CN103289736A - Inferior heavy oil catalyst combined hydrotreating process for furthest improving catalyst utilization rate - Google Patents
Inferior heavy oil catalyst combined hydrotreating process for furthest improving catalyst utilization rate Download PDFInfo
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- CN103289736A CN103289736A CN2012100520933A CN201210052093A CN103289736A CN 103289736 A CN103289736 A CN 103289736A CN 2012100520933 A CN2012100520933 A CN 2012100520933A CN 201210052093 A CN201210052093 A CN 201210052093A CN 103289736 A CN103289736 A CN 103289736A
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- 239000001257 hydrogen Substances 0.000 claims description 11
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- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
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- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 66
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- 238000005507 spraying Methods 0.000 description 15
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- 229940010552 ammonium molybdate Drugs 0.000 description 13
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Abstract
The invention provides an inferior heavy oil hydrotreating process and catalyst grading combination for improving the catalyst utilization rate to the maximum extent, which comprises two upflow type deferrization decalcification reactors, an upflow type demetalization reactor, a fixed bed desulfurization reactor and a fixed bed denitrification reactor. The present invention is especially suitable for treating residual oil with high sulfur content, high metal content and high asphaltene content, and can realize long-period operation of the apparatus.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for hydrofining and the hydrotreatment of heavy distillate and the residual oil of high metal, high asphalt content.The inventive method has and not only has higher demetalization, desulfurization, denitrogenation and diasphaltene activity, and has the long device cycle of operation.
Background technology
At present, oil product market will be the trend that continues rising to the demand of light, middle matter oil product both at home and abroad, and is then on a declining curve to the demand of fuel wet goods heavy oil product.In addition, because the pressure of environment protection increases day by day, the quality standard requirement of the especially automobile-used petrol and diesel oil product of petroleum products has generally improved in various countries.Under above-mentioned market trend, can realize that heavy oil lighting, the oil Refining Technologies that can make resulting product satisfy constantly harsh petrol and diesel oil product specification have again become one of technology of domestic and international oil Refining Technologies developer's focus development with the rational cost of less expensive.
Shortening is the most effective heavy oil feed preconditioning technique.By hydrogenation, significantly reduce metal, sulphur, nitrogen, asphalt content in these raw materials, improve hydrogen-carbon ratio, and then provide good raw material for devices such as catalytic cracking and delayed cokings.Main hydrogenation technique mainly contains ebullated bed, suspension bed, moving-bed and fixed-bed process at present, and wherein suspension bed and moving bed process are also very immature, and cost is higher.The ebullated bed investment is higher, and operation easier is bigger.Fixed bed is low, simple to operate and security is little because of cost, technology maturation, thereby development is very fast.
But in the fixed-bed catalytic hydrotreatment, if the raw material viscosity is big, metallic impurity or bituminous matter are higher, in hydrogenation process, metal and coke can be deposited on the catalyzer gradually, make the catalyzer rapid deactivation easily, and bed stops up, pressure raises, and makes device operation frequent shutdowns.
This class raw material of hydrotreatment must guarantee the cyclical operation grown as far as possible to need not arrestment.Many investigators have proposed multiple solution.
But CN1322097C discloses a kind of method that adopts replaceable reactor and short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction.In the first hydrodemetallation (HDM) section, hydrotreatment in second hydrodesulfurizationsection section then wherein has a protective belt at least before the hydrodemetallation (HDM) section earlier.Described hydroprocessing process comprises the steps: a) step, wherein uses the protective belt; B) step, this protective belt short circuit during this step, and regeneration and/or change the contained catalyzer of this section; C) step connects during this step again and has regenerated and/or the protective belt of catalyst changeout more; D) step, wherein the reactor of at least one hydrodemetallation (HDM) section and/or hydrodesulfurizationsection section can short circuit, and regeneration and/or change the contained catalyzer of this section.But such method needs higher initial outlay.
CN1349554 discloses a kind of method of up-flow reactor system hydrotreating heavy feedstocks of belt shape beds.The heavy feed stock that pollutes with the residual matter of upflow fixed bed reactor hydrotreatment metal, sulphur and the carbon containing of the catalyzer of at least two different hydrogenation activities.But this method cycle of operation is short, generally is no more than 1 year.
CN1144860 discloses a kind of method of residual hydrocracking.First reactor in heavy residual hydrogenation reactive system is set up one or more opening for feeds, change original catalyzer grating simultaneously, when an anticatalyzer bed pressure drop designs 0.4-0.8 times of maximum pressure drop for device, use next opening for feed successively instead, original opening for feed can advance the mixture of turning oil or turning oil and stock oil simultaneously.This technology can prevent bed pressure drop effectively and prolong the work-ing life of residual oil hydrocatalyst, and can increase the processing power of device.
CN00110714.3 discloses a kind of residual oil treatment process.By before heavy residual hydrogenation reactive system, adopt one section absorption filter agent bed or one section absorption filter agent bed and one section adsorption filtration beds to use simultaneously, not only can farthest remove the suspended particle that carries in the stock oil, but also can remove Iron sulfuret and the most of easily material of green coke that the iron naphthenate in the crude oil generates, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times that because of fouling cause of device in running period.
Summary of the invention
The purpose of this invention is to provide a kind of inferior heavy oil or process for hydrogenating residual oil, by adopting unique hydrotreatment flow process, and select effective hydrogenation catalyst rightly, and finally reaching and both improved catalyst hydrogenation and take off the impurity ability, assurance device has long cycle of operation this purpose again.
