CN103789004B - Hydrodemetalization process - Google Patents
Hydrodemetalization process Download PDFInfo
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- CN103789004B CN103789004B CN201210427733.4A CN201210427733A CN103789004B CN 103789004 B CN103789004 B CN 103789004B CN 201210427733 A CN201210427733 A CN 201210427733A CN 103789004 B CN103789004 B CN 103789004B
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Abstract
The invention discloses a hydrodemetalization process. Raw oil and hydrogen in a down flow mode are sent into a reactor for hydrodemetalization reaction; and when the metal removal rate drops to 50-65%, the raw oil and hydrogen are switched into an up flow mode and sent into the reactor to continue the hydrodemetalization reaction. Raw oil comprises a vacuum residual oil, atmospheric pressure residual oil, wax oil or residuum raw material blended with part of cutback oil. The lower part of the reactor uses an up flow distribution plate, and the upper part uses a down flow distribution plate. The method prolongs the running period of the device while keeping the high metal removal rate, and can prevent or solve the hot spot problems.
Description
Technical field
The present invention relates to a kind of hydrodemetallation (HDM) processing method, relate in particular to a kind of heavy oil hydrogenation demetal processing method.
Background technology
As everyone knows, the reaction in heavy-oil hydrogenation treating processes mainly comprises the hydrocracking of the saturated and various hydro carbons of hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), alkene and aromatic hydrogenation.As a whole, heavy-oil hydrogenation reaction is thermopositive reaction, and hydrodemetallation (HDM) reaction comparatively relaxes, and desulphurization reaction and denitrification reaction belong to strong exothermal reaction.Most widely used general, the most ripe technique of industrial heavy-oil hydrogenation process is fixed bed.
CN1197105A discloses a kind of method of hydrocarbonaceous raw material of hydrotreatment metallic pollution, boiling temperature>=370 DEG C of this hydrocarbonaceous raw material at least 60% (weight), the method comprises: in the presence of hydrogen gas, at elevated temperature and pressure, make this raw material and the first catalyzer, second catalyzer contacts with the one or more beds in the 3rd catalyzer, wherein, first catalyzer comprises VI race and/or VIII hydrogenation metal component carries on an inorganic, its pore volume of at least 40% is in the scope of aperture 17-25nm, surface-area is at 100-160m
2in the scope of/g, second catalyzer comprises VI race and/or VIII hydrogenation metal component is loaded in inorganic oxide support, and its pore volume of at least 40% is in the scope of aperture 3-17nm, and surface-area is at 160-350m
2in the scope of/g, 3rd catalyzer comprises VI race and/or VIII hydrogenation metal component carries on an inorganic, and its pore volume of at least 40% is in the scope of aperture 17-25nm, and surface-area is at 100-160m
2in the scope of/g, wherein, when contaminant metals deposition is less than 5% (weight), the metal removal activity of the 3rd catalyzer is at least 1.5 times of the first catalyzer.The method effectively can remove the metal in hydrocarbonaceous raw material.
CN01114167 discloses a kind of method of catalyst for hydrotreatment of residual oil, the principle that the method adopts the activity along logistics direction catalyzer to reduce gradually, change the grating of desulfurization catalyst, denitrification catalyst bed, and between bed, set up a transition catalyst bed, make the temperature rise of catalyzer each bed more steady.Compared with traditional method, the method catalyst stability is good, and each beds temperature rise easily controls, and greatly reduces hydrogen consumption.
CN94117660 discloses a kind of method of hydrogenation demetalization.High-voidage granules of catalyst and low voidage granules of catalyst, mainly in fixed-bed reactor, are carried out the physical mixed of different ratio, realize the smooth change of high-voidage material to low Void-rich material by the method, and improve the filter effect evenly changed.The method can improve the deposition of the impurity such as Fe, Ca in catalyzer outside.
CN00807042 discloses the up-flow reactor system of layered catalyst bed.This reactive system mainly considers that raw material and hydrogen upwards flow, and cause catalyzer to produce certain expansion, rate of expansion is no more than 5%.Compared with fixed bed, catalyzer expand flow distribution can be avoided to bring focus, but due to hydrogen-oil ratio lower, cause new focus thereupon bringing due to scarce hydrogen.
In aforesaid method, although can raising hydrodemetallation (HDM) efficiency in various degree, the life cycle of Hydrodemetalation catalyst be general shorter, and major cause is that fixed bed downflow system and upflowing all cannot suppress when there is focus, and along with running period extends, demetalization degradation.
Summary of the invention
For the deficiencies in the prior art, the present invention discloses a kind of hydrodemetallation (HDM) processing method.The method, under the condition keeping high demetallization per, extends the running period of device, can prevent or solve hot issue simultaneously.
