 0.26 | 0.21 | 0.31 |
| Carbon residue, % | 14.1 | 12.1 | 13.1 | 13.2 | 13.6 | 13.3 | 14.32 |
Table 4 processing condition and product property
Table 5 processing condition and product property
Claims (22)
1. inferior heavy oil hydroprocessing technique, inferior heavy oil is or/and residual oil raw material and hydrogen enter deferrization decalcification reactor successively, fixed bed demetalization reactor, the fixed bed desulphurization reactor, the fixed bed denitrification reactor is processed, it is characterized in that being connected to two arms the material house steward, be equipped with check valve on two arms, link to each other with a upflowing deferrization decalcification reactor respectively behind the valve, the outlet line of two upflowing deferrization decalcification reactors is provided with check valve, after being merged into a pipeline behind the check valve, be connected with upflowing demetalization reactor from the bottom, more successively with the fixed bed desulphurization reactor, the fixed bed denitrification reactor links to each other; Inlet line at upflowing demetalization reactor is connected to 3-way valve, is connected by the outlet line of 3-way valve arm with upflowing demetalization reactor; The processing condition of each reactor are: hydrogen pressure 5.0MPa～20.0MPa, 300 ℃～450 ℃ of temperature, volume space velocity 0.2h during liquid
-1～3h
-1, hydrogen to oil volume ratio 300～2000.
2. inferior heavy oil hydroprocessing technique according to claim 1 is characterized in that the processing condition of each reactor are: hydrogen pressure 8.0MPa～18.0MPa, 360 ℃～440 ℃ of temperature, volume space velocity 0.2h during liquid
-1～2h
-1, hydrogen to oil volume ratio 400～1500.
3. the inferior heavy oil hydroprocessing technique shown in according to claim 1 is characterized in that upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, and from the granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces.
4. the inferior heavy oil hydroprocessing technique shown in according to claim 1 is characterized in that upflowing demetalization reactor charge Hydrodemetalation catalyst, and from the granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces.
5. the inferior heavy oil hydroprocessing technique shown in according to claim 1 is characterized in that desulphurization reactor bed filling Hydrobon catalyst, and the active metal component concentration of Hydrobon catalyst is evenly distributed.
6. the inferior heavy oil hydroprocessing technique shown in according to claim 1 is characterized in that denitrification reactor bed filling hydrodenitrogenation catalyst, from the granules of catalyst center to outside surface, and the active metal component step increase of catalyzer.
7. the inferior heavy oil hydroprocessing technique shown in according to claim 1 is characterized in that upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, and from the granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces; Upflowing demetalization reactor charge Hydrodemetalation catalyst, from the granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces; Desulphurization reactor bed filling Hydrobon catalyst, the active metal component concentration of Hydrobon catalyst is evenly distributed; Denitrification reactor bed filling hydrodenitrogenation catalyst, from the granules of catalyst center to outside surface, the active metal component step increase of hydrodenitrogenation catalyst.
8. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, upflowing demetalization reactor charge Hydrodemetalation catalyst, desulphurization reactor bed filling Hydrobon catalyst, denitrification reactor bed filling hydrodenitrogenation catalyst, hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, the catalyzer aperture reduces gradually, granularity reduces gradually, and porosity reduces gradually.
9. inferior heavy oil hydroprocessing technique according to claim 1, the upflowing deferrization decalcification reactor that it is characterized in that two parallel connections, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor loads respectively more than one catalyzer in above-mentioned 4 classification reactors, along the logistics direction, the aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
10. inferior heavy oil hydroprocessing technique according to claim 7, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, catalyzer is take porous inorganic oxide such as aluminum oxide as carrier, and group vib metal and/or VIII family metal oxide are active ingredient.
11. inferior heavy oil hydroprocessing technique according to claim 10, it is characterized in that catalyzer physical property, consist of:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.1～3.Oml/g;
3) specific surface is 20～400m
2/ g;
4) catalyzer contains 1.0～20.0% group vib metal in corresponding burning amount, and/or the VIII family metal of 0.5～8.O%.
12. inferior heavy oil hydroprocessing technique according to claim 11, it is characterized in that catalyzer physical property, consist of:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.3～1.3ml/g;
3) specific surface is 100～240m
2/ g;
4) catalyzer is in corresponding burning amount, contains 3.0～16% group vib metal and/or 1.0～5.5% VIII family metal.
13. according to claim 10 or 11 or 12 described inferior heavy oil hydroprocessing techniques, it is characterized in that the group vib metal is Mo and/or W.
14. according to claim 10 or 11 or 12 described inferior heavy oil hydroprocessing techniques, it is characterized in that VIII family metal is Co and/or Ni.
15. according to claim 3 or 4 or 7 described inferior heavy oil hydroprocessing techniques, when it is characterized in that catalyst activity metal component distributed density autocatalysis agent particle center is from high to low Gradient distribution to outside surface, the preparation process of catalyzer is:
With Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, Z rO
2Al
2O
3As carrier, VIB and/or VIII compound and deionized water or ammoniacal liquor are mixed and made into dipping solution, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, then descended dry 1～8 hour at 80～150 ℃, then at 300～650 ℃, roasting made catalyzer in 2～6 hours; Resulting catalyzer requires catalyst activity metal component distributed density autocatalysis agent particle center to be from high to low Gradient distribution to outside surface, is the Gradient distribution that a reactive metal or a plurality of active metal component distributed density are above situation.