A kind of inferior heavy oil hydroprocessing technique, inferior heavy oil is or/and residual oil raw material and hydrogen enter deferrization decalcification reactor successively, fixed bed demetalization reactor, the fixed bed desulphurization reactor, the fixed bed denitrification reactor is handled, it is characterized in that being connected to two arms the material house steward, be equipped with check valve on two arms, link to each other with a upflowing deferrization decalcification reactor respectively behind the valve, before the outlet line check valve of upflowing deferrization decalcification reactor with behind another upflowing deferrization decalcification Reactor inlet pipeline check valve, be connected with a pipeline, make material be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, be equipped with check valve on the pipeline; The outlet line of two upflowing deferrization decalcification reactors is connected with upflowing demetalization reactor from the bottom after being merged into a pipeline, link to each other with fixed bed desulphurization reactor, fixed bed denitrification reactor successively again, on the inlet line of upflowing demetalization reactor and outlet line, all be equipped with 3-way valve, have a pipeline to be connected between two 3-way valves; The processing condition of each reactor are: hydrogen pressure 5.0MPa～20.0MPa, 300 ℃～450 ℃ of temperature, volume space velocity 0.2h during liquid
-1～3h
-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; To outside surface, hydrogenation deferrization decalcification activity of such catalysts metal component is " yolk " and distributes from the granules of catalyst center; 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.
Mink cell focus and/or residual oil raw material at first enter two upflowing deferrization decalcification reactors, and filling hydrogenation deferrization decalcification catalyzer carries out deferrization decalcification reaction here in the reactor; Its resultant of reaction has two operation scheme afterwards: the one, directly enter upflowing demetalization reactor without separating, in the presence of catalyst for demetalation, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter the fixed bed desulphurization reactor, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter desulphurization reactor, in the presence of catalyzer, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters the fixed bed denitrification reactor without separation.
Deferrization decalcification device operational process step 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), enter another reactor (representing with B) again and carry out deferrization decalcification reaction.
(2) after reaction for some time, A reactor catalyst activity is near the middle and later periods, at this moment can change feedstream to, the advanced B reactor of raw material advances the A reactor again.
(3) deferrization decalcification catalyzer is in the inactivation stage in the A reactor, closes A reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the B reactor.
(4) after A finished and changes agent, the advanced B reactor of material advanced the reactor A of having changed agent again.
(5) deferrization decalcification catalyzer is in the inactivation stage in the B reactor, closes B reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the A reactor.
(6) after the B reactor is finished and changed agent, continue repeating step (1)-step (5).
For the demetalization reactor, in operational process, especially in the active inactivation stage of catalyst for demetalation, the material autoreactor desulphurization reactor that comes out directly to enter.Use the catalyst for demetalation of regenerating and/or replacing reactor with live catalyst simultaneously.After finishing catalyzer and replacing, material autoreactor come out to enter successively again demetalization reactor, desulphurization reactor and denitrification reactor.
This method of method provided by the present invention can be handled high metal content, high-sulfur, high nitrogen, high bitum residual oil, and can effectively slow down the lift velocity of reactor pressure decrease, thus the long-term operation of implement device.
The logistics direction of up-flow reactor of the present invention is to flow through beds from bottom to top, slightly microdilatancy of the catalyzer in the bed.Mink cell focus or residual oil raw material and hydrogen mix the back from the up-flow reactor bottom feed, make whole beds produce slight expansion, thereby slow down the rate of growth that the pressure of beds falls, the running period of extension fixture.Same ebullated bed, moving-bed and suspension bed are compared, and up-flow reactor has the characteristics such as low, simple to operate of investing.
The present invention also provides a kind of can effectively bring into play all kinds of catalyst actions, improves catalyst hydrogenation demetalization (HDM), hydrogenating desulfurization (HDS), hydrodenitrification (HDN), removal of ccr by hydrotreating activity and stable heavy distillate and residual oil hydrocatalyst grading composition.
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 the catalyzer grading composition, cubage by weight, hydrogenation deferrization decalcification catalyzer accounts for 10～55%, is preferably 10～30%, and 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 among the present invention, along the logistics direction, preferably the 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, preferably the catalyzer aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, be carrier with porous inorganic oxide such as aluminum oxide generally, group vib metal (as W or/and Mo) and/or VIII family metal (as Co or/and Ni) oxide compound is active ingredient, the rerum natura of catalyzer, forms preferably:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.1～3.0mL/g, is preferably 0.3～1.3mL/g;
3) specific surface is 20～400m
2/ g is preferably 100～240m
2/ g;
4) catalyzer contains 1.0～20.0% in corresponding burning amount (as follows), is preferably 3.0～16% group vib metal (as MoO
3And/or WO
3), and/or 0.5～8.0%, be preferably 1.0～5.5% VIII family metal (as CoO and/or NiO).
The preparation process that hydrogenation deferrization decalcification catalyzer is recommended is:
Adopt unsaturated dipping (dipping solution volume be preferably saturated dipping volume about 1/3) in conjunction with quick-drying method, preparation hydrogenation deferrization decalcification catalyzer.With Al
2O
3Or contain 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, the dipping solution volume is about about 1/3 of saturated dipping volume, the method that employing sprays, solution sprays on carrier with atomizing state, at 80～180 ℃ of following rapid drying 5-30 minutes, then at 300～650 ℃, be preferably in 400～550 ℃ of following roastings and made catalyzer in 2～6 hours then.Resulting catalyzer requires catalyst activity metal component distributed density to be " yolk " and distributes.
The preparation process that Hydrodemetalation catalyst and Hydrobon catalyst are recommended is:
With Al
2O
3Or contain 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 that sprays, solution sprays on carrier with atomizing state, following dry 1～8 hour at 80～150 ℃ then, at 300～650 ℃, be preferably in 400～550 ℃ of following roastings and made catalyzer in 2～6 hours then.Resulting catalyzer, requiring catalyst activity metal component distributed density autocatalysis agent particle center to be from high to low Gradient distribution to outside surface, can be that a reactive metal also can be the Gradient distribution that a plurality of active metal component distributed densities are above situation.
