CN103289736B - Improve the inferior heavy oil catalyst combination hydroprocessing technique of catalyst utilization to greatest extent - Google Patents
Improve the inferior heavy oil catalyst combination hydroprocessing technique of catalyst utilization to greatest extent Download PDFInfo
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Abstract
The invention provides a kind of the inferior heavy oil hydroprocessing technique and the catalyzer grading composition that improve catalyst utilization to greatest extent, containing two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, the present invention is by adopting simply and flexibly hydrotreatment flow process, finally reach and 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.The present invention is particularly suitable for processing high-sulfur, high metal content, high bitum residual oil, can the long-term operation of implement device.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for high metal, 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 adopting unique hydrotreatment flow process, and select effective hydrogenation catalyst rightly, finally reach and both improve catalyst hydrogenation removing impurities mass-energy power, assurance device has longer 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, 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, a pipeline is connected with before the outlet line check valve of upflowing deferrization decalcification reactor with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, material is made to be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, pipeline is equipped with check valve, be connected from bottom with upflowing demetalization reactor after the outlet line of two upflowing deferrization decalcification reactors is merged into a pipeline, be connected with fixed bed desulphurization reactor, fixed bed denitrification reactor successively again, the inlet line and outlet line of upflowing demetalization reactor are all equipped with 3-way valve, between two 3-way valves, have a pipeline to be connected, 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
-1the combination employing mode of hydrogen to oil volume ratio 300 ~ 2000 catalyzer is: upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, demetalization reactor bed filling Hydrodemetalation catalyst, desulphurization reactor bed filling Hydrobon catalyst, denitrification reactor bed filling hydrodenitrogenation catalyst, from granules of catalyst center to outside surface, active metal component distribution in " yolk " of hydrogenation deferrization decalcification catalyzer, the active metal component concentration gradient of Hydrodemetalation catalyst and Hydrobon catalyst reduces distribution, and the active metal component gradient of hydrodenitrogenation catalyst increases distribution.
First mink cell focus and/or residual oil raw material enter two upflowing deferrization decalcification reactors, and reactor is in-built doses hydrogen deferrization decalcification catalyzer, carries out deferrization decalcification reaction here; Its resultant of reaction has two operation scheme afterwards: one is directly enter upflowing demetalization reactor 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, carry out hydrodesulfurization reaction in the presence of a catalyst; Two is directly enter desulphurization reactor, carries out hydrodesulfurization reaction in the presence of a catalyst.Its desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor.
Deferrization decalcification plant running process steps is as follows:
(1) in initial reaction stage, two deferrization decalcification reactors use together, and heavy oil or residual oil raw material are introduced into one of them reactor (representing with A), then enter another reactor (representing with B) and carry out deferrization decalcification reaction.
(2) after reacting for some time, A reactor catalyst is active in the middle and later periods, at this moment can flow to by feed change, and the advanced B reactor of raw material enters A reactor again.
(3) in A reactor, deferrization decalcification catalyzer is in deactivation phases, closes A reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters B reactor.
(4) after A completes and changes agent, the advanced B reactor of material, then enter to change the reactor A of agent.
(5) in B reactor, deferrization decalcification catalyzer is in deactivation phases, closes B reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters A reactor.
(6), after B reactor completes and changes agent, repeating step (1)-step (5) is continued.
For demetalization reactor, in operational process, especially at the active deactivation phases of catalyst for demetalation, material autoreactor out directly enters desulphurization reactor.Simultaneously with regeneration and/or the catalyst for demetalation replacing reactor with live catalyst.After completing catalyzer replacement, material autoreactor out enters demetalization reactor, desulphurization reactor and denitrification reactor more successively.
Method the method provided by the present invention can process high metal content, high-sulfur, high nitrogen, high bitum residual oil, and effectively can 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 flows through beds from bottom to top, and the catalyzer in bed expands slightly.From up-flow reactor bottom feed after mink cell focus or residual oil raw material and hydrogen mixing, make whole beds produce slight expansion, thus slow down the rate of growth of the Pressure Drop of beds, the running period of extension fixture.Same ebullated bed, moving-bed are compared with suspension bed, and up-flow reactor has invests the features such as low, simple to operate.
