CN103059936B - Hydrotreating method of heavy oil - Google Patents
Hydrotreating method of heavy oil Download PDFInfo
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- CN103059936B CN103059936B CN201110320987.1A CN201110320987A CN103059936B CN 103059936 B CN103059936 B CN 103059936B CN 201110320987 A CN201110320987 A CN 201110320987A CN 103059936 B CN103059936 B CN 103059936B
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Abstract
The invention provides a hydrotreating method of heavy oil. The method comprises the steps of introducing the heavy oil and hydrogen successively into a plurality of hydrogenation reactors connected in series under a hydrotreating reaction condition, and contacting with a plurality of hydrogenation catalyst bed layers of the hydrogenation reactors, wherein the hydrogenation reactors comprise a first hydrogenation reactor and subsequent hydrogenation reactors which are behind the first hydrogenation reactor according to a flow direction of the heavy oil. The first hydrogenation reactor comprises a hydrogenation protection catalyst bed layer and a macroporous hydrotreating catalyst bed layer, wherein the average pore size of the macroporous hydrotreating catalyst in the macroporous hydrotreating catalyst bed layer is 10-40 nm, pore volume is 0.1-2 cm3/g, and a specific surface area is 100-250 m2/g. Compared with a conventional method, the method provided by the invention can obtain a hydrotreating product with better performance, and particularly transfer the asphaltene in the heavy oil better.
Description
Technical field
The present invention relates to a kind of hydroprocessing process of heavy oil product.
Background technology
Along with the heaviness of crude oil is day by day serious, oil variety is increasing, also more and more higher to the requirement of heavy oil product lighting, and the importance of this processing method manifests day by day, and has good application prospect.
" heavy oil product " refers to the hydro carbons of the high asphalt content that obtained by topped crude, petroleum residual oil, oil-sand, pitch, shale oil, liquefaction coal or recovered oil. heavy oil product contains various pollutents conventionally, such as the residual matter of carbon containing, sulphur, nitrogen and metal etc.Generally in processing heavy oil product reactor sequences, load successively hydrodemetallation (HDM) agent, hydrodemetallation (HDM) sweetening agent, hydrogen desulfurization agent, hydrodenitrification agent, removal of ccr by hydrotreating agent, thereby remove metal, sulphur, nitrogen and carbon residue in heavy oil product, produce qualified catalytically cracked material.
The hydrogenation technique of heavy oil product is a kind of heavy oil deep processing technology, this technique is under the existence of hydrogen and catalyzer, the heavy oil such as residual oil are carried out to hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM) and carbon residue to be transformed and hydrocracking reaction, residual oil after resulting hydrogenation can be used as the charging of fine quality catalytic cracking and produces light-end products, to reach residual oil lighting to greatest extent, realize sludgeless oil refinery.
Residual oil after hydrotreatment can reduce the sulphur content of FCC gasoline as FCC charging, can reduce the discharge of SOx and NOx in FCC flue gas simultaneously, can also make benzoline maximize, thereby make full use of crude resources.
In current heavy oil product hydrogenation catalyst grating, mainly consider demetalization, desulfurization, denitrogenation and de-carbon residue.Therefore, in heavy oil product hydrogenation process, the main reaction occurring has hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification and carbon residue conversion and bitum hydrocracking reaction etc.In all components of heavy oil product, bituminous matter is the most unmanageable component.Bitum molecular weight is very large, and contains sulphur, nitrogen, heavy metal and multinuclear aromatic compound.Therefore, bitum changing effect has determined the effect of heavy oil product hydrotreatment to a great extent.
A method that has the processing asphaltenes heavy oil product of guard reactor has been proposed in US4118310; in guard reactor, be mainly sulphur and the metal removing in raw material, the further demetalization of catalyzer, desulfurization, denitrogenation and carbon residue in recycling follow-up hydrogenation reactor.Operator scheme is also the operator scheme that adopts conventional residual hydrogenation.