The Gradient distribution that catalyst activity metal component distributed density autocatalysis agent particle center is from high to low to outside surface can be by the denseer dipping solution of preparation, spray in the process at carrier, the saturated spray-stain carrier of method that progressively adds deionized water or ammoniacal liquor dilution dipping solution obtains; Or by the preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain at carrier.
The preparation process that hydrodenitrogenation catalyst is recommended is:
With Al
2O
3Or contain SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with VIB and/or VIII family metallic compound, preferred molybdenum and/or tungsten and/or nickel and/or cobalt compound and deionized water or ammoniacal liquor are mixed and made into dipping solution, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, descended dry 1～8 hour at 80～150 ℃ then, at 300～650 ℃, be preferably in 400～550 ℃ of following roastings and made catalyzer in 2～6 hours.Resulting catalyzer requires active metal component distributed density autocatalysis agent particle center to be from low to high Gradient distribution to outside surface, can be that a reactive metal also can be the Gradient distribution that a plurality of reactive metal concentration are above situation.
The Gradient distribution that catalyst activity metal component distributed density autocatalysis agent particle center is from low to high to outside surface can be by preparation rarer VIB and/or VIII family metallic solution or deionized water, spray in the process, progressively adding the saturated sprayed carrier of denseer dipping solution obtains, or the dipping solution by the preparation different concns, spray at carrier from low to high by dipping solution concentration and to obtain.
In the hydrogenation deferrization decalcification granules of catalyst, metal component concentration is " yolk " and distributes, the granules of catalyst outside surface is 0～0.05 with the ratio of center reactive metal mass content, be preferably 0.005～0.02,0.66R (the particle center is point of beginning, R is the granules of catalyst radius) ratio located with center reactive metal mass content is 0.03～0.2, be preferably 0.05～0.1,0.33R the ratio that (R is the granules of catalyst radius) located with center reactive metal mass content is 0.5～0.95, is preferably 0.75～0.95.
In Hydrodemetalation catalyst and the Hydrobon catalyst particle, the metal component concentration distribution reduces distribution in gradient from the particle center to outside surface, the granules of catalyst outside surface is 0.05～0.70 with the ratio of center reactive metal mass content, be preferably 0.15～0.45,0.66R (the particle center is point of beginning, R is the granules of catalyst radius) ratio located with center reactive metal mass content is 0.2～0.8, be preferably 0.35～0.6,0.33R the ratio that (R is the granules of catalyst radius) located with center reactive metal mass content is 0.4～0.9, is preferably 0.5～0.8.
In the hydrodenitrogenation catalyst particle, active metal component concentration increases gradually from the particle center to face.The granules of catalyst center is 0.05～0.70 with the ratio of outside surface reactive metal mass content, be preferably 0.15～0.45,0.33R (center is point of beginning, R is the granules of catalyst radius) ratio located with outside surface reactive metal mass content is 0.2～0.8, be preferably 0.3～0.6,0.66R the ratio that (R is the granules of catalyst radius) located with outside surface reactive metal mass content is 0.4～0.9, is preferably 0.5～0.8.
The carrier that uses in the method for preparing catalyst of the present invention can be to drip ball forming, spin granulation, extrusion molding, compression molding etc., is best to drip 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 suitable this area, general processing condition are as follows: hydrogen pressure 5.0MPa～20.0MPa, be preferably 8.0MPa～18.0MPa, and that best is 10.0MPa～16.0MPa; 300 ℃～450 ℃ of temperature are preferably 360 ℃～440 ℃, and best is 360 ℃～430 ℃; Volume space velocity 0.2h during liquid
-1～3h
-1, be preferably 0.2h
-1～2h
-1, that best is 0.2h
-1～1h
-1Hydrogen to oil volume ratio 300～2000 is preferably 400～1500, and best is 500～1000.
Because deferrization decalcification reactor, demetalization reactor have been selected up-flow reactor among the present invention, the logistics direction of up-flow reactor is to flow from bottom to top, and liquid phase is continuous in the reactor, slightly microdilatancy of the catalyzer in the bed.Same ebullated bed, moving-bed and suspension bed are compared, and up-flow reactor has the characteristics such as low, simple to operate of investing.Mink cell focus of the present invention, residual oil raw material and hydrogen mix the back from the bottom feed of upflowing deferrization decalcification reactor, make whole beds produce slight expansion, thereby the rate of growth that the pressure that slows down beds falls, when the technical process of adopting can be avoided deferrization decalcifying agent and demetalization inactivation, the situation that sweetening agent and denitrfying agent activity also have sizable potentiality effectively not bring into play took place.Be recommended in simultaneously in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and the denitrification reactor and select special catalyst, be particularly suitable for handling high-sulfur, high metal content, high bitum residual oil, the long-term operation of implement device.
The present invention had both improved catalyst hydrogenation and had taken off the impurity ability by adopting simply and flexibly hydrotreatment flow process, finally reaching, and guaranteed again to improve device cycle of operation this purpose to greatest extent, if select effective hydrogenation catalyst rightly, effect can be better.
Description of drawings
Fig. 1 inferior heavy oil of the present invention, residual hydrocracking process flow diagram.
Inferior heavy oil in Fig. 2 Comparative Examples 3, residual hydrocracking process flow diagram.
Fig. 3 in the present invention operable Hydrodemetalation catalyst and Hydrobon catalyst particle center to the reactive metal concentration profile of outside surface.
Fig. 4 in the present invention operable Hydrodemetalation catalyst and Hydrobon catalyst particle center to the reactive metal concentration distribution of outside surface.
Fig. 5 in the present invention operable hydrodenitrogenation catalyst particle center to the reactive metal concentration distribution of outside surface.
Fig. 6 in the present invention operable hydrodenitrogenation catalyst particle center to the reactive metal concentration distribution of outside surface.
