CN102952580B - Process for hydrotreating inferior heavy oil with high content of metal, sulfur and nitrogen - Google Patents
Process for hydrotreating inferior heavy oil with high content of metal, sulfur and nitrogen Download PDFInfo
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- CN102952580B CN102952580B CN201110248359.7A CN201110248359A CN102952580B CN 102952580 B CN102952580 B CN 102952580B CN 201110248359 A CN201110248359 A CN 201110248359A CN 102952580 B CN102952580 B CN 102952580B
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Abstract
The invention provides a process for hydrotreating inferior heavy oil with high content of metal, sulfur and nitrogen. Two serially connected upflow iron-removing decalcifying reactor, a fixed-bed metal-removing reactor, a fixed-bed desulphurization reactor and a fixed-bed denitrification reactor are provided. By the simple and flexible hydrotreating process, the capacity of catalysts in hydrogenation removal of impurities is improved and operational cycle of equipment is maximized. Proper selection on effective hydrogenation catalysts may allow for better effect.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for high metal, high-sulfur, the heavy distillate of high asphalt content and the hydrofining of residual oil and hydrotreatment.The inventive method has and not only has higher demetalization, desulfurization, denitrogenation and diasphaltene activity, and has the longer plant running cycle.
Background technology
At present, domestic and international refined products market will be the trend continuing to rise to the demand of light, middle matter oil product, 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, various countries generally improve the quality criteria requirements of the especially automobile-used petrol and diesel oil product of petroleum products.Under above-mentioned market trend, heavy oil lighting can be realized with the rational cost of less expensive, the oil Refining Technologies that obtained product can be made to meet constantly harsh petrol and diesel oil product specification again become one of technology of domestic and international oil Refining Technologies developer focus development.
Shortening is the most effective heavy oil feed preconditioning technique.By hydrogenation, significantly reduce metal, sulphur, nitrogen, the asphalt content in these raw materials, improve hydrogen-carbon ratio, and then provide excellent raw material for the device such as catalytic cracking and delayed coking.Hydrogenation technique main at present mainly contains ebullated bed, suspension bed, moving-bed and fixed-bed process, and wherein suspension bed and moving bed process are also very immature, and cost is higher.Ebullated bed investment is higher, and operation easier is larger.Fixed bed is because cost is low, simple to operate and security is little, technology maturation, and thus development is very fast.
But in fixed-bed catalytic hydrotreatment, if raw material viscosity is comparatively large, metallic impurity or bituminous matter higher, in hydrogenation process, metal and coke can deposit on a catalyst gradually, easily make rapid catalyst deactivation, and bed blocks, pressure raises, and device frequent operation is stopped work.
This kind of raw material of hydrotreatment must ensure the cyclical operation grown as far as possible, without the need to arrestment.Many investigators propose multiple solution.
CN1322097C discloses a kind of replaceable reactor and can the method for short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction of adopting.First in the first hydrodemetallation (HDM) section, then hydrotreatment in the second hydrodesulfurizationsection section, wherein has a protective belt at least before hydrodemetallation (HDM) section.Described hydroprocessing process comprises the steps: an a) step, wherein uses protective belt; B) step, this protective belt short circuit during this step, and the catalyzer regenerating and/or change contained by this section; C) step, connects again and has regenerated and/or the protective belt of more catalyst changeout during this step; D) step, wherein the reactor of at least one hydrodemetallation (HDM) section and/or hydrodesulfurizationsection section can short circuit, and regeneration and/or the catalyzer changed contained by 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 stratiform beds.With the heavy feed stock that the residual matter of the upflow fixed bed reactor hydrotreatment metal of the catalyzer of at least two different hydrogenation activities, sulphur and carbon containing is polluted.But the method cycle of operation is short, be generally no more than 1 year.
CN1144860 discloses a kind of method of residual hydrocracking.First reactor in heavy resid hydrogenation reaction system sets up one or more opening for feed, change original catalyzer grating simultaneously, when an anticatalyzer bed pressure drop is the 0.4-0.8 times of apparatus design maximum pressure drop, use next opening for feed successively instead, original opening for feed can enter the mixture of turning oil or turning oil and stock oil simultaneously.This technique effectively can prevent bed pressure drop and extend 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 resid hydrogenation reaction system, adopt one section of absorption filter agent bed or one section of absorption filter agent bed and one section of adsorption filtration beds to use simultaneously, not only can farthest remove the suspended particle carried in stock oil, but also the Iron sulfuret of the iron naphthenate generation in crude oil and the material of the easy green coke of major part can be removed, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times caused because of fouling in device running period.
Summary of the invention
The object of this invention is to provide a kind of inferior heavy oil or process for hydrogenating residual oil, by selecting effective hydrogenation catalyst rightly, finally reach and both improve catalyst hydrogenation removing impurities mass-energy power, assurance device has the longer cycle of operation again.
A kind of inferior heavy oil hydroprocessing technique, mink cell focus and/or residual oil raw material and hydrogen enter deferrization decalcification reactor successively, deferrization decalcification reactor, fixed bed demetalization reactor, fixed bed desulphurization reactor, fixed bed denitrification reactor processes, it is characterized in that on material house steward, be connected to two arms, two arms are equipped with check valve, be connected with a upflowing deferrization decalcification reactor respectively after valve, the outlet line of one of them upflowing deferrization decalcification reactor accesses the source line of another upflowing deferrization decalcification reactor, the outlet line of this upflowing deferrization decalcification reactor is connected to three-dimensional valve, in the other two ends of three-dimensional valve: one end is connected with fixed bed demetalization reactor inlet pipeline by pipeline, to connect successively after fixed bed demetalization reactor fixed bed desulphurization reactor and fixed bed denitrification reactor, the other end is by the source line of pipeline access fixed bed desulphurization reactor, the processing condition of each reactor are: hydrogen pressure 5.0MPa ~ 20.0MPa, temperature 300 DEG C ~ 450 DEG C, volume space velocity 0.2h during liquid
-1~ 3h
-1, hydrogen to oil volume ratio 300 ~ 2000.