But because asphaltene molecules is larger, the method still can not well transform bituminous matter, thereby the effect that heavy oil product demetalization, desulfurization, denitrogenation and carbon residue are transformed is unsatisfactory.
Summary of the invention
Object of the present invention is exactly to improve the deficiency of prior art heavy oil product hydroprocessing process, from the angle of catalyzer and technique, has proposed a kind of new heavy oil product hydroprocessing process, and the method can be good at transforming the bituminous matter in heavy oil product.
The present inventor finds under study for action, in prior art, the unsatisfactory reason of heavy oil product hydrotreatment effect is that the asphaltene molecules in heavy oil product is larger, and contain a large amount of heteroatomss, and these heteroatomss " bury " all dearly at bitum intramolecule, utilize conventional catalyst for demetalation to be difficult to asphaltenes conversion, therefore be also difficult to " to bury " impurity removal in asphaltene molecules inside.
Hydrotreating catalyst is comprised of infusibility carrier and the metal active constituent of porous conventionally.And the pore structure of hydrotreating catalyst affects the desulfurization, denitrogenation of catalyzer and the activity that carbon residue transforms, and affect metal pollutant and how to make rapidly catalyst deactivation.Therefore, select to be a kind ofly applicable to the hydrotreating catalyst that bituminous matter is processed and to coordinate the corresponding technique should be able to be effectively by the asphaltenes conversion in heavy oil product, thereby improve the effect of heavy oil product hydrotreatment.Based on this, the present inventor has completed the present invention just.
The invention provides a kind of hydroprocessing process of heavy oil product, it is characterized in that, the method comprises, under hydrotreatment reaction conditions, heavy oil product and hydrogen are introduced in a plurality of hydrogenators of series connection successively, and contact with a plurality of hydrogenation catalyst beds in the plurality of hydrogenator, the flow direction according to described heavy oil product, described a plurality of hydrogenator comprises the first hydrogenator and is positioned at described the first hydrogenator follow-up hydrogenation reactor afterwards, the first hydrogenator comprises hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds setting gradually, wherein, the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in beds is 10-40nm, pore volume is 0.1-2cm
3/ g, specific surface area is 100-250m
2/ g.
The relative prior art of method of the present invention has obtained the better hydrotreatment product of performance, has particularly better transformed the bituminous matter in heavy oil product, and also explanation, is applied to method of the present invention will obtain good economic benefit in large-scale commercial production simultaneously.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the process flow sheet of one embodiment of the present invention;
Fig. 2 is the process flow sheet of prior art.
Embodiment
The invention provides a kind of hydroprocessing process of heavy oil product, it is characterized in that, the method comprises, under hydrotreatment reaction conditions, heavy oil product and hydrogen are introduced in a plurality of hydrogenators of series connection successively, and contact with a plurality of hydrogenation catalyst beds in the plurality of hydrogenator, the flow direction according to described heavy oil product, described a plurality of hydrogenator comprises the first hydrogenator and is positioned at described the first hydrogenator follow-up hydrogenation reactor afterwards, the first hydrogenator comprises hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds setting gradually, wherein, the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in beds is 10-40nm, be preferably 20-30nm, pore volume is 0.1-2cm
3/ g, is preferably 0.3-1.0cm
3/ g, specific surface area is 100-250m
2/ g, be preferably 130-200m
2/ g.
In the present invention, the object of using macropore hydrogenation to process catalyzer is to make the bituminous matter that molecular weight is larger can better be converted into small molecules, and and then conversion heteroatoms wherein.Therefore, the present invention processes the tap density of catalyzer to described macropore hydrogenation, and there is no particular limitation for the composition of carrier, hydrogenation active metals etc., can be the various selections of routine.Preferably, described macropore hydrogenation processing catalyst buildup density is 0.3-0.7g/cm
3.The macropore hydrogenation of the mean pore size in above-mentioned preferable range, pore volume, specific surface area and tap density is processed catalyzer can obtain better asphaltenes conversion effect.