16. inferior heavy oil hydroprocessing technique according to claim 15, it is characterized in that catalyst activity metal component distributed density autocatalysis agent particle center is by the denseer dipping solution of preparation to the Gradient distribution that outside surface is from high to low, spray in the process at carrier, the saturated spray-stain carrier of method that progressively adds deionized water or ammoniacal liquor dilution dipping solution obtains; Or by the preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain at carrier.
17. according to claim 6 or 7 described inferior heavy oil hydroprocessing techniques, it is characterized in that the preparation process of hydrodenitrogenation catalyst is:
With Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with VIB and/or VIII family metallic compound, be mixed and made into dipping solution with deionized water or ammoniacal liquor, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, then descended dry 1～8 hour at 80～150 ℃, made catalyzer in 2～6 hours 300～650 ℃ of lower roastings; Resulting catalyzer requires active metal component distributed density autocatalysis agent particle center to be from low to high Gradient distribution to outside surface, is the Gradient distribution that a reactive metal or a plurality of reactive metal concentration are above situation.
18. inferior heavy oil hydroprocessing technique according to claim 17, it is characterized in that catalyst activity metal component distributed density autocatalysis agent particle center is from low to high Gradient distribution to outside surface, by preparation rarer VIB and/or VIII family metallic solution or deionized water, spray in the process, progressively adding the saturated sprayed carrier of denseer dipping solution obtains, or the dipping solution by the preparation different concns, spray at carrier from low to high by dipping solution concentration and to obtain.
19. according to claim 3 or 4 or 7 described inferior heavy oil hydroprocessing techniques, it is characterized in that in the granules of catalyst, the metal component concentration distribution reduces distribution in gradient from the particle center to outside surface, the granules of catalyst outside surface is 0.05～0.70 with the ratio of center reactive metal mass content, the particle center is point of beginning, when R is the granules of catalyst radius, 0.66R locating ratio with center reactive metal mass content and be the ratio of 0.2～0.8,0.33R place and center reactive metal mass content is 0.4～0.9.
20. inferior heavy oil hydroprocessing technique according to claim 19, it is characterized in that in hydrogenation deferrization decalcification catalyzer and the Hydrodemetalation catalyst particle, the granules of catalyst outside surface is 0.15～0.45 with the ratio of center reactive metal mass content, 0.66R locating ratio with center reactive metal mass content and be the ratio of 0.35～0.6,0.33R place and center reactive metal mass content is 0.5～0.8.
21. according to claim 6 or 7 described inferior heavy oil hydroprocessing techniques, it is characterized in that in the hydrodenitrogenation catalyst particle, active metal component concentration increases gradually from the particle center to face; The granules of catalyst center is 0.05～0.70 with the ratio of outside surface reactive metal mass content, the center is point of beginning, when R is the granules of catalyst radius, 0.33R locating ratio with outside surface reactive metal mass content and be the ratio of 0.2～0.8,0.66R place and outside surface reactive metal mass content is 0.4～0.9.
22. inferior heavy oil hydroprocessing technique according to claim 21, it is characterized in that in the hydrodenitrogenation catalyst particle, the granules of catalyst center is 0.15～0.45 with the ratio of outside surface reactive metal mass content, 0.33R locating ratio with outside surface reactive metal mass content and be the ratio of 0.3～0.6,0.66R place and outside surface reactive metal mass content is 0.5～0.8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194827A (en) * | 2014-09-11 | 2014-12-10 | 山东大王金泰集团有限公司 | Hydrorefining treatment process of aromatic hydrocarbon oil |
| CN111748370A (en) * | 2019-03-28 | 2020-10-09 | 中国石油天然气股份有限公司 | Thermal modification method for heavy oil by aid of aid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105145A (en) * | 1986-07-28 | 1988-04-27 | 切夫伦公司 | Staged catalyst system for removal of calcium and sodium from hydrocarbon feeds |
| CN1393515A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil |
| CN1484684A (en) * | 2000-12-11 | 2004-03-24 | 法国石油公司 | Method for hydrotreatment of heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
| CN101928593A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Graded composition of heavy oil hydrogenation catalysts |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
| CN101927197A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient descending distribution of active metal and acidic assistant concentration and preparation method thereof |
-
2011
- 2011-08-26 CN CN201110249474.6A patent/CN102952581B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105145A (en) * | 1986-07-28 | 1988-04-27 | 切夫伦公司 | Staged catalyst system for removal of calcium and sodium from hydrocarbon feeds |
| CN1484684A (en) * | 2000-12-11 | 2004-03-24 | 法国石油公司 | Method for hydrotreatment of heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
| CN1393515A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Process for hydrogenating residual oil |
| CN101928593A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Graded composition of heavy oil hydrogenation catalysts |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
| CN101927197A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient descending distribution of active metal and acidic assistant concentration and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李永存: "重油加氢处理技术", 《抚顺石油学院学报》 * |
| 胡长禄等: "上流式渣油加氢保护剂的开发", 《石油炼制与化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194827A (en) * | 2014-09-11 | 2014-12-10 | 山东大王金泰集团有限公司 | Hydrorefining treatment process of aromatic hydrocarbon oil |
| CN104194827B (en) * | 2014-09-11 | 2016-05-11 | 山东大王金泰集团有限公司 | A kind of aromatic naphtha hydrofinishing treatment process |
| CN111748370A (en) * | 2019-03-28 | 2020-10-09 | 中国石油天然气股份有限公司 | Thermal modification method for heavy oil by aid of aid |
| CN111748370B (en) * | 2019-03-28 | 2022-08-05 | 中国石油天然气股份有限公司 | Thermal modification method for heavy oil by aid of aid |
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