CN102311794B - Diesel hydrogenation method - Google Patents
Diesel hydrogenation method Download PDFInfo
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- CN102311794B CN102311794B CN201010220954.5A CN201010220954A CN102311794B CN 102311794 B CN102311794 B CN 102311794B CN 201010220954 A CN201010220954 A CN 201010220954A CN 102311794 B CN102311794 B CN 102311794B
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Abstract
The invention discloses a diesel hydrogenation method, which comprises: reacting a diesel raw material in a conventional liquid-phase circulating hydrogenation reactor, and subjecting the efflux to gas-liquid separation; after hydrogen dissolved in a liquid phase is saturated, delivering the liquid phase to a liquid phase circulating hydrogenation reactor for reaction; and after liquid-phase circulating oil passes through a hydrogen sulfide removal reactor, circulating the liquid-phase circulating oil to the entrance of a liquid phase hydrogenation reactor. In the method, the raw material oil is pretreated by gas-phase circulating hydrogenation, the sulfur content in the generated oil is reduced to 500 mu g/g; and after a liquid-phase hydrogenation reaction, the hydrogen sulfide removal content in the circulating oil is reduced; and after hydrogen sulfide is removed from the circulating oil by absorption, the hydrogen sulfide content can be reduced to below 100 mu g/g, a sulfur-containing environment required by a catalyst is maintained, the activity of the catalyst is not inhibited, and thus, smooth deep removal of aromatics and deep desulfuration reaction in the liquid-phase hydrogenation reactor are promoted.
Description
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, a kind of diesel oil liquid phase circulation hydrogen addition technology improves one's methods specifically.
Background technology
Along with the raising of people's environmental consciousness and the increasingly stringent of environmental regulation, produce and use fuel for cleaning vehicle more and more to become a kind of development trend.And for the cleaning of diesel oil, desulfurization and de-aromatic hydrocarbons are its keys cleaning.
In traditional hydrotreatment, need hydrogen to be transformed into liquid phase from vapor phase, in liquid phase it can be on catalyst surface with petroleum hydrocarbon in the impurity such as sulfocompound react.By with very a large amount of hydrogen with oil circulationly realize this point by beds.Oil and hydrogen are by beds, and absorption of hydrogen enters to be distributed in the oily film of catalyst surface.Because the requirement of hydrogen may be larger, so reactor is very large.In addition, in traditional reactor assembly, be difficult to control temperature of reactor, can pass through to control the feeding temperature of oily in reactor and hydrogen, but the temperature of inside reactor need cold hydrogen to regulate.And liquid phase circulation hydrogen addition technology solves these problems, in liquid phase circulation hydrogenation technique, hydrogen is first dissolved in stock oil by mixed hydrogen device, then enters reactor and react, and gas phase does not circulate, liquid phase effluent partly loops back reactor, like this, make liquid phase hydrogenation reactor size less, cost-saving, meanwhile, in reaction process without injecting cold hydrogen.Because liquid phase circulation hydrogenator size is less, be normally used in diesel hydrotreating unit transformation, at a liquid phase circulation hydrogenation pretreatment reaction device of the anterior increase of conventional gas phase circulation hydrogenator, but simultaneously, there is a problem in liquid phase circulation hydrogenation, be that the hydrogen sulfide that generates after hydrogenation of stock oil continues to circulate in oil, cause in turning oil hydrogen sulfide content higher, be unfavorable for that deep desulfuration, aromatic saturation reaction carry out.
CN200680018017.3 discloses a kind of liquid phase circulation method of hydrotreating, and the hydrogen sulfide in this patent in turning oil cannot remove, and deep desulfuration, de-virtue are had to considerable influence.
Summary of the invention
For hydrogen sulfide content in existing liquid phase circulation hydrogen addition technology liquid phase is too high, affect the problem that desulphurization reaction carries out, the invention provides a kind of improved diesel hydrogenation process.
Diesel hydrogenation process of the present invention comprises following content:
(1) diesel raw material is mixed with hydrogen and after process furnace heating, is entered the first reactor and react, and to remove most of sulfocompound, described the first reactor is gas phase circulation hydrogenator;
(2) reaction effluent of step (1) enters gas-liquid separation device, and gained gas phase loops back the first reactor after washing hydrogen sulfide;
(3) liquid phase that step (2) obtains enters gas liquid mixer, after saturated dissolved hydrogen, enters the second reactor and reacts, and with deep desulfuration, de-aromatic hydrocarbons, described the second reactor is liquid phase circulation hydrogenator;
(4) part in the reaction effluent that step (3) obtains enters depriving hydrogen sulphide reactor, loops back the second reactor inlet after adsorbing and removing hydrogen sulfide.
According to diesel hydrogenation process provided by the invention, the another part in the reaction effluent that step (3) obtains directly goes out device as clean diesel product.
Depriving hydrogen sulphide reactor described in step (4) can comprise single reactor, also can comprise two reactors in parallel.After the absorption of sorbent material in one of them adsorptive reactor is saturated, switches and use another adsorptive reactor, the reactor of saturated adsorption carries out the regenerative operation of sorbent material.