A kind of hydrodemetallation (HDM) processing method, stock oil and hydrogen employing downflow system enter reactor and carry out hydrodemetallation (HDM) reaction, when demetallization per is down to 50 ~ 65%, switch stock oil and hydrogen, adopt upflowing to enter reactor and proceed hydrodemetallation (HDM) reaction.
Stock oil described in the inventive method comprises vacuum residuum, long residuum, wax oil or mixes refining part of dilution oil residual oil raw material etc.
Reactor lower part described in the inventive method adopts upflowing distribution plate, and top adopts downflow system distribution plate.
Hydrodemetalation catalyst described in the inventive method is seated in the middle part of reactor, and the protective material of 10 ~ 30% of this reactor charge cumulative volume is respectively loaded in the top of Hydrodemetalation catalyst and bottom.Protective material and catalyst for demetalation are regular industrial applications catalyst, as: the catalyzer of Fushun Petrochemical Research Institute's exploitations such as FZC-102K, FZC-11UH.Catalyst shape is preferably spherical, as: five tooth balls, seven apertures in the human head ball or ellipsoid etc.Catalyzer has at least 60% aperture to be greater than 15nm, and specific surface area is 80 ~ 150 m
2g
-1, pore volume is greater than 0.6 mLg
-1.Catalyst activity metal is VI B race and VIII race's metal; wherein protectant VI B race weight metal content is 0 ~ 4.0%; VIII race's weight metal content is 0 ~ 1.0%, and VI B race weight metal content of catalyst for demetalation is 5 ~ 12.0%, VIII race's weight metal content is 2 ~ 4%.
In the inventive method, downflow system hydrodemetallation (HDM) processing condition are as follows: temperature of reaction: 330 ~ 450 DEG C, hydrogen dividing potential drop: 14 ~ 22Mpa, volume space velocity: 0.1 ~ 2.0h
-1, hydrogen to oil volume ratio: 700 ~ 1500.The 900h-3500h demetallization per that operates at the process conditions is down to 50 ~ 65%, and upflowing now can be switched to react.
In the inventive method, upflowing hydrodemetallation (HDM) processing condition are as follows: temperature of reaction: 330 ~ 450 DEG C, hydrogen dividing potential drop: 14 ~ 22Mpa, volume space velocity: 0.1 ~ 2.0h
-1, hydrogen to oil volume ratio: 300 ~ 800.
The mode that the inventive method adopts downflow system and upflowing to combine carries out the hydrodemetallation (HDM) treating processes of mink cell focus, effectively can delay high temperature hotspot to produce, slow down the lift velocity of beds pressure drop, the catalyzer of different sites in beds all can be fully used, thus realize residual hydrogenation equipment long-term operation, and when hot spot phenomenon appears in downflow system, upflowing expansion can be utilized to solve or delay focus generation.After switching the feeding manner of stock oil in the inventive method, hydrodemetallation (HDM) efficiency obtains certain recovery and raising.
Embodiment
Below in conjunction with embodiment, a kind of hydrodemetallation (HDM) processing method of the present invention is further detailed, but does not therefore limit the present invention.
Embodiment 1
Stock oil and hydrogen adopt downflow system to enter reactor, when demetallization per is down to 60%, switch stock oil and hydrogen, adopt upflowing to enter reactor and proceed hydrodemetallation (HDM) reaction.Described reactor lower part and top are separately installed with upflowing distribution plate and downflow system distribution plate, load protective material and Hydrodemetalation catalyst between distribution plate.Protective material and Hydrodemetalation catalyst are the trade mark that Fushun Petrochemical Research Institute produces is protective material and the Hydrodemetalation catalyst of FZC-102K and FZC-11UH.Hydrodemetalation catalyst is seated in middle part, and admission space is 140ml, and protective material is seated in the two ends up and down of Hydrodemetalation catalyst, and admission space is 30ml.Catalyst property is in table 1, and stock oil character is in table 2, and processing condition are in table 3, and demetallization per is in table 4.
Implementation column 2
Stock oil and hydrogen adopt downflow system to enter reactor, when demetallization per is down to 54%, switch stock oil and hydrogen, adopt upflowing to enter reactor and proceed hydrodemetallation (HDM) reaction.Described reactor lower part and top are separately installed with upflowing distribution plate and downflow system distribution plate, load protective material and Hydrodemetalation catalyst between distribution plate.Protective material and Hydrodemetalation catalyst are the trade mark that Fushun Petrochemical Research Institute produces is protective material and the Hydrodemetalation catalyst of FZC-10UH and FZC-11UH.Hydrodemetalation catalyst is seated in middle part, and admission space is 140ml, and protective material is seated in the two ends up and down of Hydrodemetalation catalyst, and admission space is 50ml.Catalyst property is in table 1, and stock oil character is in table 2, and processing condition are in table 3, and demetallization per is in table 4.
Comparative example 1
Do not switch, all the other are with embodiment 1.
Contrast row 2
Do not switch, all the other are with embodiment 2.