Technical process of the present invention is changeable, strong adaptability, mink cell focus or residual oil raw material and hydrogen both can from bottom to top successively enter in the upflowing deferrization decalcification reactors of two series connection, also wherein rearmounted upflowing deferrization decalcification reactor can only be entered, also can be that part material is first through a upflowing deferrization decalcification reactor reaction, then enter another upflowing deferrization decalcification reactor reaction together with other raw material; Reactor is in-built doses hydrogen deferrization decalcification catalyzer, carries out deferrization decalcification reaction; Its resultant of reaction has two operation scheme afterwards: one is directly enter fixed bed demetalization reactor without separation, filling catalyst for demetalation in reactor, mainly remove Ni, the V in raw material, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor, carry out hydrodesulfurization reaction in the presence of a catalyst; Two is directly enter fixed bed desulphurization reactor, under desulfurization catalyst exists, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor.
In operational process, in the upflowing deferrization decalcification reactor of two series connection, during preposition upflowing deferrization decalcification reactor catalyst inactivation, the material inlet valve of this reactor is closed, mink cell focus, residual oil raw material directly enter rearmounted upflowing deferrization decalcification reactor and react, like this can the extension fixture cycle of operation, and improve the catalyst utilization of demetalization reactor, desulphurization reactor and denitrification reactor.
In operational process, for fixed bed demetalization reactor, especially at the active deactivation phases of catalyst for demetalation, material autoreactor out directly enters desulphurization reactor, like this can the extension fixture cycle of operation.
Upflowing deferrization decalcification reactor bed filling hydrogenation deferrization decalcification catalyzer, preferably from granules of catalyst center to outside surface, the active metal component concentration gradient of hydrogenation deferrization decalcification catalyzer reduces; Demetalization reactor bed filling Hydrodemetalation catalyst, preferably from granules of catalyst center to outside surface, the active metal component concentration gradient of Hydrodemetalation catalyst reduces; Desulphurization reactor bed filling Hydrobon catalyst, the active metal component concentration of best Hydrobon catalyst is evenly distributed; Denitrification reactor bed filling hydrodenitrogenation catalyst, preferably from granules of catalyst center to outside surface, the active metal component gradient of hydrodenitrogenation catalyst increases.
In the present invention, hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, preferably: catalyzer aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Can load one or more catalyzer respectively in 4 classification reactors in the present invention, along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, general with porous inorganic oxide if aluminum oxide is for carrier, group vib metal (as W or/and Mo) and/or group VIII metal (as Co or/and Ni) oxide compound are active ingredient, the physical property of catalyzer, composition preferably:
1) with Al
2o
3or containing 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 is in corresponding burning amount (as follows), containing 1.0 ~ 20.0%, is preferably the group vib metal of 3.0 ~ 16% (as MoO
3and/or WO
3), and/or 0.5 ~ 8.0%, be preferably the group VIII metal (as CoO and/or NiO) of 1.0 ~ 5.5%.
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 containing SiO
2, TiO
2, ZrO
2al
2o
3as carrier, VIB and/or VIII compound (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 sprayed, solution sprays on carrier with atomizing state, then at 80 ~ 150 DEG C dry 1 ~ 8 hour, then at 300 ~ 650 DEG C, preferably roasting 2 ~ 6 hours obtained catalyzer at 400 ~ 550 DEG C.The catalyzer obtained is preferably: catalyst activity metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from high to low, the Gradient distribution of above situation that can be an active metal also can be multiple active metal component distributed density be.
Catalyst activity metal component distributed density autocatalysis agent granular center can by preparing denseer dipping solution in Gradient distribution from high to low to outside surface, spray in process at carrier, the saturated spray-stain carrier of method progressively adding deionized water or ammoniacal liquor dilution dipping solution obtains; Or by preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain on carrier.
The preparation process that hydrodenitrogenation catalyst is recommended is:
With Al
2o
3or containing SiO
2, TiO
2, ZrO
2al
2o
3as carrier, by VIB and/or group VIII metal 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 sprayed, solution sprays on carrier with atomizing state, then at 80 ~ 150 DEG C dry 1 ~ 8 hour, at 300 ~ 650 DEG C, preferably roasting 2 ~ 6 hours obtained catalyzer at 400 ~ 550 DEG C.The catalyzer obtained, requires active metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from low to high, the Gradient distribution of above situation that can be an active metal also can be multiple active metal concentrations be.
Catalyst activity metal component distributed density autocatalysis agent granular center can by the rarer VIB of preparation and/or group VIII metal solution or deionized water in Gradient distribution from low to high to outside surface, spray in process, progressively add the saturated sprayed carrier of denseer dipping solution to obtain, or by preparing the dipping solution of different concns, spraying from low to high by dipping solution concentration and obtaining on carrier.
In hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst particle, metal component concentration distribution reduces distribution in gradient from granular center to outside surface, granules of catalyst outside surface is 0.05 ~ 0.70 with the ratio of center active metal mass content, be preferably 0.15 ~ 0.45, (granular center is point of beginning to 0.66R, R is granules of catalyst radius) place is 0.2 ~ 0.8 with the ratio of center active metal mass content, be preferably 0.35 ~ 0.6, 0.33R (R is granules of catalyst radius) place is 0.4 ~ 0.9 with the ratio of center active metal mass content, be preferably 0.5 ~ 0.8.
In hydrodenitrogenation catalyst particle, active metal component concentration increases gradually from granular center to surface.Granules of catalyst center is 0.05 ~ 0.70 with the ratio of outside surface active metal mass content, be preferably 0.15 ~ 0.45, (center is point of beginning to 0.33R, R is granules of catalyst radius) place is 0.2 ~ 0.8 with the ratio of outside surface active metal mass content, be preferably 0.3 ~ 0.6,0.66R (R is granules of catalyst radius) place is 0.4 ~ 0.9 with the ratio of outside surface active metal mass content, is preferably 0.5 ~ 0.8.