Embodiment
Below in conjunction with accompanying drawing the method that the present invention improves is given further instruction, but therefore do not limit the present invention.
Fig. 1 is the hydroprocessing process synoptic diagram of inferior heavy oil, residual oil.
Heavy oil or residual oil raw material are entered the up-flow reactor R-1A of hydrotreater and/or the bottom of R-1B together, contact with the up-flow reactor catalyzer and to carry out deferrization decalcification reaction, its resultant of reaction has two operation scheme: the one, without separating the bottom that directly enters up-flow reactor R-2, in the presence of catalyzer, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter desulphurization reactor, in the presence of catalyzer, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters fixed bed denitrification reactor R-4 without separation.
Deferrization decalcification device operational process step is as follows:
(1) in initial reaction stage, R-1A and R-1B reactor use together, and heavy oil or residual oil raw material are introduced into R-1A, enter R-1B again and carry out deferrization decalcification reaction.
(2) after reaction for some time, R-1A reactor catalyst activity is near the middle and later periods, at this moment can change feedstream to, the advanced R-1B reactor of raw material advances the R-1A reactor again.
(3) deferrization decalcification catalyzer is in the inactivation stage in the R-1A reactor, closes R-1A reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the R-1B reactor.
(4) after R-1A finished and changes agent, the advanced R-1B reactor of material advanced the reactor R-1A that has changed agent again.
(5) deferrization decalcification catalyzer is in the inactivation stage in the R-1B reactor, closes R-1B reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the R-1A reactor.
(6) continue repeating step (1)-step (5).
For demetalization reactor R-2, in operational process, especially in catalyst for demetalation active latter stage, material comes out directly to enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regeneration and/or replace the catalyst for demetalation of reactor with live catalyst.After finishing the catalyzer replacement, material comes out to enter successively demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 from deferrization decalcification reactor again.
The activity of such catalysts component can obtain by electron spectroscopy analysis (EDX) analysis.The active ingredient of Hydrodemetalation catalyst provided by the invention and desulfurization catalyst distributes as shown in Figure 3 and Figure 4.Wherein, to outside surface, active metal component concentration can distribute with Fig. 3 form, also can distribute with Fig. 4 form from catalyst for demetalation and desulfurization catalyst particle center.Can find from Fig. 4: to outside surface, a platform has appearred in concentration distribution from the granules of catalyst center, two steps.Here need to prove that concentration distribution can exist with one or more stepped form.But total trend is: autocatalysis agent particle center is to outside surface, and active metal component concentration in gradient reduces distribution.
The used denitrification catalyst particle center of denitrification reactor to the reactive metal concentration distribution of outside surface as shown in Figure 5 and Figure 6.Wherein, to outside surface, in the denitrification catalyst particle, active metal component concentration can distribute with Fig. 5 form, also can distribute with Fig. 6 form by the center of denitrification catalyst particle; Can find from Fig. 6: to outside surface, three platforms have appearred in concentration distribution from the granules of catalyst center, two steps.Here need to prove that concentration distribution can exist with one or more stepped form.But total trend is: to outside surface, active metal component concentration in gradient increases distribution from denitrogenation granules of catalyst center.
Embodiment 1 (described concentration % is quality %)
The preparation process of catalyzer grading composition is as follows:
1 kind of hydrogenation deferrization of upflowing deferrization decalcification reactor charge decalcifying agent is numbered DFC-1#, and the Preparation of catalysts method is as follows:
Present embodiment is with hollow wheel gear shape Al
2O
3Make carrier, adopt unsaturated spraying in conjunction with quick-drying method to prepare the catalyzer that active metal component is Mo.
Take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 50mL and contains the 4.3g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) dipping solution sprayed in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 150 ℃ dry 20 minutes down, roasting 3 hours in 500 ℃ of air again makes 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%, 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 of spraying to prepare the catalyzer DM-1# that active metal component is Mo, Ni.
Take by weighing 150g, water-intake rate is that 1.10mL/g contains 2.5%K
2The Al of O
2O
3Carrier sprays 82.5mL and contains the 3.2g ammonium molybdate and (contain MoO
382%) and the ammonia soln of 6.80g nickelous nitrate (containing NiO 25.2%), at the uniform velocity splashing into 82.5mL in the spray-stain process contains the 3.2g ammonium molybdate and (contains MoO
382%) ammonia soln also stirs in above-mentioned solution, sprays while splashing into, and sprays in 10 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DM-1#.The physical data of DM-1# is as follows: MoO
3Content is that 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%, particle diameter is 6mm.
To contain 1.5%TiO
2Al
2O
3Make carrier, adopt the saturated method that sprays to prepare the catalyzer DM-2# that active metal component is Mo, Co.
Take by weighing 150g, water-intake rate is the Al that 1.10mL/g contains 1.5%MgO
2O
3Carrier sprays 50mL and contains the 9.3g ammonium molybdate and (contain MoO
382%) the aqueous solution at the uniform velocity splashes into the 115mL deionized water in soaking solution and stirs in spray-stain process moderate, sprays while splashing into, and sprays in 15 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 5 hours down, roasting 4 hours in 500 ℃ of air again makes 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%, particle diameter is 3mm.
The catalyzer that the fixed bed desulphurization reactor loads from top to bottom successively is numbered DS-1# and DS-2#, and adding proportion (weight) is 1: 1.
Take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 82.5mL by the saturated absorption amount of solution and contains the 22.6g ammonium molybdate and (contain MoO
382%) and the ammonia soln of 11.5g nickelous nitrate (containing NiO 25.2%), in the spray-stain process, at the uniform velocity splashes into 82.5mL concentration and be 15% ammonia soln in soaking solution and stir, spray while splashing into.Homogenizing is after 5 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DS-1#.The physical data of DS-1# is as follows: MoO
3Content is that 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%, particle diameter is 1.3mm.