Carrier and hydrogenation active metals that macropore hydrogenation described in the present invention is processed catalyzer can be various carriers and hydrogenation active metals conventional in residual hydrocracking, preferably, the weight that the macropore hydrogenation of take is processed catalyzer is benchmark, in the oxide compound of hydrogenation active metals, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier that loads on of the carrier that contains 80-97 % by weight in catalyzer and 3-20 % by weight.Further preferably, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier that loads on of the carrier that contains 80-92 % by weight in catalyzer and 8-20 % by weight.Described carrier is preferably aluminum oxide and/or silicon oxide.Hydrogenation active metals in described hydrogenation active metals component is group vib metal and/or group VIII metal, more preferably at least two kinds in W, Mo, Ni and Co.
Most preferably, in the present invention, described hydrogenation active metals is Mo and Ni, and the weight that the macropore hydrogenation of take is processed catalyzer is benchmark, in the oxide compound of hydrogenation active metals, the content that described macropore hydrogenation is processed Mo in catalyzer is 2-15 % by weight, and the content of Ni is 1-5 % by weight.Further preferably, in the oxide compound of hydrogenation active metals, described macropore hydrogenation is processed the content 5-15 % by weight of Mo in catalyzer, and the content of Ni is 3-5 % by weight.
The present invention is specially adapted to process the heavy oil product of asphaltenes, and for example, it is 0.5-20 % by weight that the present invention is applicable to process asphaltene content, is preferably the heavy oil product of 2-12 % by weight.Described heavy oil product can be crude oil, the long residuum being obtained by crude oil and vacuum residuum, the various oil that obtained by coal, tar sand, resinous shale and pitch, and their mixture.Sulphur content in these residual oil raw materials, nitrogen content, asphalt content, beavy metal impurity content and carbon residue content are all higher to some extent.
In the present invention, heavy oil product refers in particular to and contains bitum long residuum or vacuum residuum.The boiling range of long residuum is more than approximately 345 ℃.The boiling range of vacuum residuum is more than approximately 500 ℃, and conventionally than long residuum, has higher viscosity.
According to the present invention, preferably, the flow direction according to described heavy oil product, described follow-up hydrogenation reactor comprises at least one Hydrodemetalation catalyst bed, at least one Hydrobon catalyst bed and at least one the removal of ccr by hydrotreating beds setting gradually, and each Hydrodemetalation catalyst bed, each Hydrobon catalyst bed and each removal of ccr by hydrotreating beds are arranged in identical or different hydrogenator.
According to the present invention, the number of described a plurality of hydrogenators is preferably 2-6; The number of the hydrogenation catalyst bed in each hydrogenator is preferably 1-4, more preferably 1-3.The number of the hydrogenation catalyst bed in the number of described hydrogenator and each hydrogenator can carry out suitable adjustment as required.As, in heavy oil product, metal content is very high, and the Hydrodemetalation catalyst bed of a plurality of numbers can be set.Similarly, in each beds, the loadings of catalyzer also can be adjusted as required.
Specifically preferably, for conventional residual oil, in last reactor in described follow-up hydrogenation reactor, be provided with removal of ccr by hydrotreating beds or Hydrobon catalyst bed and removal of ccr by hydrotreating beds, in remaining reactor in follow-up hydrogenation reactor, be provided with Hydrodemetalation catalyst bed and/or Hydrobon catalyst bed.
Further preferably, as shown in Figure 1, the number of described a plurality of hydrogenators is 5, the flow direction according to described heavy oil product, in the first hydrogenator, be disposed with hydrogenation protecting catalyst bed and macropore hydrogenation and process beds, in the second hydrogenator, be all provided with Hydrodemetalation catalyst bed, in the 3rd hydrogenator, be disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed, in the 4th hydrogenator, be all provided with Hydrobon catalyst bed, in last hydrogenator, be disposed with Hydrobon catalyst bed and removal of ccr by hydrotreating beds.