The carrier used in method for preparing catalyst of the present invention can be drip ball forming, spin granulation, extrusion molding, compression molding etc., is best with a ball forming and extrusion molding.Catalyst shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.Be best with spherical and bar shaped.
The inferior heavy oil hydroprocessing technique of high metal of the present invention, high-sulfur and high nitrogen, each reactor can adopt the hydroprocessing technique condition of any applicable this area, general processing condition are as follows: hydrogen pressure 5.0MPa ~ 20.0MPa, be preferably 8.0MPa ~ 18.0MPa, it is preferred that 10.0MPa ~ 16.0MPa; Temperature 300 DEG C ~ 450 DEG C, is preferably 360 DEG C ~ 440 DEG C, it is preferred that 360 DEG C ~ 430 DEG C; Volume space velocity 0.2h during liquid
-1~ 3h
-1, be preferably 0.2h
-1~ 2h
-1, it is preferred that 0.2h
-1~ 1h
-1; Hydrogen to oil volume ratio 300 ~ 2000, is preferably 400 ~ 1500, it is preferred that 500 ~ 1000.
Flow from bottom to top in the logistics direction of up-flow reactor of the present invention, in reactor, liquid phase is continuous, and the catalyzer in bed expands slightly.Same ebullated bed, moving-bed are compared with suspension bed, and up-flow reactor has invests the features such as low, simple to operate.From the bottom feed of upflowing deferrization decalcification reactor after the mixing of mink cell focus of the present invention, residual oil raw material and hydrogen, whole beds is made to produce slight expansion, thus slow down the rate of growth of the Pressure Drop of beds, in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and denitrification reactor, select special catalyst simultaneously, be particularly suitable for processing high-sulfur, high metal content, high bitum residual oil, the long-term operation of implement device.
The present invention, by adopting simply and flexibly hydrotreatment flow process, finally reaches and had both improved catalyst hydrogenation removing impurities mass-energy power, ensure again to improve plant running cycle this purpose to greatest extent, if select effective hydrogenation catalyst rightly, effect can be better.
Accompanying drawing explanation
Fig. 1 inferior heavy oil of the present invention, residual hydrocracking process flow diagram.
Inferior heavy oil, residual hydrocracking process flow diagram in Fig. 2 comparative example 3 and comparative example 4.
Fig. 3 in the present invention operable hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst granular center to the active metal concentrations distribution plan of outside surface.
Fig. 4 in the present invention operable hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst granular center distributes to the active metal concentrations of outside surface.
Fig. 5 in the present invention operable Hydrobon catalyst granular center distributes to the active metal concentrations of outside surface.
Fig. 6 in the present invention operable hydrodenitrogenation catalyst granular center distributes to the active metal concentrations of outside surface.
Fig. 7 in the present invention operable hydrodenitrogenation catalyst granular center distributes to the active metal concentrations of outside surface.
Embodiment
Below in conjunction with accompanying drawing, the method that the present invention improves is further described, but does not thereby limit the invention.
Fig. 1 is the hydroprocessing process schematic diagram of application inferior heavy oil of the present invention or residual oil.
Heavy oil or residual oil are successively entered upflowing deferrization decalcification reactor R-1 and R-2 of hydrotreater, deferrization decalcification reaction is carried out with hydrogenation deferrization decalcification catalyst exposure, its resultant of reaction has two operation scheme afterwards: one is directly enter demetalization reactor R-3 without separation, hydrodemetallation (HDM) (Ni, V) reaction is carried out under catalyst for demetalation exists, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-4, carry out hydrodesulfurization reaction in the presence of a catalyst; Two is directly enter fixed bed desulphurization reactor R-4, carries out hydrodesulfurization reaction in the presence of a catalyst.Its desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor R-5.
In operational process, when R-1 reactor catalyst inactivation, by this reactor feed valve closes, mink cell focus or residual oil raw material directly enter R-2 reactor and react.
For demetalization reactor R-3, in operational process, especially in catalyst for demetalation active latter stage, material out can directly enter desulphurization reactor R-4 from deferrization decalcification reactor.
The Active components distribution of catalyzer can pass through electron spectroscopy analysis (EDX) analysis and obtain.The Active components distribution of the catalyzer of upflowing deferrization decalcification reactor provided by the invention and demetalization reactor as shown in Figures 2 and 3.Wherein, from hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst granular center to outside surface, active metal component concentration can with Fig. 2 formal distribution, also can with Fig. 3 formal distribution.Can find from Fig. 3: from granules of catalyst center to outside surface, there is a platform in concentration distribution, two steps.Here it should be noted that, concentration distribution can exist with one or more stepped form.But total trend is: autocatalysis agent granular center is to outside surface, and active metal component concentration in gradient reduces distribution.
Desulphurization reactor Hydrobon catalyst granular center used to outside surface active metal component concentration distribution as shown in Figure 4.Wherein, from the surface of Hydrobon catalyst particle to center, active metal component concentration is evenly distributed form substantially.
Denitrification reactor hydrodenitrogenation catalyst granular center used to outside surface active metal concentrations distribution as shown in Figure 5 and Figure 6.Wherein, by the center of hydrodenitrogenation catalyst particle to outside surface, in hydrodenitrogenation catalyst particle, active metal component concentration can with Fig. 5 formal distribution, also can with Fig. 6 formal distribution; Can find from Fig. 6: from granules of catalyst center to outside surface, there are three platforms in concentration distribution, two steps.Here it should be noted that, concentration distribution can exist with one or more stepped form.But total trend is: from hydrodenitrogenation catalyst granular center to outside surface, active metal component concentration in gradient increases distribution.