Take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 82.5mL by the saturated absorption amount of solution and contains the 29.8g ammonium molybdate and (contain MoO
382% quality) and the phosphoric acid solution of 27.0g nickelous nitrate (containing NiO 25.2%), in the spray-stain process, at the uniform velocity splash into 82.5mL concentration and be 15% ammonia soln in soaking solution and stir, spray while splashing into.Homogenizing is after 5 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DS-2#.The physical data of DS-2# is as follows: MoO
3Content is that 13.5%, NiO mass content is 3.72%, specific surface area 175m
2/ g, pore volume 0.63m L/g, bulk density 0.65g/mL, porosity is 41%, particle diameter is 1.3mm.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, method for preparing catalyst is as follows:
The hydrodenitrogenation catalyst preparation method is as follows:
With Al
2O
3Make carrier, water-intake rate is 1.10mL/g.Adopt infusion method to prepare the catalyzer that active metal component is W, Ni.
Take by weighing 150g, water-intake rate is 1.10mL/g Al
2O
3Carrier sprays 100mL concentration and is 5% ammonia soln, at the uniform velocity splashes into 65mL and contain the 63g ammonium metawolframate and (contain WO in the spray-stain process
388%) and the ammonia soln of 18g nickelous nitrate (containing NiO 25.2%) in above-mentioned solution and stir, spray while splashing into, sprayed in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DN-1#.Wherein, WO
3Content is that 25.6%, NiO content is 2.5%, and specific surface area is 193m
2/ g, pore volume are 0.46mL/g, and bulk density is 0.83g/mL, and porosity is 40%, and particle diameter is 1.1mm.
Below be the device operating scheme:
Residual oil raw material is entered the up-flow reactor R-1A of hydrotreater and/or the bottom of R-1B together, contact with the up-flow reactor catalyzer and to carry out deferrization decalcification reaction, its resultant of reaction has two operation scheme: the one, without separating the bottom that directly enters up-flow reactor R-2, in the presence of catalyzer, carry out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, in the presence of catalyzer, carry out hydrodesulfurization reaction; The 2nd, directly enter desulphurization reactor, in the presence of catalyzer, carry out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction directly enters fixed bed denitrification reactor R-4 without separation.
Deferrization decalcification device operational process step is as follows:
(1) in initial reaction stage, R-1A and R-1B reactor use together, and heavy oil or residual oil raw material are introduced into R-1A, enter R-1B again and carry out deferrization decalcification reaction.
(2) after reaction for some time, R-1A reactor catalyst activity is near the middle and later periods, at this moment can change feedstream to, the advanced R-1B reactor of raw material advances the R-1A reactor again.
(3) deferrization decalcification catalyzer is in the inactivation stage in the R-1A reactor, closes R-1A reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the R-1B reactor.
(4) after R-1A finished and changes agent, the advanced R-1B reactor of material advanced the reactor R-1A that has changed agent again.
(5) deferrization decalcification catalyzer is in the inactivation stage in the R-1B reactor, closes R-1B reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.This moment, material only advanced the R-1A reactor.
(6) continue repeating step (1)-step (5).
For demetalization reactor R-2, in operational process, especially in catalyst for demetalation active latter stage, material comes out directly to enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regeneration and/or replace the catalyst for demetalation of reactor with live catalyst.After finishing the catalyzer replacement, material comes out to enter successively demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 from deferrization decalcification reactor again.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 25%, 25%, 20%, 30%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer is numbered DFC-2#, and the preparation method is as follows:
Select Raschig ring Al
2O
3Make carrier, take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 50mL and contains the 8.6g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) and the ammonia soln of 3.10g nickelous nitrate (containing NiO 25.2%, Beijing chemical reagents corporation), sprayed in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 130 ℃ dry 15 minutes down, roasting 3 hours in 500 ℃ of air again, roasting 3 hours in 500 ℃ of air again makes catalyzer.The physical data of DFC-2# is as follows: MoO
3Content is that 4.09%, NiO content is 0.48%, and specific surface area is 112m
2/ g, pore volume are 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.The Hydrodemetalation catalyst preparation method is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogenating desulfurization agent from top to bottom successively, and numbering is respectively DS-1# and DS-2#, and adding proportion (weight) is 1: 3.The desulfurization catalyst preparation method is with embodiment 1.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalysts from top to bottom successively, numbering DN-1# and DN-2#.Wherein the DN-1# method for preparing catalyst is with embodiment 1.
The DN-2# method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10mL/g contains 10.0%TiO
2Al
2O
3Carrier sprays 82.5mL and contains the 21.35g ammonium molybdate and (contain MoO
382%) and the aqueous solution of 39.7g nickelous nitrate (containing NiO 25.2%), at the uniform velocity splashing into 82.5mL in the spray-stain process contains the 21.35g ammonium molybdate and (contains MoO
382%) the aqueous solution also stirs in solution, sprays while splashing into, and sprays in 10 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DN-2#.The physical data of DN-2# is as follows: MoO
3Content is that 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%, particle diameter is 1.1mm.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 15%, 20%, 25%, 40%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-1#, catalyzer is with embodiment 1.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-2#, catalyzer is with embodiment 1.
1 kind of hydrogenating desulfurization agent of desulphurization reactor filling, numbering is respectively DS-2#.Catalyzer is with embodiment 1.
1 kind of hydrodenitrogenation catalyst DN-2# of fixed bed denitrification reactor filling, catalyzer is with embodiment 2.
Estimating raw materials used oily C is residual oil raw material, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 15%, 15%, 20%, 50%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-1#, catalyzer is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogenating desulfurization agent 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.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, catalyzer is with embodiment 1.
Estimating raw materials used oily D is residual oil raw material, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 18%, 20%, 30%, 32%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and adding proportion (weight) is 1: 2.The preparation method is with embodiment 1.