According to the present invention, described hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer can be the catalyzer with these functions of this area routine.Carbon residue, nitrogen and sulphur exist in residual oil usually used as pollutent, although these pollutents may exist as relatively simple molecule, they remain in hydrocarbon molecules more firmly by chemical bond conventionally.So, remove carbon residue, sulphur and nitrogen and remove metallographic phase than conventionally needing more highly active hydrogenation catalyst.Usually, above-mentioned catalyzer be all take porous inorganic oxide as aluminum oxide as carrier, take group vib and/or group VIII metal if one or more the oxide compound in W, Mo, Co and Ni is as active ingredient, optionally add other various auxiliary agents as one or more catalyzer in P, Si, F and B.During use; after can being purchased separately various catalyzer, be used in combination; also can directly be purchased the complete series catalyst for hydrotreatment of residual oil that comprises above-mentioned various catalyzer, as the RG purchased from catalyzer Chang Ling branch office, RDM, RMS and RSC series weight, hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer.
The preparation method that described macropore hydrogenation is processed catalyzer (CAT-A) can comprise: after macropore pseudo-boehmite dry glue powder is mixed with polyvinyl alcohol, add Semen Maydis oil and the aqueous solution to carry out kneading, and the plastic obtaining is carried out to moulding, after dry and roasting, make carrier.Can adopt the method for saturated dipping that active metal component is carried on to described carrier and make catalyzer.Described macropore pseudo-boehmite dry glue powder is available commercially.
Method of the present invention can adopt the reactor of different structure, preferably adopts fixed-bed reactor.
The present invention to raw material the flow direction in hydrotreatment district there is no particular limitation, each hydrogenator can be both also downflow reactor for up-flow reactor.
According to the present invention, described hydrotreatment reaction conditions can specifically comprise for the hydrotreatment reaction conditions of this area routine, and temperature of reaction is preferably 300-420 ℃, more preferably 340-420 ℃; Reaction pressure is preferably 10-17MPa, more preferably 13-16MPa; Hydrogen to oil volume ratio is preferably 200-2000, more preferably 420-1500; During the liquid of heavy oil product, volume space velocity is preferably 0.10-0.45h
-1, 0.14-0.30h more preferably
-1.
The present inventor finds, when using macropore hydrogenation to process catalyzer, use relatively high temperature of reaction can access better hydrotreatment effect, therefore, preferably, the temperature of reaction in described the first hydrogenator is higher than the temperature of reaction in follow-up hydrogenation reactor.Specifically preferably, the temperature of reaction in described the first hydrogenator is than the high 5-50 ℃ of the temperature of reaction in follow-up hydrogenation reactor, more preferably 10-40 ℃.
According to the present invention; preferably; in the first hydrogenator, the hydrogenation protecting catalyst in hydrogenation protecting catalyst bed and macropore hydrogenation are processed the admission space of the macropore hydrogenation processing catalyzer in beds than being 2-60: 98-40, more preferably 10-30: 70-90.
In the present invention, in described a plurality of reactors, the setting of a plurality of beds can, according to practical situation adjustment, as the height of each bed, number and position, preferably, can arrange as shown in Figure 1.
Below, the flow process of brief description the inventive method by reference to the accompanying drawings, as shown in Figure 1, this device adopts five reactors in series, the top-down technical process of stock oil, stock oil and hydrogen enter a, b, c, d and the e reactor of series connection successively from 101 pipelines, wherein, in a reactor, be disposed with three beds, comprise RG-10A (hydrogenation protecting catalyst) and RG-10B (hydrogenation protecting catalyst) bed, and be positioned at CAT-A (the macropore hydrogenation processing catalyzer) bed after RG-10A and RG-10B; In b reactor, being provided with a bed, is RDM-2B (Hydrodemetalation catalyst) bed; In c reactor, be disposed with two beds, comprise RDM-2B bed and RMS-3B (Hydrobon catalyst) bed; In d reactor, being provided with a bed, is RMS-1B (Hydrobon catalyst) bed; In e reactor, be disposed with two beds, comprise RMS-1B bed and RSC-1 (removal of ccr by hydrotreating catalyzer) bed.
