CN103059936A - Hydrotreating method of heavy oil - Google Patents
Hydrotreating method of heavy oil Download PDFInfo
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- CN103059936A CN103059936A CN2011103209871A CN201110320987A CN103059936A CN 103059936 A CN103059936 A CN 103059936A CN 2011103209871 A CN2011103209871 A CN 2011103209871A CN 201110320987 A CN201110320987 A CN 201110320987A CN 103059936 A CN103059936 A CN 103059936A
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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, and is 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 preferably application prospect is arranged.
" 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 usually, 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 the 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 in the presence of hydrogen and catalyzer, the heavy oil such as residual oil are carried out hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM) and carbon residue to be transformed and hydrocracking reaction, residual oil behind the resulting hydrogenation can be used as the charging of fine quality catalytic cracking and produces light-end products, to reach to greatest extent lighting of residual oil, realize the sludgeless oil refinery.
Residual oil after hydrotreatment can reduce the sulphur content of FCC gasoline as the FCC charging, can reduce the discharging of SOx and NOx in the FCC flue gas simultaneously, can also make the benzoline maximization, thereby take full advantage of crude resources.
In the present heavy oil product hydrogenation catalyst grating, mainly consider demetalization, desulfurization, denitrogenation and take off carbon residue.Therefore, the main reaction that occurs has hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification and carbon residue conversion and bitum hydrocracking reaction etc. in the heavy oil product hydrogenation process.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 the processing asphaltenes heavy oil product of guard reactor is arranged has been proposed among the US4118310; mainly be sulphur and the metal that removes in the raw material in guard reactor, the further demetalization of catalyzer, desulfurization, denitrogenation and carbon residue in the recycling follow-up hydrogenation reactor.Operator scheme also is to adopt the operator scheme of conventional residual hydrogenation.
But because asphaltene molecules is larger, the method still can not well transform bituminous matter, thereby so that the effect that heavy oil product demetalization, desulfurization, denitrogenation and carbon residue transform is unsatisfactory.
Summary of the invention
Purpose 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 the heavy oil product.
The present inventor finds under study for action, the unsatisfactory reason of heavy oil product hydrotreatment effect is that the asphaltene molecules in the heavy oil product is larger in the prior art, 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 also be difficult to " to bury " impurity removal in asphaltene molecules inside.
Hydrotreating catalyst is comprised of infusibility carrier and the metal active constituent of porous usually.And the pore structure of hydrotreating catalyst affects the desulfurization, denitrogenation of catalyzer and the activity that carbon residue transforms, and affects metal pollutant and how to make rapidly catalyst deactivation.Therefore, select a kind ofly to be fit to the hydrotreating catalyst that bituminous matter is processed and to cooperate the corresponding technique should be able to be effectively with the asphaltenes conversion in the heavy oil product, thereby improve the effect of heavy oil product hydrotreatment.Just be based on this, the present inventor has finished the present invention.
The invention provides a kind of hydroprocessing process of heavy oil product; it is characterized in that; the method comprises; under the 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 these a plurality of hydrogenators; 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; comprise the hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds that set gradually in the first hydrogenator; wherein; the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in the beds is 10-40nm, and 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 the heavy oil product, and also explanation is applied to method of the present invention will obtain good economic benefit in the large-scale commercial production simultaneously.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.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 the 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 these a plurality of hydrogenators, 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, comprise the hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds that set gradually in the first hydrogenator, wherein, the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in the beds is 10-40nm, is 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.
Among the present invention, the purpose of using macropore hydrogenation to process catalyzer is to make the larger bituminous matter of molecular weight 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
3The 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 commonly used in the residual hydrocracking, preferably, process the weight of catalyzer as benchmark take macropore hydrogenation, in the oxide compound of hydrogenation active metals, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier of loading on of the carrier that contains the 80-97 % by weight in the catalyzer and 3-20 % by weight.Further preferably, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier of loading on of the carrier that contains the 80-92 % by weight in the catalyzer and 8-20 % by weight.Described carrier is preferably aluminum oxide and/or silicon oxide.Hydrogenation active metals in the described hydrogenation active metals component is group vib metal and/or group VIII metal, more preferably at least two kinds among W, Mo, Ni and the Co.