Desulphurization reactor loads 2 kinds of hydrogenating desulfurization agent 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.
The fixed bed denitrification reactor loads 2 kinds of hydrodenitrogenation catalyst DN-1# from top to bottom successively, and catalyzer is with embodiment 1.
Estimating raw materials used oily E is vacuum residuum, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 15%, 20%, 35%, 30%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
1 kind of hydrodemetallation (HDM) agent of upflowing demetalization reactor charge DM-1#, the preparation method is with embodiment 1.
1 kind of hydrogenating desulfurization agent of desulphurization reactor filling, numbering is respectively DS-1#.Catalyzer is with embodiment 1.
1 kind of hydrodenitrogenation catalyst DN-1# of fixed bed denitrification reactor filling, catalyzer is with embodiment 1.
Estimating raw materials used oily F is vacuum residuum, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Hydrogenation technique combination among the 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, load hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent and hydrodenitrification agent respectively in reactor, additional proportion is respectively 15%, 30%, 30%, 25%.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer DFC-2#, catalyzer is with embodiment 2.
Upflowing demetalization reactor loads 2 kinds of hydrodemetallation (HDM) agent DM-1# and DM-2# from top to bottom successively, and adding proportion (weight) is 1: 3.The preparation method is with embodiment 1.
The fixed bed desulphurization reactor loads 2 kinds of hydrogenating desulfurization agent 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.
The 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.
Estimating raw materials used oily G is vacuum residuum, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 5.
Comparative Examples 1
Hydrogenation technique combination in the Comparative Examples 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 from top to bottom.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load hydrogenating desulfurization agent and hydrodenitrification agent respectively.Catalyst combination and level mixing ratio are with embodiment 1.
Comparative Examples 1 raw materials used oily A is vacuum residuum, and its character is as shown in table 1.The device operation is with embodiment 1.Its reaction conditions and reaction product character are as shown in table 4, and as can be seen from Table 4, under the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 1 all are higher than Comparative Examples.And the operational cycle of Comparative Examples also is starkly lower than embodiment 1.
Comparative Examples 2
Hydrogenation technique combination in the Comparative Examples 2 comprises 5 fixed-bed reactor, 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 from top to bottom.Two deferrization decalcification reactor charge hydrogenation deferrization decalcifying agents, the agent of demetalization reactor charge hydrodemetallation (HDM), desulphurization reactor and denitrification reactor load hydrogenating desulfurization agent and hydrodenitrification agent respectively.Catalyst combination and level mixing ratio are with embodiment 2.
Comparative Examples 2 raw materials used oily B are vacuum residuum, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.As can be seen from Table 4, under the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 2 all are higher than Comparative Examples.And the operational cycle of Comparative Examples 2 also is starkly lower than embodiment 2.
Comparative Examples 3
The combination of hydrogenation technique in the Comparative Examples 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 as shown in Figure 2, and it is all identical with embodiment 3 to move other condition, catalyst combination and level mixing ratio, and its its reaction conditions of reaction conditions and reaction result are as shown in table 4.As shown in Table 4, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of Comparative Examples 3 all are lower than embodiment 3.Operational cycle also is starkly lower than embodiment 3.
Comparative Examples 4
Hydrogenation technique combination in the Comparative Examples 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 from top to bottom.Catalyst combination and level mixing 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 Examples is residual oil raw material, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.Under the identical situation of operational condition, deferrization decalcification rate, demetallization per, desulfurization degree and the denitrification percent of embodiment 4 all are higher than Comparative Examples 4 as can be seen from Table 4.And the operational cycle of Comparative Examples also is starkly lower than embodiment 4.
Comparative Examples 5
Comparative Examples 5 is used the same with embodiment 3 hydrogenation technique to make up and is installed operating scheme, comprises 2 upflowing deferrization decalcification reactors, 1 upflowing demetalization reactor, 1 desulphurization reactor and 1 denitrification reactor.The catalyst grade mixing ratio is also with embodiment 3, but catalyzer model difference.
1 kind of hydrogenation deferrization of upflow fixed bed deferrization decalcification reactor charge decalcification catalyzer is numbered DFC-3#, and the Preparation of catalysts method is as follows:
With hollow cam face Al
2O
3Make carrier, adopt the saturated method of spraying to prepare the catalyzer that active metal component is Mo.
Take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 165mL and contains the 4.3g ammonium molybdate and (contain MoO
382%, Beijing chemical reagents corporation) ammonia soln sprayed in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes 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%, catalyst particle size is 13mm.
1 kind of Hydrodemetalation catalyst of upflowing demetalization reactor charge is numbered DM-3#.Method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10mL/g contains 1.5%m TiO
2Al
2O
3Carrier sprays 165mL and contains the 18.6g ammonium molybdate and (contain MoO
382%) the aqueous solution sprayed in 15 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 5 hours down, roasting 4 hours in 500 ℃ of air again makes 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%, particle diameter is 3mm.
The catalyzer of fixed bed desulphurization reactor filling is selected DS-3# for use, and method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is the Al of 1.10mL/g
2O
3Carrier sprays 165mL by the saturated absorption amount of solution and contains the 29.8g ammonium molybdate and (contain MoO
382% quality) and the ammonia soln of 22.0g nickelous nitrate (containing NiO 25.2%).Homogenizing is after 15 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DS-3#.The physical data of DS-3# is as follows: MoO
3Content is that 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%, particle diameter is 1.3mm.