In each bed, the loadings of catalyzer can adopt conventional amount used of the prior art, if the volume ratio of the RG-10A loading in a reactor, RG-10B and RDM-2B (or CAT-A) can be 1: 0.5-2: 4-20; In b reactor, can all load RDM-2B catalyzer; In c reactor, the RDM-2B of filling and the volume ratio of RMS-3B can be 2-5: 1; In d reactor, all load RMS-1B catalyzer; The RMS-1B loading in e reactor and the volume ratio of RSC-1 can be 2-5: 1.
And in the method for prior art, as shown in Figure 2, in a reactor, what the position suitable with CAT-A arranged is RDM-2B bed.
Below, by embodiment, method of the present invention is described in detail.
In the embodiment of the present invention, equipment therefor is fixed bed hydrogenation Processing Test device as shown in Figure 1, and 5 volumes of this device employing are the top-down technical process of reactors in series, stock oil of 1 liter.
RG used, RDM and RMS, RSC series weight, hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst and Hydrobon catalyst are that China Petrochemical Industry's catalyzer Chang Ling branch office produces.
The filling situation of each catalyst reactor is:
Catalyzer in a reactor is from top to bottom: RG-10A, RG-10B and CAT-A;
In b reactor, all load RDM-2B catalyzer;
In c reactor, the catalyzer of filling is RDM-2B and RMS-3B catalyzer from top to bottom, and the ratio of admission space is 75: 25;
In d reactor, all load RMS-1B catalyzer;
In e reactor, load RMS-1B and RSC-1 catalyzer, the ratio of admission space is 80: 20.
It is laboratory preparation that the macropore hydrogenation adopting is processed catalyzer CAT-A, particularly, the preparation method of CAT-A-1 comprises: take 300 grams of the macropore pseudo-boehmite dry glue powders (butt is 72 % by weight) that Chang Ling catalyzer branch office produces, 12 grams of polyvinyl alcohol, after mixing, add 12 grams of Semen Maydis oils, 360 milliliters of the aqueous solution, kneading 0.5 hour, gained plastic, on double screw banded extruder, be extruded into the trilobal bar of ￠ 1.1-1.8 millimeter, wet bar in 940 ℃ of roastings 2 hours, obtains carrier after 140 ℃ are dried 4 hours.Adopt general saturated dipping method, with active metal solution (ammonium metawolframate+nickel nitrate solution; Ammonium molybdate+ammonia soln+nickel nitrate solution), impregnated carrier is then dried respectively 2-3 hour at 80-120 ℃, and roasting 1-2 hour at 350-480 ℃, makes catalyzer CAT-A-1.The preparation method of CAT-A-2 and CAT-A-3 roughly the same.
The character of the CAT-A-1 using in the embodiment 1 making comprises: mean pore size is 30nm, and pore volume is 0.8cm
3/ g, specific surface area is 200m
2/ g, tap density is 0.54g/cm
3; The carrier of CAT-A-1 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and to take the weight of CAT-A-1 be benchmark, and in described CAT-A-1, the content of carrier is 88 % by weight, and in oxide compound, the content of Mo is 8 % by weight, and the content of Ni is 4 % by weight.
The character of the CAT-A-2 using in the embodiment 2 making comprises: mean pore size is 20nm, and pore volume is 1cm
3/ g, specific surface area is 175m
2/ g, tap density is 0.68g/cm
3; The carrier of CAT-A-2 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and to take the weight of CAT-A-2 be benchmark, and in described CAT-A-2, the content of carrier is 90 % by weight, and in oxide compound, the content of Mo is 5 % by weight, and the content of Ni is 5 % by weight.