The present invention also provides one can effectively play all kinds of catalyst action, improves heavy distillate and the residual oil hydrocatalyst grading composition of the active and stability of catalyst hydrogenation demetalization (HDM), hydrogenating desulfurization (HDS), hydrodenitrification (HDN), removal of ccr by hydrotreating.
The grading composition of the catalyzer that the present invention adopts adopts common type of feed, and hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst can be made up of one or more catalyzer; In catalyzer grading composition, cubage by weight, hydrogenation deferrization decalcification catalyzer accounts for 10 ~ 55%, and be preferably 10 ~ 30%, Hydrodemetalation catalyst accounts for 5 ~ 55%, is preferably 15 ~ 40%; Hydrobon catalyst accounts for 5 ~ 55%, is preferably 20 ~ 40%; Hydrodenitrogenation catalyst accounts for 5 ~ 55%, is preferably 10 ~ 50%.
Can load one or more catalyzer respectively in 4 classification reactors in the present invention, along logistics direction, best aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, best catalyzer 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 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 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%.
The preparation process that hydrogenation deferrization decalcification catalyzer is recommended is:
Adopt unsaturated dipping (dipping solution volume is preferably about 1/3 of saturated dipping volume) in conjunction with quick-drying method, prepare hydrogenation deferrization decalcification catalyzer.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, dipping solution volume is about about 1/3 of saturated dipping volume, adopt the method sprayed, solution sprays on carrier with atomizing state, then rapid drying 5-30 minute at 80 ~ 180 DEG C, then at 300 ~ 650 DEG C, preferably roasting 2 ~ 6 hours obtained catalyzer at 400 ~ 550 DEG C.The catalyzer obtained, requires the distribution in " yolk " of catalyst activity metal component distributed density.
The preparation process that Hydrodemetalation catalyst and Hydrobon 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, require that catalyst activity metal component distributed density autocatalysis agent granular center is Gradient distribution from high to low to outside surface, 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 granules of catalyst, metal component concentration is distribution in " yolk ", granules of catalyst outside surface is 0 ~ 0.05 with the ratio of center active metal mass content, be preferably 0.005 ~ 0.02, (granular center is point of beginning to 0.66R, R is granules of catalyst radius) place is 0.03 ~ 0.2 with the ratio of center active metal mass content, be preferably 0.05 ~ 0.1,0.33R (R is granules of catalyst radius) place is 0.5 ~ 0.95 with the ratio of center active metal mass content, is preferably 0.75 ~ 0.95.
In Hydrodemetalation catalyst and Hydrobon 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.
Heavy-oil hydrogenation treatment process of the present invention, 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, is 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.
Because in the present invention, deferrization decalcification reactor, demetalization reactor have selected up-flow reactor, flow from bottom to top in the logistics direction of up-flow reactor, and 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, when the technical process adopted can avoid deferrization decalcifying agent and demetalization inactivation, the situation that sweetening agent and denitrfying agent activity also have sizable potentiality effectively not play occurs.Be recommended in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and denitrification reactor simultaneously and select special catalyst, 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 in Fig. 2 comparative example 3, residual hydrocracking process flow diagram.
Fig. 3 in the present invention operable Hydrodemetalation catalyst and Hydrobon catalyst granular center to the active metal concentrations distribution plan of outside surface.
Fig. 4 in the present invention operable Hydrodemetalation catalyst and Hydrobon catalyst granular center distributes to the active metal concentrations of outside surface.
Fig. 5 in the present invention operable hydrodenitrogenation 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.
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 inferior heavy oil, residual oil.
Heavy oil or residual oil raw material are entered together the bottom of up-flow reactor R-1A and/or R-1B of hydrotreater, deferrization decalcification reaction is carried out with up-flow reactor catalyst exposure, its resultant of reaction has two operation scheme: one is without being separated the bottom directly entering up-flow reactor R-2, carry out hydrodemetallation (HDM) (Ni, V) reaction in the presence of a catalyst, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, carry out hydrodesulfurization reaction in the presence of a catalyst; Two is directly enter desulphurization reactor, 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-4.
Deferrization decalcification plant running process steps is as follows:
(1) in initial reaction stage, use together with R-1A with R-1B reactor, heavy oil or residual oil raw material are introduced into R-1A, then enter R-1B and carry out deferrization decalcification reaction.