Embodiment 1 (described concentration % is quality %)
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflowing deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcifying agent, be numbered DFC-1#, the preparation method of catalyzer is as follows:
The present embodiment is with cylindrical Al
2o
3make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is Mo, Ni.
Take 150g, water-intake rate is the Al of 1.10ml/g
2o
3carrier, sprays 50ml containing 8.6g ammonium molybdate (containing MoO
382%, Beijing chemical reagents corporation) and 3.10g nickelous nitrate (containing NiO 25.2%, Beijing chemical reagents corporation) dipping solution, at the uniform velocity to instill in spray-stain process 115ml concentration be 15% ammonia soln stir in dipping solution, instillation limit, limit sprays, and within 5 minutes, has sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer DFC-1#.Its physical data is as follows: MoO
3content is 4.1%, NiO mass content 0.47%, specific surface area 115m
2/ g, pore volume 0.85ml/g, bulk density 0.44g/ml, porosity is 50%, and catalyst particle size is 5.1mm.
Fixed bed 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, Ni.
Take 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2al
2o
3carrier, sprays 82.5ml containing 6.33g ammonium molybdate (containing MoO
382%) in spray-stain process, 82.5ml and the ammonia soln of 6.80g nickelous nitrate (containing NiO 25.2%), is at the uniform velocity instilled containing 6.33g ammonium molybdate (containing MoO
382%) ammonia soln is in above-mentioned solution and stir, and instillation limit, limit sprays, and within 10 minutes, has sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DM-1#.The physical data of DM-1# is as follows: MoO
3content is 6.32%, NiO mass content is 1.1%, specific surface area 119m
2/ g, pore volume 0.76ml/g, bulk density 0.54g/m, porosity is 45%, and particle diameter is 1.5mm.
To contain 1.5%TiO
2al
2o
3make carrier, adopt the saturated method sprayed to prepare catalyzer DM-2# that active metal component is Mo, Co.
Take 150g, water-intake rate is that 1.10ml/g contains 1.5%TiO
2al
2o
3carrier, sprays 50ml containing 18.6g ammonium molybdate (containing MoO
382%) and 17.5g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (containing CoO 25.2%, Beijing chemical reagents corporation) ammonia soln, spray-stain process moderate at the uniform velocity instill 115ml concentration be 15% ammonia soln in leaching solution in and stir, instillation limit, limit sprays, and within 15 minutes, has sprayed.To spray in equipment homogenizing after 10 minutes, at 120 DEG C dry 5 hours, then roasting 4 hours in 500 DEG C of air, obtained catalyzer.Be numbered DM-2#.The physical data of DM-2# is as follows: MoO
3content is 8.92%, CoO mass content is 2.52%, specific surface area 142m
2/ g, pore volume 0.73ml/g, bulk density 0.55g/ml, porosity is 43%, and particle diameter is 1.5mm.
The catalyzer that fixed bed desulphurization reactor loads from top to bottom is successively numbered DS-1# and DS-2#.
Take 150g, water-intake rate is the Al of 1.10ml/g
2o
3carrier, sprays 165ml containing 22.6g ammonium molybdate (containing MoO by saturated absorption amount of solution
382%) and the ammonia soln of 17.10g nickelous nitrate (containing NiO 25.2%).To spray in equipment homogenizing after 5 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DS-1#.The physical data of DS-1# is as follows: MoO
3content is 10.78%, NiO mass content is 2.53%, specific surface area 159m
2/ g, pore volume 0.66ml/g, bulk density 0.64g/ml, porosity is 42%, and particle diameter is 1.3mm.
Take 150g, water-intake rate is the Al of 1.10ml/g
2o
3carrier, sprays 165ml containing 29.8g ammonium molybdate (containing MoO by saturated absorption amount of solution
382% quality) and the ammonia soln of 27.0g nickelous nitrate (containing NiO 25.2%).To spray in equipment homogenizing after 5 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DS-2#.
The physical data of DS-2# is as follows: MoO
3content is 13.5%, NiO mass content is 3.72%, specific surface area 182m
2/ g, pore volume 0.60ml/g, bulk density 0.68g/ml, porosity is 41%, and particle diameter is 1.3mm.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst DN-1#, and method for preparing catalyst is as follows:
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 150g, water-intake rate is that 1.10ml/g is to contain 2.0%ZrO
2al
2o
3carrier, sprays the ammonia soln that 100ml concentration is 5%, at the uniform velocity instills 65ml containing 63g ammonium metawolframate (containing WO in spray-stain process
388%) and the aqueous solution of 33.7g nickelous nitrate (containing NiO 25.2%) stir in above-mentioned solution, instillation limit, limit sprays, within 5 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DN-1#.Wherein, WO
3content is 25.7%, NiO content is 4.7%, and specific surface area is 185m
2/ g, pore volume is 0.55ml/g, and bulk density is 0.75g/ml, and porosity is 40%, and particle diameter is 1.1mm.
The raw materials used oily A of embodiment 1 is vacuum residuum, and its character is as shown in table 3.Stock oil A and hydrogen are mixed into hydrogenation unit and react, its reaction conditions is as shown in table 4, in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Reaction result is as shown in table 4.
Embodiment 2
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor, as shown in Figure 1.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer, be numbered DFC-2#, preparation method is as follows:
Select the Al of hollow cam face
2o
3make carrier, take 150g, water-intake rate is the Al of 1.10ml/g
2o
3carrier, sprays 50ml containing 8.6g ammonium molybdate (containing MoO
382%, Beijing chemical reagents corporation) and 3.10g nickelous nitrate (containing NiO 25.2%, Beijing chemical reagents corporation) ammonia soln, at the uniform velocity to instill in spray-stain process 115ml concentration be 15% ammonia soln stir in above-mentioned solution, instillation limit, limit sprays, and within 5 minutes, has sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.The physical data of DFC-2# is as follows: MoO
3content is 4.09%, NiO content is 0.48%, and specific surface area is 112m
2/ g, pore volume is 0.82ml/g, and bulk density is 0.43g/ml, and porosity is 50%, and catalyst particle size is 5.1mm.