The character of the CAT-A-3 using in the embodiment 3 making comprises: mean pore size is 25nm, and pore volume is 0.37cm
3/ g, specific surface area is 155m
2/ g, tap density is 0.34g/cm
3; The carrier of CAT-A-3 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and to take the weight of CAT-A-3 be benchmark, and in described CAT-A-3, the content of carrier is 85 % by weight, and in oxide compound, the content of Mo is 12 % by weight, and the content of Ni is 3 % by weight.
Wherein, the mean pore size of macropore hydrogenation processing catalyzer records by BET method; Pore volume records by BET method; Specific surface area records by BET method; In product after residual hydrocracking, sulphur content records by GB/T 17040-2008 method; Nitrogen content records by SH/T 0704-2001 method; Carbon residue records by GB/T 17144-1997 method; Heavy metal (Ni+V) content records by ICP-AEP, and asphalt content records by adsorption separating method.
Embodiment 1
Adopt the equipment and process flow process shown in Fig. 1, wherein, the catalyzer in a reactor is from top to bottom: RG-10A, RG-10B and CAT-A-1, each catalyst loading volume ratio is 10: 10: 80.
Make the residual oil raw material M (main character is listed in table 1) of high asphalt content be mixed into a reactor with hydrogen, and enter successively subsequently b, c, d and e reactor and carry out hydrotreatment, hydroprocessing condition comprises: reaction pressure is 14.7MPa, hydrogen to oil volume ratio is 600, and during liquid, volume space velocity is 0.216h
-1, the temperature of reaction of a reactor is 390 ℃, the temperature of reaction of b, c, d and e reactor is 380 ℃.
The character of the product P 1 obtaining after residual hydrocracking comprises: sulphur content is 0.33 % by weight, nitrogen content is 0.18 % by weight, and carbon residue is 6.8 % by weight, and heavy metal (Ni+V) content is 13.6 μ g/g, asphalt content is 1.2 % by weight, meets the requirement of RFCC charging.
Table 1
| Residual oil raw material M | |
| Density (20 ℃), g/cm 3 | 0.9939 |
| Viscosity (100 ℃), mm 2/s | 165.1 |
| MCR (% by weight) | 14.6 |
| Sulphur content (% by weight) | 4.6 |
| Nitrogen content (% by weight) | 0.22 |
| Heavy metal (Ni+V) content (μ g/g) | 131.7 |
| Four component concentrations (% by weight) | |
| Stable hydrocarbon | 21.5 |
| Aromatic hydrocarbons | 48.1 |
| Colloid | 22.2 |
| Bituminous matter (C 7Insolubles) | 8.0 |
Embodiment 2
Adopt the equipment and process flow process shown in Fig. 1, make residual oil raw material M and hydrogen be mixed into a reactor, and enter successively b, c subsequently, d and e reactor carry out hydrotreatment, hydroprocessing condition comprises: reaction pressure is 13.2MPa, hydrogen to oil volume ratio is 1500, and during liquid, volume space velocity is 0.142h
-1, the temperature of reaction of a reactor is 375 ℃, the temperature of reaction of b, c, d and e reactor is 355 ℃.
Wherein, according to each reactor of the type of the catalyzer loading in a, b, c, d and e reactor in embodiment 1 and volume filling the present embodiment, different is, catalyzer in a reactor is from top to bottom: RG-10A, RG-10B and CAT-A-2, the ratio of each catalyst loading volume is 15: 15: 70.
The character of the product P 2 obtaining after residual hydrocracking comprises: sulphur content is 0.4 % by weight, nitrogen content is 0.21 % by weight, and carbon residue is 8.0 % by weight, and heavy metal (Ni+V) content is 17.0 μ g/g, asphalt content is 2.1 % by weight, meets the requirement of RFCC charging.