(2) after reacting for some time, R-1A reactor catalyst is active in the middle and later periods, at this moment can flow to by feed change, and the advanced R-1B reactor of raw material enters R-1A reactor again.
(3) in R-1A reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1A reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1B reactor.
(4) after R-1A completes and changes agent, the advanced R-1B reactor of material, then enter to change the reactor R-1A of agent.
(5) in R-1B reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1B reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1A reactor.
(6) repeating step (1)-step (5) is continued.
For demetalization reactor R-2, in operational process, especially in catalyst for demetalation active latter stage, material out can directly enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regenerating and/or replace with live catalyst the catalyst for demetalation of reactor.After completing catalyzer replacement, material out enters demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 more successively from deferrization decalcification reactor.
The active ingredient of catalyzer can be passed through electron spectroscopy analysis (EDX) analysis and obtain.The Active components distribution of Hydrodemetalation catalyst provided by the invention and desulfurization catalyst as shown in Figure 3 and Figure 4.Wherein, from catalyst for demetalation and desulfurization catalyst granular center to outside surface, active metal component concentration can with Fig. 3 formal distribution, also can with Fig. 4 formal distribution.Can find from Fig. 4: 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.
Denitrification reactor denitrification catalyst granular center used to outside surface active metal concentrations distribution as shown in Figure 5 and Figure 6.Wherein, by the center of denitrification catalyst particle to outside surface, in denitrification 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 denitrogenation granules of catalyst center to outside surface, active metal component concentration in gradient increases distribution.
Embodiment 1 (described concentration % is quality %)
Embodiment 1 uses the hydrogenation technique shown in Fig. 1 to combine, and comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 20%, 25%, 20%, 35%.
The preparation process of catalyzer grading composition is as follows:
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 hollow tooth wheel shape Al
2o
3make carrier, adopt unsaturated spraying to prepare in conjunction with quick-drying method the catalyzer that active metal component is Mo.
Take 150g, water-intake rate is the Al of 1.10mL/g
2o
3carrier, sprays 50mL containing 4.3g ammonium molybdate (containing MoO
382%, Beijing chemical reagents corporation) dipping solution, within 5 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 150 DEG C dry 20 minutes, then roasting 3 hours in 500 DEG C of air, obtained catalyzer DFC-1#.Its physical data is as follows: MoO
3content is 2.29%, specific surface area 78m
2/ g, pore volume 0.83mL/g, bulk density 0.44g/mL, porosity is 51%, and catalyst particle size is 13mm.
Upflowing demetalization reactor loads 2 kinds of Hydrodemetalation catalysts from top to bottom successively, and numbering is respectively DM-1# and DM-2#, and adding proportion (weight) is 1: 1.Method for preparing catalyst is as follows:
To contain 2.0%Z rO
2trifolium 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 2.5%K
2the Al of O
2o
3carrier, sprays 82.5mL containing 3.2g 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 3.2g 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 3.1%, NiO mass content is 1.1%, specific surface area 98m
2/ g, pore volume 0.82mL/g, bulk density 0.49g/m, porosity is 47%, and particle diameter is 6mm.
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 the Al that 1.10mL/g contains 1.5%MgO
2o
3carrier, sprays 50mL containing 9.3g ammonium molybdate (containing MoO
382%) the aqueous solution, spray-stain process moderate at the uniform velocity instill 115mL deionized water 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 4.5%, specific surface area 118m
2/ g, pore volume 0.80mL/g, bulk density 0.52g/mL, porosity is 45%, and particle diameter is 3mm.
The catalyzer that fixed bed desulphurization reactor loads from top to bottom is successively numbered DS-1# and DS-2#, and adding proportion (weight) is 1: 1.
Take 150g, water-intake rate is the Al of 1.10mL/g
2o
3carrier, sprays 82.5mL containing 22.6g ammonium molybdate (containing MoO by saturated absorption amount of solution
382%) and the ammonia soln of 11.5g nickelous nitrate (containing NiO 25.2%), at the uniform velocity instill in spray-stain process 82.5mL concentration be 15% ammonia soln stir in the leaching solution, instillation limit, limit sprays.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 1.93%, specific surface area 129m
2/ g, pore volume 0.66m L/g, bulk density 0.59g/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 82.5mL containing 29.8g ammonium molybdate (containing MoO by saturated absorption amount of solution
382% quality) and the phosphoric acid solution of 27.0g nickelous nitrate (containing NiO 25.2%), at the uniform velocity instill in spray-stain process 82.5mL concentration be 15% ammonia soln stir in leaching solution, instillation limit, limit sprays.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 175m
2/ g, pore volume 0.63m L/g, bulk density 0.65g/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:
With Al
2o
3make carrier, water-intake rate is 1.10mL/g.Infusion method is adopted to prepare the catalyzer that active metal component is W, Ni.