Fixed bed demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent from top to bottom successively, and numbering is respectively DM-1# and DM-2#.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#.Desulfurization catalyst preparation method is with embodiment 1.
Fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalysts from top to bottom successively, numbering DN-1# and DN-2#.Wherein DN-1# method for preparing catalyst is with embodiment 1.
DN-2# method for preparing catalyst is as follows:
Take 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2al
2o
3carrier, sprays 82.5ml containing 21.35g ammonium molybdate (containing MoO
382%) and 39.7g nickelous nitrate (containing NiO 25.2%) and phosphorus aqueous acid, in spray-stain process, 82.5ml is at the uniform velocity instilled containing 21.35g ammonium molybdate (containing MoO
382%) and phosphorus aqueous acid stir in solution, instillation limit, limit sprays, within 10 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DN-2#.The physical data of DN-2# is as follows: MoO
3content is 17.89%, NiO mass content is 5.12%, specific surface area 229m
2/ g, pore volume 0.53ml/g, bulk density 0.78g/ml, porosity is 40%, and particle diameter is 1.1mm.
The raw materials used oily B of embodiment 2 is residual oil raw material, and its character is as shown in table 3.Stock oil B and hydrogen are mixed into hydrogenation unit and react, and its reaction conditions is as shown in table 4.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Reaction result is as shown in table 4.
Embodiment 3
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-1#, catalyzer is with embodiment 1.
Fixed bed demetalization reactor charge a kind of hydrodemetallation (HDM) agent DM-2#, catalyzer is with embodiment 1.
Desulphurization reactor loads a kind of hydrogen desulfurization agent, and numbering is respectively DS-2#.Catalyzer is with embodiment 1.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst DN-2#, and catalyzer is with embodiment 2.
Evaluating raw materials used oily C is residual oil raw material, and its character is as shown in table 3.Stock oil C and hydrogen are mixed into hydrogenation unit and react, and its reaction conditions is as shown in table 4.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Reaction result is as shown in table 4.
Embodiment 4
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Fixed bed demetalization reactor charge a kind of hydrodemetallation (HDM) agent 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.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst DN-1#, and catalyzer is with embodiment 1.
Evaluating raw materials used oily D is residual oil raw material, and its character is as shown in table 3.Stock oil D and hydrogen are mixed into hydrogenation unit and react, and its reaction conditions is as shown in table 4.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Reaction result is as shown in table 4.
Embodiment 5
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Fixed bed demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and 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.
Fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-1# from top to bottom successively, and catalyzer is with embodiment 1.
Evaluating raw materials used oily E is vacuum residuum, and its character is as shown in table 3.Stock oil E and hydrogen are mixed into hydrogenation unit and react, and in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Embodiment 6
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Fixed bed demetalization reactor charge a kind of hydrodemetallation (HDM) agent DM-1#, preparation method is with embodiment 1.
Desulphurization reactor loads a kind of hydrogen desulfurization agent, and numbering is respectively DS-1#.Catalyzer is with embodiment 1.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst DN-1#, and catalyzer is with embodiment 1.
Evaluating raw materials used oily F is vacuum residuum, and its character is as shown in table 3.Stock oil F and hydrogen are mixed into hydrogenation unit and react, and in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions of its reaction conditions and reaction result as shown in table 5.
Embodiment 7
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Fixed bed demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and preparation method is with embodiment 1.
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.
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.
Evaluating raw materials used oily G is vacuum residuum, and its character is as shown in table 3.Stock oil G and hydrogen are mixed into hydrogenation unit and react.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Embodiment 8
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 fixed-bed reactor, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer, be numbered DFC-3#, the preparation method of catalyzer is as follows:
With hollow cam face Al
2o
3make carrier, adopt the saturated method that sprays to prepare the catalyzer that active metal component is Mo, Ni.
Take 150g, water-intake rate is the Al of 1.10ml/g
2o
3carrier, sprays 165ml containing 8.6g ammonium molybdate (containing MoO
382%, Beijing chemical reagents corporation) and the ammonia soln of 3.10g nickelous nitrate (containing NiO 25.2%, Beijing chemical reagents corporation), within 5 minutes, spray.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer DFC-3#.Its physical data is as follows: MoO
3content is 4.1%, NiO mass content 0.47%, specific surface area 116m
2/ g, pore volume 0.85ml/g, bulk density 0.44g/ml, porosity is 50%, and catalyst particle size is 5.1mm.
Fixed bed demetalization reactor charge a kind of Hydrodemetalation catalyst, is numbered DM-3#.Method for preparing catalyst is as follows:
Take 150g, water-intake rate is that 1.10ml/g contains 1.5%m TiO
2al
2o
3carrier, sprays 165ml containing 18.6g ammonium molybdate (containing MoO
382%) and the ammonia soln of 17.5g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (containing CoO 25.2m%, Beijing chemical reagents corporation), within 15 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 120 DEG C dry 5 hours, then roasting 4 hours in 500 DEG C of air, obtained catalyzer.Be numbered DM-3#.The physical data of DM-3# is as follows: MoO
3content is 8.92%, CoO mass content is 2.52%, specific surface area 141m
2/ g, pore volume 0.72ml/g, bulk density 0.55g/ml, porosity is 45%, and particle diameter is 1.5mm.
DS-2# selected by the catalyzer of fixed bed desulphurization reactor filling, and preparation method is same with embodiment 1.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst, is numbered DN-3#.