Comparative example 1
According to the hydroprocessing condition identical with embodiment 2, residual oil raw material M is carried out to residual hydrocracking, different, adopt equipment and process flow process as shown in Figure 2, that is, the catalyzer RDM-2B of weight such as use to replace the CAT-A-2 in a reactor.
The character of the product DP1 obtaining after residual hydrocracking comprises: sulphur content is 0.43 % by weight, and nitrogen content is 0.24 % by weight, and carbon residue is 9.3 % by weight, and heavy metal (Ni+V) content is 19.5 μ g/g, and asphalt content is 3.5 % by weight.
Embodiment 3
Adopt the equipment and process flow process shown in Fig. 1, make residual oil raw material M and hydrogen be mixed into a reactor, and enter successively b, c subsequently, d and e reactor carry out hydrotreatment, hydroprocessing condition comprises: reaction pressure is 14.2MPa, hydrogen to oil volume ratio is 420, and during liquid, volume space velocity is 0.188h
-1, the temperature of reaction of a reactor is 420 ℃, the temperature of reaction of b, c, d and e reactor is 385 ℃.
Wherein, according to each reactor of the type of the catalyzer loading in a, b, c, d and e reactor in embodiment 1 and volume filling the present embodiment, different is, catalyzer in a reactor is from top to bottom: RG-10A, RG-10B and CAT-A-3, the ratio of each catalyst loading volume is 5: 5: 90.
The character of the product P 3 obtaining after residual hydrocracking comprises: sulphur content is 0.30 % by weight, nitrogen content is 0.15 % by weight, and carbon residue is 6.0 % by weight, and heavy metal (Ni+V) content is 12.0 μ g/g, asphalt content is 0.8 % by weight, meets the requirement of RFCC charging.
Embodiment 4
According to the equipment described in embodiment 1 and method, residual oil raw material M is carried out to hydrotreatment, different, the temperature of all reactors is 380 ℃.
The character of the product P 4 obtaining after residual hydrocracking comprises: sulphur content is 0.34 % by weight, nitrogen content is 0.18 % by weight, and carbon residue is 6.8 % by weight, and heavy metal (Ni+V) content is 13.7 μ g/g, asphalt content is 1.6 % by weight, meets the requirement of RFCC charging.
Data by embodiment 1-3 and comparative example 1 can be found out, the method according to this invention is carried out the hydrotreatment of heavy oil product, can obtain the product that sulphur content, nitrogen content, carbon residue and heavy metal content all reduce, especially the content of product studies on asphaltene significantly reduces especially, thereby has improved the overall quality of product.
Data by embodiment 4 and embodiment 1 can find out, a temperature of reactor can obtain better asphaltenes conversion effect a little more than the temperature of follow-up reactor, is the preferred embodiment of the present invention.
Claims (12)
1. the hydroprocessing process of a heavy oil product, it is characterized in that, the method comprises, under hydrotreatment reaction conditions, heavy oil product and hydrogen are introduced in a plurality of hydrogenators of series connection successively, and contact with a plurality of hydrogenation catalyst beds in the plurality of hydrogenator, the flow direction according to described heavy oil product, described a plurality of hydrogenator comprises the first hydrogenator and is positioned at described the first hydrogenator follow-up hydrogenation reactor afterwards, the first hydrogenator comprises hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds setting gradually, wherein, the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in beds is 10-40nm, pore volume is 0.1-2cm
3/ g, specific surface area is 100-250m
2/ g,
Wherein, the content of described heavy oil product studies on asphaltene is 0.5-20 % by weight,
The flow direction according to described heavy oil product, follow-up hydrogenation reactor comprises at least one Hydrodemetalation catalyst bed, at least one Hydrobon catalyst bed and at least one the removal of ccr by hydrotreating beds setting gradually, and each Hydrodemetalation catalyst bed, each Hydrobon catalyst bed and each removal of ccr by hydrotreating beds are arranged in identical or different hydrogenator.