1 kind of hydrodenitrogenation catalyst of fixed bed denitrification reactor filling is numbered DN-3#.Method for preparing catalyst is as follows:
Take by weighing 150g, water-intake rate is that 1.10mL/g contains 10.0%TiO
2Al
2O
3Carrier sprays 165mL and contains the 42.7g ammonium molybdate and (contain MoO
382%) and the aqueous solution of 39.7g nickelous nitrate (containing NiO 25.2%) and phosphoric acid, sprayed in 10 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyzer.Be numbered DN-3#.The physical data of DN-3# is as follows: MoO
3Content is that 17.85%, NiO mass content is 5.2%, specific surface area 200m
2/ g, pore volume 0.41mL/g, bulk density 0.79g/mL, porosity is 40%, particle diameter is 1.1mm.
Raw materials used oily C is residual oil raw material, and its character is as shown in table 3.The device operation is with embodiment 1.Its reaction conditions of its reaction conditions and reaction result are as shown in table 4.
Adopt the EDX characterization method that catalyzer DFC-1, DFC-2, DM-1, DM-2, DS-1, DS-2, DN-1, DN-2 are characterized, describe the distribution situation of active ingredient on granules of catalyst, the result is referring to table 1 and table 2.As can be seen, among catalyzer DFC-1, the DFC-2 reactive metal be that " yolk " distributes, granules of catalyst from interior to outside, among DM-1, DM-2, DS-1, the DS-2, the downtrending of single or multiple reactive metal concentration in gradient; Among DN-1 and the DN-2, single or multiple reactive metal concentration in gradient increase trend; Among DFC-3, DM-3, DS-3 and the DN-3, the reactive metal substep is comparatively even.
Reactive metal concentration distribution on table 1 granules of catalyst
| Numbering | DFC-1 | DFC-2 | DFC-3 | DM-1 | DM-2 | DM-3 | 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 |
Annotate: be starting point with the particle center, R is the granules of catalyst radius.
Reactive metal concentration distribution on table 2 granules of catalyst
| Numbering | DN-1 | DN-2 | DN-3 |
| The reactive metal concentration distribution | |||
| 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 |
Annotate: be starting point with the particle center, R is the granules of catalyst radius.
Table 3 test raw material oil main character
| Material name | A | B | C | D | E | F | G |
| Density (20 ℃), kg/m 3 | 968.1 | 956.2 | 962.2 | 971.3 | 976.2 | 982.3 | 955.2 |
| Fe，μg/g | 25 | 7.8 | 10 | 15 | 2 | 3 | 8 |
| Ca，μg/g | 2.2 | 40 | 30.25 | 10 | 3 | 5 | 15 |
| (Ni+V)，μg/g | 90.6 | 50.2 | 42 | 60 | 110.1 | 105.2 | 60 |
| Sulphur, % | 3.01 | 2.32 | 2.6 | 1.9 | 3.8 | 3.5 | 4.2 |
| Nitrogen, % | 0.19 | 0.39 | 0.16 | 0.3 | 0.26 | 0.21 | 0.31 |
| Carbon residue, % | 14.1 | 12.1 | 13.1 | 13.2 | 13.6 | 13.3 | 14.32 |
Table 4 processing condition and product property
Table 5 processing condition and product property
| | Embodiment | 5 | |
|
| 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 | |
| The fixed bed desulphurization reactor | 850 | 850 | 850 | |
| The fixed bed denitrification reactor | 850 | 850 | 850 | |
| Liquid hourly space velocity, h -1 | 0.22 | 0.22 | 0.22 | |
| Temperature of reaction, ℃ | ||||
| Upflowing deferrization decalcification reactor | 380 | 380 | 380 | |
| Upflowing demetalization reactor | 385 | 385 | 385 | |
| The fixed bed desulphurization reactor | 390 | 390 | 390 | |
| The 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, month | 25 | 25 | 22 |
Claims (21)
1. inferior heavy oil hydroprocessing technique, sequentially, contain two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, it is characterized in that being connected to two arms the material house steward, be equipped with check valve on two arms, link to each other with a upflowing deferrization decalcification reactor respectively behind the valve, before the outlet line check valve of upflowing deferrization decalcification reactor with behind another upflowing deferrization decalcification Reactor inlet pipeline check valve, be connected with a pipeline, make material be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, be equipped with check valve on the pipeline; The outlet line of two upflowing deferrization decalcification reactors is connected with upflowing demetalization reactor from the bottom after being merged into a pipeline, link to each other with fixed bed desulphurization reactor, fixed bed denitrification reactor successively again, on the inlet line of upflowing demetalization reactor and outlet line, all be equipped with 3-way valve, have a pipeline to be connected between two 3-way valves; The processing condition of each reactor are: hydrogen pressure 5.0MPa～20.0MPa, 300 ℃～450 ℃ of temperature, volume space velocity 0.2h during liquid
-1～3h
-1, hydrogen to oil volume ratio 300～2000; 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; To outside surface, hydrogenation deferrization decalcification activity of such catalysts metal component is " yolk " and distributes from the granules of catalyst center; 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 hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and the hydrodenitrogenation catalyst combination, 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 hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and the hydrodenitrogenation catalyst combination, 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, 360 ℃～440 ℃ of temperature, 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, the catalyzer aperture reduces gradually, granularity reduces gradually, and porosity reduces gradually.
6. inferior heavy oil hydroprocessing technique according to claim 1, the upflowing deferrization decalcification reactor that it is characterized in that two parallel connections, a fixed bed demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor loads one or more catalyzer respectively in above-mentioned 4 classification reactors, along the logistics direction, the aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
7. according to claim 1,2,3,5 arbitrary described inferior heavy oil hydroprocessing techniques, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst, catalyzer is carrier with the porous inorganic oxide, and group vib metal and/or VIII family metal oxide are active ingredient.
8. inferior heavy oil hydroprocessing technique according to claim 7, it is characterized in that catalyzer rerum natura, consist of:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.1～3.0mL/g;
3) specific surface is 20～400m
2/ g;
4) catalyzer contains 1.0～20.0% group vib metal in corresponding burning amount, and/or 0.5～8.0% VIII family metal.