Most preferably, among the present invention, described hydrogenation active metals is Mo and Ni, and process the weight of catalyzer as benchmark take macropore hydrogenation, in the oxide compound of hydrogenation active metals, the content that described macropore hydrogenation is processed Mo in the catalyzer is the 2-15 % by weight, and the content of Ni is the 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 the catalyzer, and the content of Ni is the 3-5 % by weight.
The present invention is specially adapted to process the heavy oil product of asphaltenes, and for example, it is the 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 and the vacuum residuum that are obtained by crude oil, 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.
Among 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 approximately more than 345 ℃.The boiling range of vacuum residuum is approximately more than 500 ℃, and usually than long residuum higher viscosity is arranged.
According to the present invention, preferably, the flow direction according to described heavy oil product, comprise at least one the Hydrodemetalation catalyst bed, at least one Hydrobon catalyst bed and at least one the removal of ccr by hydrotreating beds that set gradually in the described follow-up hydrogenation reactor, and each Hydrodemetalation catalyst bed, each Hydrobon catalyst bed and each removal of ccr by hydrotreating beds are arranged in the 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, metal content is very high in the heavy oil product, and the Hydrodemetalation catalyst bed of a plurality of numbers then can be set.Similarly, the loadings of catalyzer also can be adjusted as required in each beds.
Specifically preferably, residual oil for routine, be provided with removal of ccr by hydrotreating beds or Hydrobon catalyst bed and removal of ccr by hydrotreating beds in last reactor in the described follow-up hydrogenation reactor, be provided with Hydrodemetalation catalyst bed and/or Hydrobon catalyst bed in remaining reactor in the follow-up hydrogenation reactor.
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; be disposed with hydrogenation protecting catalyst bed and macropore hydrogenation in the first hydrogenator and process beds; all be provided with the Hydrodemetalation catalyst bed in the second hydrogenator; be disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed in the 3rd hydrogenator; all be provided with the Hydrobon catalyst bed in the 4th hydrogenator, be disposed with Hydrobon catalyst bed and removal of ccr by hydrotreating beds in last hydrogenator.
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 as pollutent usually, although these pollutents may exist as relatively simple molecule, they remain in the hydrocarbon molecules more firmly by chemical bond usually.So, remove carbon residue, sulphur and nitrogen and remove metallographic phase than usually needing more highly active hydrogenation catalyst.Usually, above-mentioned catalyzer all is that one or more oxide compound take porous inorganic oxide such as aluminum oxide as carrier, in group vib and/or group VIII metal such as W, Mo, Co and the Ni is as active ingredient, optionally add among other various auxiliary agents such as P, Si, F and the B one or more catalyzer.During use; be used in combination after can being purchased separately various catalyzer; also can directly be purchased the complete series catalyst for hydrotreatment of residual oil that comprises above-mentioned various catalyzer, such as RG, RDM, RMS and RSC series weight, hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst, Hydrobon catalyst and the removal of ccr by hydrotreating catalyzer available from catalyzer Chang Ling branch office.
The preparation method that described macropore hydrogenation is processed catalyzer (CAT-A) can comprise: adding Semen Maydis oil and the aqueous solution carried out kneading after macropore pseudo-boehmite dry glue powder was mixed with polyvinyl alcohol, and the plastic that obtains carried out moulding, make carrier after the dry and roasting.Can adopt the method for saturated dipping that active metal component is carried on 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.
There is no particular limitation to the flow direction of raw material in the hydrotreatment district in the present invention, and each hydrogenator both can also can be 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; Volume space velocity is preferably 0.10-0.45h during the liquid of heavy oil product
-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 the 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 the follow-up hydrogenation reactor ℃, more preferably 10-40 ℃.
According to the present invention; preferably; in the first hydrogenator, the macropore hydrogenation that the hydrogenation protecting catalyst in the hydrogenation protecting catalyst bed and macropore hydrogenation are processed in the beds is processed the admission space of catalyzer than being 2-60: 98-40, more preferably 10-30: 70-90.
Among the present invention, the setting of a plurality of beds can according to the practical situation adjustment, such as height, number and the position of each bed, preferably, can arrange as shown in Figure 1 in described a plurality of reactors.
Below, the flow process of bright the inventive method briefly 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, be disposed with three beds in a reactor, 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 the RG-10B; Be provided with a bed in the b reactor, be RDM-2B (Hydrodemetalation catalyst) bed; Be disposed with two beds in the c reactor, comprise RDM-2B bed and RMS-3B (Hydrobon catalyst) bed; Be provided with a bed in the d reactor, be RMS-1B (Hydrobon catalyst) bed; Be disposed with two beds in the e reactor, comprise RMS-1B bed and RSC-1 (removal of ccr by hydrotreating catalyzer) bed.