2. method according to claim 1, wherein, described macropore hydrogenation is processed macropore hydrogenation in beds, and to process the mean pore size of catalyzer be 20-30nm, pore volume is 0.3-1.0cm
3/ g, specific surface area is 130-200m
2/ g.
3. method according to claim 1, wherein, the weight that the macropore hydrogenation of take is processed catalyzer is benchmark, oxide compound in hydrogenation active metals, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier that loads on of the carrier that contains 80-97 % by weight in catalyzer and 3-20 % by weight, described carrier is aluminum oxide and/or silicon oxide, and the hydrogenation active metals in described hydrogenation active metals component is group vib metal and/or group VIII metal.
4. method according to claim 3, wherein, described hydrogenation active metals is at least two kinds in W, Mo, Ni and Co.
5. method according to claim 4, wherein, described hydrogenation active metals is Mo and Ni, and the weight that the macropore hydrogenation of take is processed catalyzer is benchmark, oxide compound in hydrogenation active metals, the content that described macropore hydrogenation is processed Mo in catalyzer is 2-15 % by weight, and the content of Ni is 1-5 % by weight.
6. according to the method described in any one in claim 1-5, wherein, the number of described a plurality of hydrogenators is 2-6, and the number of the hydrogenation catalyst bed in each hydrogenator is 1-4.
7. method according to claim 1, wherein, is provided with removal of ccr by hydrotreating beds or Hydrobon catalyst bed and removal of ccr by hydrotreating beds in last reactor in described follow-up hydrogenation reactor; In remaining reactor in follow-up hydrogenation reactor, be provided with Hydrodemetalation catalyst bed and/or Hydrobon catalyst bed.
8. method according to claim 7, wherein, the number of described a plurality of hydrogenators is 5, the flow direction according to described heavy oil product, in the first hydrogenator, be disposed with hydrogenation protecting catalyst bed and macropore hydrogenation and process beds, in the second hydrogenator, be provided with Hydrodemetalation catalyst bed, in the 3rd hydrogenator, be disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed, in the 4th hydrogenator, be provided with Hydrobon catalyst bed, in last hydrogenator, be disposed with Hydrobon catalyst bed and removal of ccr by hydrotreating beds.
9. according to the method described in any one in claim 1-5 and 7-8, wherein, described hydrotreatment reaction conditions comprises, temperature of reaction is 300-420 ℃, reaction pressure is 10-17MPa, and hydrogen to oil volume ratio is 200-2000, and during the liquid of heavy oil product, volume space velocity is 0.10-0.45h
-1.
10. method according to claim 9, wherein, the temperature of reaction in described the first hydrogenator is higher than the temperature of reaction in follow-up hydrogenation reactor.
11. methods according to claim 10, wherein, the temperature of reaction in described the first hydrogenator is than the high 5-50 ℃ of the temperature of reaction in follow-up hydrogenation reactor.
12. according to the method described in any one in claim 1-5,7-8 and 10-11; wherein; in the first hydrogenator, the hydrogenation protecting catalyst in hydrogenation protecting catalyst bed and macropore hydrogenation are processed the admission space of the macropore hydrogenation processing catalyzer in beds than being 2-60:98-40.
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|---|---|---|---|
| CN201110320987.1A CN103059936B (en) | 2011-10-20 | 2011-10-20 | Hydrotreating method of heavy oil |
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| US4118310A (en) * | 1977-06-28 | 1978-10-03 | Gulf Research & Development Company | Hydrodesulfurization process employing a guard reactor |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1597856A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Heavy slag oil fixed bed hydrogenating treatment process |
| CN1990834A (en) * | 2005-12-30 | 2007-07-04 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
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| US4118310A (en) * | 1977-06-28 | 1978-10-03 | Gulf Research & Development Company | Hydrodesulfurization process employing a guard reactor |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1597856A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Heavy slag oil fixed bed hydrogenating treatment process |
| CN1990834A (en) * | 2005-12-30 | 2007-07-04 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
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