Take 150g, water-intake rate is 1.10mL/g Al
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 ammonia soln of 18g nickelous nitrate (containing NiO25.2%) 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 25.6%, NiO content is 2.5%, and specific surface area is 193m
2/ g, pore volume is 0.46mL/g, and bulk density is 0.83g/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.
Be below plant running scheme:
Residual oil raw material is entered together the bottom of up-flow reactor R-1A and/or R-1B of hydrotreater, deferrization decalcification reaction is carried out with up-flow reactor catalyst exposure, its resultant of reaction has two operation scheme: one is without being separated the bottom directly entering up-flow reactor R-2, carry out hydrodemetallation (HDM) (Ni, V) reaction in the presence of a catalyst, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, carry out hydrodesulfurization reaction in the presence of a catalyst; Two is directly enter desulphurization reactor, 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-4.
Deferrization decalcification plant running process steps is as follows:
(1) in initial reaction stage, use together with R-1A with R-1B reactor, heavy oil or residual oil raw material are introduced into R-1A, then enter R-1B and carry out deferrization decalcification reaction.
(2) after reacting for some time, R-1A reactor catalyst is active in the middle and later periods, at this moment can flow to by feed change, and the advanced R-1B reactor of raw material enters R-1A reactor again.
(3) in R-1A reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1A reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1B reactor.
(4) after R-1A completes and changes agent, the advanced R-1B reactor of material, then enter to change the reactor R-1A of agent.
(5) in R-1B reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1B reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1A reactor.
(6) repeating step (1)-step (5) is continued.
For demetalization reactor R-2, in operational process, especially in catalyst for demetalation active latter stage, material out can directly enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regenerating and/or replace with live catalyst the catalyst for demetalation of reactor.After completing catalyzer replacement, material out enters demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 more successively from deferrization decalcification reactor.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.
Embodiment 2
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 25%, 25%, 20%, 30%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer, be numbered DFC-2#, preparation method is as follows:
Select Raschig ring Al
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 the ammonia soln of 3.10g nickelous nitrate (containing NiO25.2%, Beijing chemical reagents corporation), within 5 minutes, spray.To spray in equipment homogenizing after 10 minutes, at 130 DEG C dry 15 minutes, then roasting 3 hours in 500 DEG C of air, 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 11mm.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent from top to bottom successively, and numbering is respectively DM-1# and DM-2#, and adding proportion (weight) is 1: 1.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#, and adding proportion (weight) is 1: 3.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 10.0%TiO
2al
2o
3carrier, sprays 82.5mL containing 21.35g ammonium molybdate (containing MoO
382%) in spray-stain process, 82.5mL and the aqueous solution of 39.7g nickelous nitrate (containing NiO 25.2%), is at the uniform velocity instilled containing 21.35g ammonium molybdate (containing MoO
382%) the aqueous solution is in 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 DN-2#.The physical data of DN-2# is as follows: MoO
3content is 17.89%, NiO mass content is 3.6%, specific surface area 198m
2/ g, pore volume 0.42mL/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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.
Embodiment 3
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 15%, 20%, 25%, 40%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-1#, catalyzer is with embodiment 1.
Upflowing 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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.
Embodiment 4
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 15%, 15%, 20%, 50%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing 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#, and adding proportion (weight) is 1: 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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.
Embodiment 5
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 18%, 20%, 30%, 32%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization 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 adding proportion (weight) is 1: 2.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#, and adding proportion (weight) is 1: 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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 5.
Embodiment 6
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 15%, 20%, 35%, 30%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing 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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 5.
Embodiment 7
Hydrogenation technique combination in embodiment comprises 5 reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Adopt catalyst grade combo dress scheme, in reactor, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent respectively, additional proportion is respectively 15%, 30%, 30%, 25%.