Table 1 catalyzer physico-chemical property
| The catalyzer trade mark | FZC-11UH | FZC-10UH |
| Shape | Spherical | Spherical |
| Specific surface/m 2.g -1 | 150 | 145 |
| Total pore volume/cm 3.g -1 | 0.6 | 0.62 |
| Chemical constitution/m% | ||
| MoO 3 | 11 | 6 |
| NiO | 3 | 1 |
Table 2 stock oil character
| Stock oil character | The normal slag in the Middle East |
| S，w% | 4.0 |
| Ni，ug/g | 30.0 |
| V，ug/g | 120.0 |
Table 3 test conditions
Table 4 demetalization performance comparison
As can be seen from Table 4, in reference example, catalyzer is along with extending runtime, and demetalization stable performance is got off, and progressively reduces.And in reference example after changing upflowing charging into, demetalization performance obtains certain recovery.Illustrate and can improve catalyst system demetalization performance according to present method.
Claims (8)
1. a hydrodemetallation (HDM) processing method; it is characterized in that: stock oil and hydrogen employing downflow system enter reactor and carry out hydrodemetallation (HDM) reaction; when demetallization per is down to 50 ~ 65%; switch stock oil and hydrogen; adopt upflowing to enter reactor and proceed hydrodemetallation (HDM) reaction; described Hydrodemetalation catalyst is seated in the middle part of reactor, and the protective material of 10 ~ 30% of this reactor charge cumulative volume is respectively loaded in the top of Hydrodemetalation catalyst and bottom.
2. method according to claim 1, is characterized in that: described stock oil comprises vacuum residuum, long residuum, wax oil.
3. method according to claim 1, is characterized in that: described reactor lower part adopts upflowing distribution plate, and top adopts downflow system distribution plate.
4. method according to claim 1, is characterized in that: the shape of protective material and catalyst for demetalation is five tooth balls, seven apertures in the human head ball or ellipsoid.
5. method according to claim 1, is characterized in that: protective material and catalyst for demetalation have at least 60% aperture to be greater than 15nm, and specific surface area is 80 ~ 150 m
2g
-1, pore volume is greater than 0.5 mLg
-1.
6. method according to claim 1; it is characterized in that: the active ingredient of protective material and catalyst for demetalation is VI B race and VIII race's metal; wherein protectant VI B race weight metal content is 0 ~ 4.0%; VIII race's weight metal content is 0 ~ 1.0%; VI B race weight metal content of catalyst for demetalation is 5 ~ 12.0%, VIII race's weight metal content is 2 ~ 4%.
7. method according to claim 1, is characterized in that: downflow system hydrodemetallation (HDM) processing condition are as follows: temperature of reaction: 330 ~ 450 DEG C, hydrogen dividing potential drop: 14 ~ 22Mpa, volume space velocity: 0.1 ~ 2.0h
-1, hydrogen to oil volume ratio: 700 ~ 1500.
8. method according to claim 1, is characterized in that: upflowing hydrodemetallation (HDM) processing condition are as follows: temperature of reaction: 330 ~ 450 DEG C, hydrogen dividing potential drop: 14 ~ 22Mpa, volume space velocity: 0.1 ~ 2.0h
-1, hydrogen to oil volume ratio: 300 ~ 800.
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Citations (6)
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|---|---|---|---|---|
| CN1335365A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy oil and residual oil treating process |
| EP1185599A1 (en) * | 1999-04-13 | 2002-03-13 | Chevron U.S.A. Inc. | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
| JP3978064B2 (en) * | 2002-03-27 | 2007-09-19 | 日本ケッチェン株式会社 | Two-stage hydroprocessing method for heavy hydrocarbon oil |
| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| JP2011042734A (en) * | 2009-08-20 | 2011-03-03 | Idemitsu Kosan Co Ltd | Method for producing highly aromatic hydrocarbon oil |
| CN103773451A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Fixed bed residue oil hydrogenating method |
-
2012
- 2012-11-01 CN CN201210427733.4A patent/CN103789004B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1185599A1 (en) * | 1999-04-13 | 2002-03-13 | Chevron U.S.A. Inc. | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
| CN1335365A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy oil and residual oil treating process |
| JP3978064B2 (en) * | 2002-03-27 | 2007-09-19 | 日本ケッチェン株式会社 | Two-stage hydroprocessing method for heavy hydrocarbon oil |
| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| JP2011042734A (en) * | 2009-08-20 | 2011-03-03 | Idemitsu Kosan Co Ltd | Method for producing highly aromatic hydrocarbon oil |
| CN103773451A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Fixed bed residue oil hydrogenating method |
Non-Patent Citations (1)
| Title |
|---|
| "渣油加氢技术的最新进展及技术路线选择";李立权;《炼油技术与工程》;20100430;第40卷(第4期);第1-5页 * |
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