In diesel hydrogenation process of the present invention, described gas liquid mixer can be selected static mixer or dynamic mixer, static mixer is by the different shapes hybrid element arranging in mixing tank, mass-transfer efficiency between fluid is improved greatly, static mixing implement body is as static mixers such as the SV type of domestic-developed, SL type, SH type, SX type, SK types, the static mixers such as the ISG type of external exploitation, SMV type.The moving member that dynamic mixer arranges by hybrid instrument, improves the mass-transfer efficiency between fluid, concrete as star gear shape mixing tank, sound gear ring shape mixing tank, crescent moon trough mixer or ball-and-socket type mixing tank etc.
In diesel hydrogenation process of the present invention, the first reactor (being gas phase circulation hydrogenator) and the second reactor (being liquid phase circulation hydrogenator) can be used identical or different Hydrobon catalyst, preferably use different Hydrobon catalysts.Hydrobon catalyst can be used commercially available prod as required, also can be by the conventional knowledge preparation in this area.While using different Hydrobon catalysts, preferably in second reaction zone, use the relatively high Hydrobon catalyst of hydrogenation activity, desulphurizing activated relatively high Hydrobon catalyst is used in the first reaction zone.In depriving hydrogen sulphide reactor after the second reactor, adsorption desulfurize hydrogen catalyst is housed.The selectivity of Hydrobon catalyst is main relevant to contained active metal component, in general active metal component is higher containing denitrification activity and the aromatic saturation performance of the Hydrobon catalyst of W and/or Ni, and active metal component is desulphurizing activated higher containing the Hydrobon catalyst of Mo and/or Co.Adsorbing and removing hydrogen sulfide catalyzer can be used commercially available prod as required, also can be by the conventional knowledge preparation in this area.Conventionally select alkaline-earth metal catalyst.
In diesel hydrogenation process of the present invention, the operational condition that the first reactor adopts is as follows: 280 ℃～400 ℃ of temperature of reaction, preferably 300 ℃～380 ℃, reaction pressure 3.0MPa～10.0MPa, preferred 4.0MPa～8.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1, preferred 1.5h
-1～4.0h
-1, hydrogen to oil volume ratio 100～1000, preferably 400～800.The operational condition of second reaction zone is specific as follows: 300 ℃～420 ℃ of temperature of reaction, preferably 320 ℃～400 ℃, reaction pressure 3.0MPa～10.0MPa, preferred 4.0MPa～8.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1, preferred 1.5h
-1～4.0h
-1.The operational condition of depriving hydrogen sulphide reactor is specific as follows: 280 ℃～400 ℃ of temperature of reaction, preferably 300 ℃～380 ℃, reaction pressure 3.0MPa～10.0MPa, preferred 4.0MPa～8.0MPa, volume space velocity 0.5h during liquid
-1～6.0h
-1, preferred 1.0h
-1～3.0h
-1.Wherein volume space velocity can be the same or different during the liquid in differential responses district, and temperature of reaction can be the same or different.Actual conditions can require to determine according to feedstock property and quality product.
In the present invention, described " gas phase circulation " refers in conventional fixed bed hydrogenation technological process, in order to control the temperature of reaction of beds and to avoid catalyst carbon deposit inactivation, conventionally adopt larger hydrogen to oil volume ratio, after completing, hydrogenation reaction must have a large amount of hydrogen more than needed, these hydrogen more than needed continue the hydrogen feed as reaction after conventionally mixing with new hydrogen after circulating hydrogen compressor supercharging, and hydrogen recycle is used.
The present invention is added in liquid phase circulation hydrogenator after conventional gas phase circulation hydrogenator and forms combination unit, to carry out deep desulfuration, de-virtue, adopts the hydrogen sulfide in adsorbing and removing turning oil simultaneously.Conventional gas phase circulation hydrogenator above carries out pre-treatment to stock oil, and the sulphur content that makes to generate in oil is down to below 500 μ g/g, and the raw materials quality of liquid phase hydrogenation reactor processing improves like this; The corresponding reduction of hydrogen sulfide content after liquid-phase hydrogenatin reaction in turning oil, is further removing after hydrogen sulfide by depriving hydrogen sulphide reactor, and the hydrogen sulfide content in turning oil is down to and is less than 100 μ g/g.Such hydrogen sulfide content can be ignored deep hydrodesulfurizationof reaction and hydrogenation aromatics-removing reaction inhibition in liquid phase circulation hydrogenator, can make like this deep hydrodesulfurizationof of diesel oil reaction in liquid phase circulation hydrogenator be carried out smoothly.
Accompanying drawing explanation
Fig. 1 is the principle process schematic diagram of diesel hydrogenation process of the present invention.
Embodiment
In diesel oil hydrogenation technique of the present invention, the hydrogenation catalyst of employing refer to there is hydrogenating desulfurization, the non-noble metal hydrogenation catalyst of hydrodenitrification, aromatic saturation function, the function of catalyzer can stress some aspect.This non-precious metal catalyst generally exists with oxidation state form before use, need to carry out prevulcanized, makes non-noble metal oxide be converted into sulfide and just has reactive behavior, and therefore, non-precious metal catalyst in use will keep sulphided state.