DN-3# method for preparing catalyst is as follows:
Take 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2al
2o
3carrier, sprays 165ml containing 42.7g ammonium molybdate (containing MoO
382%) and 39.7g nickelous nitrate (containing NiO 25.2%) and phosphorus aqueous acid, within 10 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DN-3#.The physical data of DN-3# is as follows: MoO
3content is 17.85%, NiO mass content is 5.2%, specific surface area 229m
2/ g, pore volume 0.51ml/g, bulk density 0.78g/ml, porosity is 40%, and particle diameter is 1.1mm.
The raw materials used oily C of comparative example is residual oil raw material, and its character is as shown in table 3.Stock oil C and hydrogen are mixed into hydrogenation unit and react, and its reaction conditions is as shown in table 4.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Embodiment 9
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 fixed-bed reactor, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
DFC-3# selected by hydrogenation deferrization decalcification catalyzer; Hydrodemetalation catalyst selects DM-4#; Hydrobon catalyst selects DS-1# and DS-2#; And hydrodenitrogenation catalyst selects DN-1#.
To contain 2.0%ZrO
2two kinds of trifolium Al
2o
3make carrier, adopt the saturated method that sprays to prepare the catalyzer DM-4# that active metal component is Mo, Ni.
Take 150g, water-intake rate is that 1.10ml/g contains 2.0%ZrO
2al
2o
3carrier, sprays 165ml containing 12.66g ammonium molybdate (containing MoO
382%) and the ammonia soln of 6.80g nickelous nitrate (containing NiO 25.2%), within 10 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DM-4#.The physical data of DM-4# is as follows: MoO
3content is 6.33%, NiO mass content is 1.09%, specific surface area 116m
2/ g, pore volume 0.75ml/g, bulk density 0.534g/ml, porosity is 45%, and particle diameter is 1.5mm.
The raw materials used oily E of comparative example is vacuum residuum, and its character is as shown in table 3.Stock oil E and hydrogen are mixed into residual hydrogenation equipment and react.In operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Embodiment 10
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2.
Fixed bed demetalization reactor charge a kind of hydrodemetallation (HDM) agent DM-3#, preparation method is with embodiment 8.
Desulphurization reactor loads a kind of hydrogen desulfurization agent, and numbering is respectively DS-1#.Catalyzer is with embodiment 1.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst DN-1#, and catalyzer is with embodiment 1.
Evaluating raw materials used oily F is vacuum residuum, and its character is as shown in table 3.Stock oil F and hydrogen are mixed into hydrogenation unit and react, and in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, residual oil raw material directly enters rearmounted second reactor and reacts.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Embodiment 11
Use the hydrogenation technique combination shown in Fig. 1, comprise 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Fixed bed demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and 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.
Fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-3# and DN-4# from top to bottom successively.
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 Mo, Ni.
Take 150g, water-intake rate is that 1.10ml/g is to contain 2.0%ZrO
2al
2o
3carrier, sprays 165ml containing 63g ammonium metawolframate (containing WO
388%) and the ammonia soln of 33.7g nickelous nitrate (containing NiO 25.2%), within 5 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, at taking out latter 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyzer.Be numbered DN-4#.Wherein, WO
3content is 26.0%, NiO content is 4.72%, and specific surface area is 188m
2/ g, pore volume is 0.55ml/g, and bulk density is 0.745g/ml, and porosity is 40%, and particle diameter is 1.1mm.
Evaluating raw materials used oily G is residual oil raw material, and its character is as shown in table 3.Stock oil G and hydrogen are mixed into hydrogenation unit and react, and in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, mink cell focus or residual oil raw material directly enter rearmounted second reactor and react.In operational process, when fixed bed demetalization reactor catalyst inactivation, feed switched flows to, and residual oil material out directly enters desulphurization reactor from deferrization decalcification reactor.Its reaction conditions and reaction result as shown in table 5.
Comparative example 1
Hydrogenation technique combination in comparative example 1 comprises 5 fixed-bed reactor, and comprising 2 fixed bed deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor, feed stream all passes through reactor.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load hydrogen desulfurization agent and hydrodenitrification agent respectively.Catalyzer is with embodiment 1.
The raw materials used oily A of comparative example 1 is vacuum residuum, and its character is as shown in table 1.Stock oil A and hydrogen are mixed into hydrogenation unit and react, its reaction conditions and reaction product character as shown in table 4, as can be seen from Table 4, when operational condition is identical, the deferrization decalcification rate of embodiment 1, demetallization per, desulfurization degree and denitrification percent are all higher than comparative example 1, and the operational cycle of comparative example is lower than embodiment 1.
Comparative example 2
Hydrogenation technique combination in comparative example 2 comprises 5 fixed-bed reactor, and comprising 2 fixed bed deferrization decalcification reactors, 1 demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor, feed stream all passes through reactor.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load hydrogen desulfurization agent and hydrodenitrification agent respectively.Catalyzer is with embodiment 2.
The raw materials used oily B of comparative example 2 is vacuum residuum, and its character is as shown in table 3.Stock oil B and hydrogen are mixed into hydrogenation unit and react, its reaction conditions is as shown in table 4, in operational process, when first deferrization decalcification reactor catalyst inactivation, by this reactor feed valve closes, mink cell focus or residual oil raw material directly enter rearmounted second reactor and react.Reaction result is as shown in table 4, and as can be seen from Table 4, when operational condition is identical, the deferrization decalcification rate of embodiment 2, demetallization per, desulfurization degree and denitrification percent are all higher than comparative example., and the operational cycle of comparative example is lower than embodiment 2.
Comparative example 3
Hydrogenation technique combination in comparative example 3 comprises 5 reactors, comprising 2 parallel upflowing deferrization decalcification reactors, 1 fixed bed demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.But technical process as shown in Figure 2, raw material, processing condition, catalyzer are all identical with embodiment 3, and meeting in the qualified standard of product, its operational cycle is lower than embodiment 3.