The loadings of catalyzer can adopt conventional amount used of the prior art in each bed, can be 1 such as the RG-10A, the RG-10B that load in a reactor and the volume ratio of RDM-2B (or CAT-A): 0.5-2: 4-20; Can all load the RDM-2B catalyzer in the b reactor; The RDM-2B of filling and the volume ratio of RMS-3B can be 2-5 in the c reactor: 1; All load the RMS-1B catalyzer in the d reactor; The RMS-1B that loads in the e reactor and the volume ratio of RSC-1 can be 2-5: 1.
And in the method for prior art, namely as shown in Figure 2, in a reactor, what the position suitable with CAT-A arranged is the RDM-2B bed.
Below, by embodiment method of the present invention is described in detail.
Equipment therefor is fixed bed hydrogenation Processing Test device as shown in Figure 1 in the embodiment of the invention, and 5 volumes of this device employing are 1 liter the top-down technical process of reactors in series, stock oil.
Used RG, RDM and RMS, RSC series weight, hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst and Hydrobon catalyst are that catalyzer Chang Ling branch office of China Petrochemical Industry 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;
All load the RDM-2B catalyzer in the b reactor;
The catalyzer of filling is RDM-2B and RMS-3B catalyzer from top to bottom in the c reactor, and the ratio of admission space is 75: 25;
All load the RMS-1B catalyzer in the d reactor;
Filling RMS-1B and RSC-1 catalyzer in the e reactor, the ratio of admission space is 80: 20.
It is the laboratory preparation that the macropore hydrogenation that adopts is processed catalyzer CAT-A, particularly, the preparation method of CAT-A-1 comprises: take by weighing macropore pseudo-boehmite dry glue powder (butt is 72 % by weight) 300 grams that Chang Ling catalyzer branch office produces, polyvinyl alcohol 12 grams, add Semen Maydis oil 12 grams after mixing, 360 milliliters of the aqueous solution, kneading 0.5 hour, the gained plastic, be extruded into the trilobal bar of ￠ 1.1-1.8 millimeter at double screw banded extruder, wet bar through 140 ℃ of dryings after 4 hours in 940 ℃ of roastings 2 hours, obtain carrier.Adopt general saturated dipping method, with reactive metal solution (ammonium metawolframate+nickel nitrate solution; Ammonium molybdate+ammonia soln+nickel nitrate solution), then impregnated carrier descended dry 2-3 hour at 80-120 ℃ respectively, at 350-480 ℃ of lower roasting 1-2 hour, namely made 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 that uses among the embodiment 1 that makes 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
3The carrier of CAT-A-1 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and take the weight of CAT-A-1 as benchmark, the content of carrier is 88 % by weight among the described CAT-A-1, 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 that uses among the embodiment 2 that makes 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
3The carrier of CAT-A-2 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and take the weight of CAT-A-2 as benchmark, the content of carrier is 90 % by weight among the described CAT-A-2, 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 that uses among the embodiment 3 that makes 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
3The carrier of CAT-A-3 is aluminum oxide and silicon oxide, and hydrogenation active metals is Mo and Ni, and take the weight of CAT-A-3 as benchmark, the content of carrier is 85 % by weight among the described CAT-A-3, 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 the BET method; Pore volume records by the BET method; Specific surface area records by the BET method; In the product after the 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.
Adopt equipment and process flow process shown in Figure 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 the 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 volume space velocity is 0.216h during liquid
-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 that obtains after the 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, satisfies 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 equipment and process flow process shown in Figure 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 volume space velocity is 0.142h during liquid
-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 the type of the catalyzer that loads in a, b, c, d and the e reactor among the embodiment 1 and each reactor of 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 that obtains after the 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, satisfies the requirement of RFCC charging.
Comparative Examples 1
According to the hydroprocessing condition identical with embodiment 2 residual oil raw material M is carried out residual hydrocracking, different is, adopts equipment and process flow process as shown in Figure 2, that is, the catalyzer RDM-2B of weight such as use to replace CAT-A-2 in a reactor.
The character of the product DP1 that obtains after the 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 equipment and process flow process shown in Figure 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 volume space velocity is 0.188h during liquid
-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 the type of the catalyzer that loads in a, b, c, d and the e reactor among the embodiment 1 and each reactor of 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 that obtains after the 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, satisfies the requirement of RFCC charging.