Upflow fixed bed deferrization decalcification reactor charge a kind of hydrogenation deferrization 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 adding proportion (weight) is 1: 3.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#, and adding proportion (weight) is 1: 3.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 adding proportion (weight) is 1: 1.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.Plant running is with embodiment 1.Its reaction conditions of 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, comprising 2 fixed bed deferrization decalcification reactors, 1 fixed bed 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.Catalyst combination and grating ratio are 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.Plant running is with embodiment 1.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.And the operational cycle of comparative example is also starkly lower than embodiment 1.
Comparative example 2
Hydrogenation technique combination in comparative example 2 comprises 5 fixed-bed reactor, comprising 2 fixed bed deferrization decalcification reactors, 1 fixed bed 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.Catalyst combination and grating ratio are 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.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.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 2 is also starkly lower than embodiment 2.
Comparative example 3
Hydrogenation technique combination in comparative example 3 comprises 5 each and every one reactors, comprising 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.But technical process is as shown in Figure 2, run other condition, catalyst combination and grating ratio all identical with embodiment 3, its reaction conditions of its reaction conditions and reaction result as shown in table 4.As shown in Table 4, the deferrization decalcification rate of comparative example 3, demetallization per, desulfurization degree and denitrification percent are all lower than embodiment 3.Operational cycle is also starkly lower than embodiment 3.
Comparative example 4
Hydrogenation technique combination in comparative example 4 comprises 5 fixed-bed reactor, comprising 2 fixed bed deferrization decalcification reactors, 1 fixed bed demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Feed stream all passes through reactor.Catalyst combination and grating ratio are all with embodiment 4.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst are all with embodiment 4.
The raw materials used oily D of comparative example is residual oil raw material, and its character is as shown in table 3.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 4.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 also starkly lower than embodiment 4.
Comparative example 5
Comparative example 5 use in the same manner as in Example 3 hydrogenation technique combination and plant running scheme, comprise 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.Catalyst grade proportioning example is also with embodiment 3, but catalyzer model is different.
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.
Take 150g, water-intake rate is the Al of 1.10mL/g
2o
3carrier, sprays 165mL containing 4.3g ammonium molybdate (containing MoO
382%, Beijing chemical reagents corporation) ammonia soln, 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 DFC-3#.Its physical data is as follows: MoO
3content is 3.15%, specific surface area 80m
2/ g, pore volume 0.85mL/g, bulk density 0.43g/mL, porosity is 50%, and catalyst particle size is 13mm.
Upflowing 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%) the aqueous solution, has sprayed for 15 minutes.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 4.5%, specific surface area 120m
2/ g, pore volume 0.78mL/g, bulk density 0.51g/mL, porosity is 45%, and particle diameter is 3mm.
DS-3# selected by the catalyzer of fixed bed desulphurization reactor filling, and method for preparing catalyst is as follows:
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 22.0g nickelous nitrate (containing NiO 25.2%).To spray in equipment homogenizing after 15 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-3#.The physical data of DS-3# is as follows: MoO
3content is 13.6%, NiO mass content is 3.35%, specific surface area 179m
2/ g, pore volume 0.51mL/g, bulk density 0.69g/mL, porosity is 42%, and particle diameter is 1.3mm.
Fixed bed denitrification reactor loads a kind of hydrodenitrogenation catalyst, is numbered DN-3#.Method for preparing catalyst is as follows:
Take 150g, water-intake rate is that 1.10mL/g contains 10.0%TiO
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 200m
2/ g, pore volume 0.41mL/g, bulk density 0.79g/mL, porosity is 40%, and particle diameter is 1.1mm.