Comparative example 4
Hydrogenation technique combination in comparative example 4 comprises 5 reactors, comprising 2 parallel upflowing deferrization decalcification reactors, 1 fixed bed demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.But technical process as shown in Figure 2, raw material, processing condition, catalyzer are all identical with embodiment 4.
Reaction result is as shown in table 4, and as can be seen from Table 4 when operational condition is identical, the deferrization decalcification rate of embodiment 4, demetallization per, desulfurization degree and denitrification percent are all higher than comparative example 4.And the operational cycle of comparative example is lower than embodiment 4.
Adopt EDX characterization method to characterize catalyzer DFC-1, DFC-2, DM-1, DM-2, DS-1, DS-2, DN-1, DN-2, describe active ingredient distribution situation on the catalyst particles, result is see 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 outward, the downtrending in gradient of single or multiple active metal concentrations; Catalyzer DN-1 and DN-2 particle are from interior to outward, and single or multiple active metal concentrations increases trend in gradient; Catalyzer DS-1, DS-2, DFC-3, DN-3 and DN-4 particle is from interior to outward, and active metal substep is comparatively even.
Active metal concentrations 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) | 0.23 | 0.20 | 0.92 | 0.83 | 0.31 | 1.02 | 0.96 | 1.02 | 1.06 |
| Co (outside surface)/Co (center) | 0.27 | 0.90 | |||||||
| Ni (outside surface)/Ni (center) | 0.21 | 0.21 | 0.95 | 0.32 | 1.02 | 1.10 | 1.10 | ||
| W (2/3R)/W (center) | |||||||||
| Mo (2/3R)/Mo (center) | 0.45 | 0.35 | 1.01 | 0.95 | 0.42 | 1.02 | 0.92 | 1.02 | 1.02 |
| Co (2/3R)/Co (center) | 0.38 | 1.05 | |||||||
| Ni (2/3R)/Ni (center) | 0.42 | 0.40 | 1.05 | 0.51 | 1.01 | 0.99 | 0.99 | ||
| W (1/3R)/W (center) | |||||||||
| Mo (1/3R)/Mo (center) | 0.70 | 0.80 | 0.98 | 0.98 | 0.76 | 0.96 | 1.06 | 0.96 | 0.96 |
| Co (1/3R)/Co (center) | 0.66 | 1.02 | |||||||
| Ni (1/3R)/Ni (center) | 0.65 | 0.82 | 1.01 | 0.79 | 1.01 | 1.02 | 1.01 |
Note: take granular center as starting point, R is granules of catalyst radius.
Active metal concentrations distribution on table 2 granules of catalyst
| Numbering | DN-1 | DN-2 | DN-3 | DN-4 |
| Active metal concentrations distributes | ||||
| W (center)/W (outside surface) | 0.27 | 0.95 | ||
| Mo (center)/Mo (outside surface) | 0.90 | 1.06 | ||
| Co (center)/Co (outside surface) | ||||
| Ni (center)/Ni (outside surface) | 0.25 | 0.29 | 0.95 | 1.01 |
| W (1/3R)/W (outside surface) | 0.51 | 0.98 | ||
| Mo (1/3R)/Mo (outside surface) | 0.95 | 1.02 | ||
| Co (1/3R)/Co (outside surface) | ||||
| Ni (1/3R)/Ni (outside surface) | 0.47 | 0.53 | 1.02 | 0.99 |
| W (2/3R)/W (outside surface) | 0.78 | 1.02 | ||
| Mo (2/3R)/Mo (outside surface) | 1.02 | 0.96 | ||
| Co (2/3R)/Co (outside surface) | ||||
| Ni (2/3R)/Ni (outside surface) | 0.75 | 0.83 | 1.02 | 0.98 |
Note: take granular center as starting point, R is granules of catalyst radius.
Table 3 test raw material oil main character
| Material name | A | B | C | D | E | F | G |
| Density (20 DEG C), 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 (21)
1. an inferior heavy oil hydroprocessing technique, mink cell focus is or/and residual oil raw material and hydrogen enter deferrization decalcification reactor successively, fixed bed demetalization reactor, fixed bed desulphurization reactor, fixed bed denitrification reactor processes, it is characterized in that on material house steward, be connected to two arms, two arms are equipped with check valve, be connected with a upflowing deferrization decalcification reactor respectively after valve, the outlet line of one of them upflowing deferrization decalcification reactor accesses the source line of another upflowing deferrization decalcification reactor, the outlet line of this upflowing deferrization decalcification reactor is connected to three-dimensional valve, in the other two ends of three-dimensional valve: one end is connected with fixed bed demetalization reactor inlet pipeline by pipeline, to connect successively after fixed bed demetalization reactor fixed bed desulphurization reactor and fixed bed denitrification reactor, the other end is by the source line of pipeline access fixed bed desulphurization reactor, the processing condition of each reactor are: hydrogen pressure 5.0MPa ~ 20.0MPa, temperature 300 DEG C ~ 450 DEG C, volume space velocity 0.2h-1 ~ 3h-1 during liquid, hydrogen to oil volume ratio 300 ~ 2000, upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, from granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces.
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, temperature 360 DEG C ~ 440 DEG C, volume space velocity 0.2h during liquid
-1~ 2h
-1, hydrogen to oil volume ratio 400 ~ 1500.
3. according to the inferior heavy oil hydroprocessing technique shown in claim 1, it is characterized in that demetalization reactor charge Hydrodemetalation catalyst, from granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces.
4., according to the inferior heavy oil hydroprocessing technique shown in claim 1, it is characterized in that desulphurization reactor bed filling Hydrobon catalyst, the active metal component concentration of Hydrobon catalyst is evenly distributed.
5. according to the inferior heavy oil hydroprocessing technique shown in claim 1, it is characterized in that denitrification reactor bed filling hydrodenitrogenation catalyst, from granules of catalyst center to outside surface, the active metal component gradient of hydrodenitrogenation catalyst increases.