9. inferior heavy oil hydroprocessing technique according to claim 8, it is characterized in that catalyzer rerum natura, consist of:
1) with Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier;
2) pore volume is 0.3～1.3mL/g;
3) specific surface is 100～240m
2/ g;
4) catalyzer is in corresponding burning amount, contains 3.0～16% group vib metal and/or 1.0～5.5% VIII family metal.
10. according to Claim 8 or 9 described inferior heavy oil hydroprocessing techniques, it is characterized in that the group vib metal is Mo and/or W.
11. according to Claim 8 or 9 described inferior heavy oil hydroprocessing techniques, it is characterized in that VIII family metal is Co and/or Ni.
12. inferior heavy oil hydroprocessing technique according to claim 7 is characterized in that the preparation process of Hydrodemetalation catalyst and Hydrobon catalyst is:
With Al
2O
3Or contain 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 that sprays, solution sprays on carrier with atomizing state, descended dry 1～8 hour at 80～150 ℃ then, then at 300～650 ℃, roasting made catalyzer in 2～6 hours; Resulting catalyzer requires catalyst activity metal component distributed density autocatalysis agent particle center to be from high to low Gradient distribution to outside surface, is the Gradient distribution that a reactive metal or a plurality of active metal component distributed density are above situation.
13. inferior heavy oil hydroprocessing technique according to claim 12, it is characterized in that catalyst activity metal component distributed density autocatalysis agent particle center is by the denseer dipping solution of preparation to the Gradient distribution that outside surface is from high to low, spray in the process at carrier, the saturated spray-stain carrier of method that progressively adds deionized water or ammoniacal liquor dilution dipping solution obtains; Or by the preparation at least two kinds of different concns dipping solution, by dipping solution concentration in descending order spray-stain obtain at carrier.
14. inferior heavy oil hydroprocessing technique according to claim 7 is characterized in that the preparation process of hydrodenitrogenation catalyst is:
With Al
2O
3Or contain K
2O, MgO, SiO
2, TiO
2, ZrO
2Al
2O
3As carrier, with VIB and/or VIII family metallic compound, be mixed and made into dipping solution with deionized water or ammoniacal liquor, adopt the saturated method that sprays, solution sprays on carrier with atomizing state, descended dry 1～8 hour at 80～150 ℃ then, made catalyzer in 2～6 hours 300～650 ℃ of following roastings; Resulting catalyzer requires active metal component distributed density autocatalysis agent particle center to be from low to high Gradient distribution to outside surface, is the Gradient distribution that a reactive metal or a plurality of reactive metal concentration are above situation.
15. inferior heavy oil hydroprocessing technique according to claim 14, it is characterized in that catalyst activity metal component distributed density autocatalysis agent particle center is from low to high Gradient distribution to outside surface, be by preparation rarer VIB and/or VIII family metallic solution or deionized water, spray in the process, progressively adding the saturated sprayed carrier of denseer dipping solution obtains, or the dipping solution by the preparation different concns, spray at carrier from low to high by dipping solution concentration and to obtain.
16. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that in the hydrogenation deferrization decalcification granules of catalyst, metal component concentration is " yolk " and distributes, the granules of catalyst outside surface is 0～0.05 with the ratio of center reactive metal mass content, be point of beginning with the particle center, R is the granules of catalyst radius, be 0.03～0.2,0.33R place with the ratio of center reactive metal mass content at the ratio of 0.66R place and center reactive metal mass content is 0.5～0.95.
17. inferior heavy oil hydroprocessing technique according to claim 16, it is characterized in that in the hydrogenation deferrization decalcification granules of catalyst, the granules of catalyst outside surface is 0.005～0.02 with the ratio of center reactive metal mass content, the particle center is point of beginning, when R is the granules of catalyst radius, 0.66R locating ratio with center reactive metal mass content and be the ratio of 0.05～0.1,0.33R place and center reactive metal mass content is 0.75～0.95.
18. inferior heavy oil hydroprocessing technique according to claim 1, it is characterized in that urging in Hydrodemetalation catalyst and the Hydrobon catalyst, the metal component concentration distribution reduces distribution in gradient from the particle center to outside surface, the granules of catalyst outside surface is 0.05～0.70 with the ratio of center reactive metal mass content, the particle center is point of beginning, when R is the granules of catalyst radius, 0.66R locating ratio with center reactive metal mass content and be the ratio of 0.2～0.8,0.33R place and center reactive metal mass content is 0.4～0.9.
19. inferior heavy oil hydroprocessing technique according to claim 18, it is characterized in that in hydrogenation deferrization decalcification catalyzer and the Hydrodemetalation catalyst, the granules of catalyst outside surface is 0.15～0.45 with the ratio of center reactive metal mass content, 0.66R locating ratio with center reactive metal mass content and be the ratio of 0.35～0.6,0.33R place and center reactive metal mass content is 0.5～0.8.
20. inferior heavy oil hydroprocessing technique according to claim 1 is characterized in that in the hydrodenitrogenation catalyst that active metal component concentration increases gradually from the particle center to face; The granules of catalyst center is 0.05～0.70 with the ratio of outside surface reactive metal mass content, the center is point of beginning, when R is the granules of catalyst radius, 0.33R locating ratio with outside surface reactive metal mass content and be the ratio of 0.2～0.8,0.66R place and outside surface reactive metal mass content is 0.4～0.9.
21. inferior heavy oil hydroprocessing technique according to claim 20, it is characterized in that in the hydrodenitrogenation catalyst particle, the granules of catalyst center is 0.15～0.45 with the ratio of outside surface reactive metal mass content, 0.33R locating ratio with outside surface reactive metal mass content and be the ratio of 0.3～0.6,0.66R place and outside surface reactive metal mass content is 0.5～0.8.
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