Raw materials used oily C is residual oil raw material, and its character is as shown in table 3.Plant running is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result as shown in table 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.Can find out, in catalyzer DFC-1, DFC-2 active metal in " yolk " distribution, granules of catalyst from interior to outward, in DM-1, DM-2, DS-1, DS-2, the downtrending in gradient of single or multiple active metal concentrations; In DN-1 and DN-2, single or multiple active metal concentrations increases trend in gradient; In DFC-3, DM-3, DS-3 and DN-3, 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 | DS-1 | DS-2 | DS-3 |
| W (outside surface)/W (center) | |||||||||
| Mo (outside surface)/Mo (center) | 0.007 | 0.01 | 0.89 | 0.86 | 0.25 | 0.91 | 0.28 | 0.33 | 1.06 |
| Co (outside surface)/Co (center) | 0.95 | ||||||||
| Ni (outside surface)/Ni (center) | 0.012 | 0.30 | 0.32 | 0.29 | 1.10 | ||||
| W (2/3R)/W (center) | |||||||||
| Mo (2/3R)/Mo (center) | 0.12 | 0.09 | 1.03 | 0.95 | 0.51 | 1.05 | 0.51 | 0.45 | 1.02 |
| Co (2/3R)/Co (center) | 1.01 | ||||||||
| Ni (2/3R)/Ni (center) | 0.15 | 0.53 | 0.39 | 0.52 | 0.99 | ||||
| W (1/3R)/W (center) | |||||||||
| Mo (1/3R)/Mo (center) | 0.90 | 0.92 | 0.96 | 0.96 | 0.82 | 0.93 | 0.85 | 0.83 | 0.96 |
| Co (1/3R)/Co (center) | 0.99 | ||||||||
| Ni (1/3R)/Ni (center) | 0.9 | 0.82 | 0.88 | 0.78 | 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 |
| Active metal concentrations distributes | |||
| W (center)/W (outside surface) | 0.26 | ||
| Mo (center)/Mo (outside surface) | 0.97 | 1.01 | |
| Co (center)/Co (outside surface) | |||
| Ni (center)/Ni (outside surface) | 0.28 | 0.32 | 0.99 |
| W (1/3R)/W (outside surface) | 0.45 | ||
| Mo (1/3R)/Mo (outside surface) | 0.98 | 1.03 | |
| Co (1/3R)/Co (outside surface) | |||
| Ni (1/3R)/Ni (outside surface) | 0.48 | 0.48 | 1.02 |
| W (2/3R)/W (outside surface) | 0.81 | ||
| Mo (2/3R)/Mo (outside surface) | 1.01 | 0.98 | |
| Co (2/3R)/Co (outside surface) | |||
| Ni (2/3R)/Ni (outside surface) | 0.86 | 0.85 | 1.05 |
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
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen-oil ratio (volume) | |||
| Upflowing deferrization decalcification reactor | 650 | 650 | 650 |
| Upflowing demetalization reactor | 650 | 650 | 650 |
| Fixed bed desulphurization reactor | 850 | 850 | 850 |
| Fixed bed denitrification reactor | 850 | 850 | 850 |
| Liquid hourly space velocity, h -1 | 0.22 | 0.22 | 0.22 |
| Temperature of reaction, DEG C | |||
| Upflowing deferrization decalcification reactor | 380 | 380 | 380 |
| Upflowing demetalization reactor | 385 | 385 | 385 |
| Fixed bed desulphurization reactor | 390 | 390 | 390 |
| Fixed bed denitrification reactor | 390 | 390 | 390 |
| Generate oil nature | |||
| S，％ | 0.37 | 0.35 | 0.40 |
| N，％ | 0.08 | 0.02 | 0.03 |
| Ni+V，μg/g | 12.42 | 10.16 | 6.13 |
| Fe，μg/g | 0.12 | 0.21 | 0.71 |
| Ca，μg/g | 0.19 | 0.30 | 1.16 |
| CCR，％ | 3.88 | 3.81 | 4.09 |
| The cycle of operation, the moon | 25 | 25 | 22 |
Claims (21)
1. an inferior heavy oil hydroprocessing technique, sequentially, containing two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, 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, a pipeline is connected with before the outlet line check valve of upflowing deferrization decalcification reactor with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, material is made to be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, pipeline is equipped with check valve, be connected from bottom with upflowing demetalization reactor after the outlet line of two upflowing deferrization decalcification reactors is merged into a pipeline, be connected with fixed bed desulphurization reactor, fixed bed denitrification reactor successively again, the inlet line and outlet line of upflowing demetalization reactor are all equipped with 3-way valve, between two 3-way valves, have a pipeline to be connected, 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, the combination employing mode of catalyzer is: upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, demetalization reactor bed filling Hydrodemetalation catalyst, desulphurization reactor bed filling Hydrobon catalyst, denitrification reactor bed filling hydrodenitrogenation catalyst, from granules of catalyst center to outside surface, active metal component distribution in " yolk " of hydrogenation deferrization decalcification catalyzer, the active metal component concentration gradient of Hydrodemetalation catalyst and Hydrobon catalyst reduces distribution, and the active metal component gradient of hydrodenitrogenation catalyst increases distribution.
2. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that in the combination of hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, calculate by total catalyst weight, hydrogenation deferrization decalcification catalyzer accounts for 10 ~ 55%, Hydrodemetalation catalyst accounts for 5 ~ 55%, Hydrobon catalyst accounts for 5 ~ 55%, and hydrodenitrogenation catalyst accounts for 5 ~ 55%.
3. inferior heavy oil hydroprocessing technique according to claim 2, it is characterized in that in the combination of hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, hydrogenation deferrization decalcification catalyzer accounts for 10 ~ 30%, and Hydrodemetalation catalyst accounts for 15 ~ 40%; Hydrobon catalyst accounts for 20 ~ 40%; Hydrodenitrogenation catalyst accounts for 10 ~ 50%.
4. 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.
5. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, catalyzer aperture reduces gradually, granularity reduces gradually, and porosity reduces gradually.
6. 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.
7. according to the arbitrary described inferior heavy oil hydroprocessing technique of claim 1,2,3,5, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, catalyzer take porous inorganic oxide as carrier, and group vib metal and/or group VIII metal oxide compound are active ingredient.
8. inferior heavy oil hydroprocessing technique according to claim 7, 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 ~ 3.0mL/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 the group VIII metal of 0.5 ~ 8.0%.
9. inferior heavy oil hydroprocessing technique according to claim 8, 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 0.3 ~ 1.3mL/g;
3) specific surface is 100 ~ 240m
2/ g;
4) catalyzer is in corresponding burning amount, containing the group vib metal of 3.0 ~ 16% and/or the group VIII metal of 1.0 ~ 5.5%.
10. inferior heavy oil hydroprocessing technique according to claim 8 or claim 9, is characterized in that group vib metal is Mo and/or W.
11. inferior heavy oil hydroprocessing techniques according to claim 8 or claim 9, is characterized in that group VIII metal is Co and/or Ni.
12. inferior heavy oil hydroprocessing techniques according to claim 7, is characterized in that the preparation process of Hydrodemetalation catalyst and Hydrobon catalyst 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.
13. inferior heavy oil hydroprocessing techniques according to claim 12, 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.
14. inferior heavy oil hydroprocessing techniques according to claim 7, 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.
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 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.
16. inferior heavy oil hydroprocessing techniques according to claim 1, it is characterized in that in hydrogenation deferrization decalcification granules of catalyst, metal component concentration is distribution in " yolk ", granules of catalyst outside surface is 0 ~ 0.05 with the ratio of center active metal mass content, take granular center as point of beginning, R is granules of catalyst radius, be 0.03 ~ 0.2,0.33R place is 0.5 ~ 0.95 with the ratio of center active metal mass content at 0.66R place with the ratio of center active metal mass content.
17. inferior heavy oil hydroprocessing techniques according to claim 16, it is characterized in that in hydrogenation deferrization decalcification granules of catalyst, granules of catalyst outside surface is 0.005 ~ 0.02 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 0.05 ~ 0.1,0.33R place is 0.75 ~ 0.95 with the ratio of center active metal mass content.
18. inferior heavy oil hydroprocessing techniques according to claim 1, it is characterized in that urging in Hydrodemetalation catalyst and Hydrobon 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, 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 1, is characterized in that, in hydrodenitrogenation catalyst, 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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| JP2019530570A (en) * | 2016-09-23 | 2019-10-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for providing a fixed catalyst bed comprising a doped structured catalyst compact |
| CN109722333B (en) * | 2017-10-27 | 2021-10-08 | 中国石油化工股份有限公司 | Method for improving running period of waste lubricating oil regenerating device |
| CN110684556B (en) * | 2018-07-06 | 2021-11-16 | 中国石油化工股份有限公司 | Hydrotreating method and system |
| CN111100673A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Process for hydroprocessing heavy hydrocarbon feedstocks using upflow reactors |
| CN111100671A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw material by using up-flow reactor |
| CN111978140B (en) * | 2019-05-21 | 2022-11-18 | 中国石油化工股份有限公司 | Method for preparing 1-butene and application thereof |
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