Embodiment 4
According to embodiment 1 described equipment and method residual oil raw material M is carried out hydrotreatment, different is that the temperature of all reactors is 380 ℃.
The character of the product P 4 that obtains after the 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, satisfies the requirement of RFCC charging.
Data by embodiment 1-3 and Comparative Examples 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 preferred implementation of the present invention.
Claims (14)
1. the hydroprocessing process of a heavy oil product; it is characterized in that; the method comprises; under the 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 these a plurality of hydrogenators; 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; comprise the hydrogenation protecting catalyst bed and the macropore hydrogenation processing beds that set gradually in the first hydrogenator; wherein; the mean pore size that described macropore hydrogenation is processed the macropore hydrogenation processing catalyzer in the beds is 10-40nm, and pore volume is 0.1-2cm
3/ g, specific surface area is 100-250m
2/ g.
2. method according to claim 1, wherein, described macropore hydrogenation is processed macropore hydrogenation in the 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, process the weight of catalyzer as benchmark take macropore hydrogenation, oxide compound in hydrogenation active metals, described macropore hydrogenation is processed the hydrogenation active metals component on this carrier of loading on of the carrier that contains the 80-97 % by weight in the catalyzer and 3-20 % by weight, described carrier is aluminum oxide and/or silicon oxide, and the hydrogenation active metals in the 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 among W, Mo, Ni and the Co.
5. method according to claim 4, wherein, described hydrogenation active metals is Mo and Ni, and process the weight of catalyzer as benchmark take macropore hydrogenation, oxide compound in hydrogenation active metals, the content that described macropore hydrogenation is processed Mo in the catalyzer is the 2-15 % by weight, and the content of Ni is the 1-5 % by weight.
6. method according to claim 1, wherein, the content of described heavy oil product studies on asphaltene is the 0.5-20 % by weight.
7. the described method of any one according to claim 1-6, wherein, the number of described a plurality of hydrogenators is 2-6, the number of the hydrogenation catalyst bed in each hydrogenator is 1-4.
8. the described method of any one according to claim 1-6, wherein, the flow direction according to described heavy oil product, comprise at least one the Hydrodemetalation catalyst bed, at least one Hydrobon catalyst bed and at least one the removal of ccr by hydrotreating beds that set gradually in the follow-up hydrogenation reactor, and each Hydrodemetalation catalyst bed, each Hydrobon catalyst bed and each removal of ccr by hydrotreating beds are arranged in the identical or different hydrogenator.
9. method according to claim 8 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 the described follow-up hydrogenation reactor; Be provided with Hydrodemetalation catalyst bed and/or Hydrobon catalyst bed in remaining reactor in the follow-up hydrogenation reactor.
10. method according to claim 9; wherein; the number of described a plurality of hydrogenators is 5; the flow direction according to described heavy oil product; be disposed with hydrogenation protecting catalyst bed and macropore hydrogenation in the first hydrogenator and process beds; be provided with the Hydrodemetalation catalyst bed in the second hydrogenator; be disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed in the 3rd hydrogenator; be provided with the Hydrobon catalyst bed in the 4th hydrogenator, be disposed with Hydrobon catalyst bed and removal of ccr by hydrotreating beds in last hydrogenator.
11. the described method of any one according to claim 1-6 and among the 9-10, 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 volume space velocity is 0.10-0.45h during the liquid of heavy oil product
-1
12. method according to claim 11, wherein, the temperature of reaction in described the first hydrogenator is higher than the temperature of reaction in the follow-up hydrogenation reactor.
13. method according to claim 12, wherein, the temperature of reaction in described the first hydrogenator is than the high 5-50 of the temperature of reaction in the follow-up hydrogenation reactor ℃.
14. according to claim 1-6, the described method of any one among 9-10 and the 12-13; wherein; in the first hydrogenator, the macropore hydrogenation that the hydrogenation protecting catalyst in the hydrogenation protecting catalyst bed and macropore hydrogenation are processed in the beds is processed the admission space of catalyzer than being 2-60: 98-40.
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| CN111100679A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
| CN111100676A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst grading method and application thereof in residual oil hydrotreating method |
| CN111100680A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst grading method and residual oil hydrotreating method |
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| CN111100680A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst grading method and residual oil hydrotreating method |
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