6. inferior heavy oil hydroprocessing technique according to claim 1, is characterized in that upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, and from granules of catalyst center to outside surface, the active metal component concentration gradient of catalyzer reduces; Demetalization reactor charge Hydrodemetalation catalyst, from 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 granules of catalyst center to outside surface, the active metal component gradient of hydrodenitrogenation catalyst increases.
7. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, demetalization reactor charge Hydrodemetalation catalyst, desulphurization reactor bed filling Hydrobon catalyst, denitrification reactor bed filling hydrodenitrogenation catalyst, from hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst to hydrodenitrogenation catalyst, catalyzer aperture reduces gradually, granularity reduces gradually, and porosity reduces gradually.
8. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that two upflowing deferrization decalcification reactors in parallel, a fixed bed demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, loads one or more catalyzer in above-mentioned 4 classification reactors respectively, along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
9. inferior heavy oil hydroprocessing technique according to claim 6, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, catalyzer is with porous inorganic oxide if aluminum oxide is for carrier, and group VIB metal and/or VIII family metal oxide are active ingredient.
10. inferior heavy oil hydroprocessing technique according to claim 9, is characterized in that the physical property of catalyzer, consists of:
1) with Al
2o
3or containing 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 is in corresponding burning amount, containing the group VIB metal of 1.0 ~ 20.0%, and/or VIII race's metal of 0.5 ~ 8.O%.
11. inferior heavy oil hydroprocessing techniques according to claim 10, is characterized in that the physical property of catalyzer, consist of:
1) with Al
2o
3or containing 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, the group VIB metal containing 3.0 ~ 16% and/or 1.0 ~ 5.5% VIII race's metal.
12. inferior heavy oil hydroprocessing techniques according to claim 9 or 10 or 11, is characterized in that group VIB metal is Mo and/or W.
13. inferior heavy oil hydroprocessing techniques according to claim 9 or 10 or 11, is characterized in that VIII race's metal is Co and/or Ni.
14. inferior heavy oil hydroprocessing techniques according to claim 1 or 3 or 6, it is characterized in that catalyst activity metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from high to low time, the preparation process of catalyzer is:
With Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
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 sprayed, solution sprays on carrier with atomizing state, then at 80 ~ 150 DEG C dry 1 ~ 8 hour, then at 300 ~ 650 DEG C, roasting 2 ~ 6 hours obtained catalyzer; The catalyzer obtained, requires catalyst activity metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from high to low, the Gradient distribution of above situation that to be an active metal or multiple active metal component distributed density be.
15. inferior heavy oil hydroprocessing techniques according to claim 14, it is characterized in that catalyst activity metal component distributed density autocatalysis agent granular center is by the denseer dipping solution of preparation to outside surface in Gradient distribution from high to low, spray in process at carrier, the saturated spray-stain carrier of method progressively adding deionized water or ammoniacal liquor dilution dipping solution obtains; Or by preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain on carrier.
16. inferior heavy oil hydroprocessing techniques according to claim 5 or 6, is characterized in that the preparation process of hydrodenitrogenation catalyst is:
With Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier, by VIB and/or group VIII metal compound, dipping solution is mixed and made into deionized water or ammoniacal liquor, adopt the saturated method sprayed, solution sprays on carrier with atomizing state, then at 80 ~ 150 DEG C dry 1 ~ 8 hour, roasting 2 ~ 6 hours obtained catalyzer at 300 ~ 650 DEG C; The catalyzer obtained, requires active metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from low to high, the Gradient distribution of above situation that to be an active metal or multiple active metal concentrations be.
17. inferior heavy oil hydroprocessing techniques according to claim 16, it is characterized in that catalyst activity metal component distributed density autocatalysis agent granular center to outside surface in Gradient distribution from low to high, by the rarer VIB of preparation and/or group VIII metal solution or deionized water, spray in process, progressively add the saturated sprayed carrier of denseer dipping solution to obtain, or by preparing the dipping solution of different concns, spraying from low to high by dipping solution concentration and obtaining on carrier.
18. inferior heavy oil hydroprocessing techniques according to claim 1 or 3 or 7, it is characterized in that in granules of catalyst, metal component concentration distribution reduces distribution in gradient from granular center to outside surface, granules of catalyst outside surface is 0.05 ~ 0.70 with the ratio of center active metal mass content, granular center is point of beginning, when R is granules of catalyst radius, 0.66R place and the ratio of center active metal mass content are 0.2 ~ 0.8,0.33R place is 0.4 ~ 0.9 with the ratio of center active metal mass content.
19. inferior heavy oil hydroprocessing techniques according to claim 18, it is characterized in that in hydrogenation deferrization decalcification catalyzer and Hydrodemetalation catalyst particle, granules of catalyst outside surface is 0.15 ~ 0.45 with the ratio of center active metal mass content, 0.66R place and the ratio of center active metal mass content are 0.35 ~ 0.6,0.33R place is 0.5 ~ 0.8 with the ratio of center active metal mass content.
20. inferior heavy oil hydroprocessing techniques according to claim 5 or 6, is characterized in that in hydrodenitrogenation catalyst particle, active metal component concentration increases gradually from granular center to surface; Granules of catalyst center is 0.05 ~ 0.70 with the ratio of outside surface active metal mass content, center is point of beginning, when R is granules of catalyst radius, 0.33R place and the ratio of outside surface active metal mass content are 0.2 ~ 0.8,0.66R place is 0.4 ~ 0.9 with the ratio of outside surface active metal mass content.
21. inferior heavy oil hydroprocessing techniques according to claim 20, it is characterized in that in hydrodenitrogenation catalyst particle, granules of catalyst center is 0.15 ~ 0.45 with the ratio of outside surface active metal mass content, 0.33R place and the ratio of outside surface active metal mass content are 0.3 ~ 0.6,0.66R place is 0.5 ~ 0.8 with the ratio of outside surface active metal mass content.
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| 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 |
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