The present invention's hydrogenation catalyst used can adopt conventional diesel oil hydrofining catalyst, and general YiⅥ B family and/or group VIII metal are active ingredient, take aluminum oxide or silicon-containing alumina as carrier.The weight of catalyzer of take is benchmark, and group VIB metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～650m
2/ g, pore volume is 0.15～0.8ml/g.Group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The sorbent material using in depriving hydrogen sulphide reactor of the present invention can be used commercially available prod as required, also can be by the conventional knowledge preparation in this area.Generally take alkaline-earth metal as active ingredient, and carrier can be natural inorganic clay or gac, and wherein the content of alkaline earth metal compound is 50wt%～90wt%, and natural inorganic clay or gac content are 10wt%～50wt%.
As shown in Figure 1, diesel raw material 1 with after hydrogen from pipeline 2 mixes, and flow to into the first reactor 3, is carried out hydrogenation reaction downwards after heat exchange under sulphided state Hydrobon catalyst exists in principle technical process of the present invention; Reaction effluent enters gas-liquid separator 4 and carries out gas-liquid separation, and gas phase loops back the first reactor 3 through pipeline 2, and liquid phase enters mixed hydrogen tank 6 through pipeline 5 fully mixes with new hydrogen 7, and saturated dissolved hydrogen enters the second reactor 9 by pipeline 8; Reaction mass enters depriving hydrogen sulphide reactor 12 through the second reactor 9 reaction rear portions through pipeline 11, remove the hydrogen sulfide being dissolved in oil, effluent is got back to mixed hydrogen tank 6 through recycle pump 13 circulations and through pipeline 14 and pipeline 5, and another part effluent directly removes products pot by pipeline 10.
Below by embodiment, the present invention program and effect are described.
Adopt flow process of the present invention as Fig. 1.In following examples, use nickel-tungsten-molybdenum type Hydrobon catalyst, the composition of catalyzer and character are in Table 1, and feedstock property used is listed in table 3 in Table 2, embodiment 1～4 processing condition used, and the evaluation result of embodiment 1～4 is in Table 4.
Composition and the main character of table 1 embodiment used catalyst
| Project | Catalyst A | Catalyst B |
| Chemical constitution, quality % | ||
| MoO 3 | 6.2 | 19.8 |
| NiO | 12.3 | - |
| CoO | - | 3.7 |
| WO 3 | 15.2 | - |
| Carrier | Aluminum oxide | Aluminum oxide |
| Physico-chemical property | ||
| Pore volume, ml/g | 0.45 | 0.41 |
| Specific surface area, m 2/g | 265 | 206 |
Table 2 stock oil character
| Stock oil | Stock oil |
| Density, g/cm 3 | 0.8569 |
| Boiling range, ℃ | 199～379 |
| Sulphur content, μ g/g | 8800 |
| Nitrogen content, μ g/g | 316 |
| Aromaticity content, wt% | 21.5 |
Table 3 embodiment 1～4 operational condition that adopts
Table 4 embodiment 1～4 evaluation result
| |
|
Embodiment 3 | |
|
| Sulphur content, μ g/g | 348 | 106 | 136 | 8 |
| Aromaticity content, wt% | 18.6 | 17.3 | 17.5 | 9.2 |
Claims (11)
1. a diesel hydrogenation process, comprises the following steps:
(1) diesel raw material is mixed with hydrogen and after process furnace heating, is entered the first reactor and react, and described the first reactor is gas phase circulation hydrogenator;
(2) reaction effluent that step (1) obtains enters gas-liquid separation device, and gained gas phase loops back the first reactor after washing hydrogen sulfide;
(3) liquid phase that step (2) obtains enters gas liquid mixer, after saturated dissolved hydrogen, enters the second reactor and reacts, and described the second reactor is liquid phase circulation hydrogenator;
(4) part in the reaction effluent that step (3) obtains enters depriving hydrogen sulphide reactor, loops back the second reactor inlet after adsorbing and removing hydrogen sulfide.
2. according to processing method claimed in claim 1, it is characterized in that, the depriving hydrogen sulphide reactor described in step (4) comprises a reactor or comprises two reactors in parallel.
3. according to processing method claimed in claim 2, it is characterized in that, described depriving hydrogen sulphide reactor comprises two reactors, after the absorption of sorbent material in one of them adsorptive reactor is saturated, switch and use another adsorptive reactor, the reactor of saturated adsorption carries out the regenerative operation of sorbent material.
4. according to processing method claimed in claim 1, it is characterized in that, the first reactor and the second reactor are used identical or different Hydrobon catalyst.
5. according to processing method claimed in claim 4, it is characterized in that, the first reactor and the second reactor are used different Hydrobon catalysts, the first reactor is used desulphurizing activated relatively high Hydrobon catalyst, and the second reactor is used the relatively high Hydrobon catalyst of hydrogenation activity.
6. according to the processing method described in claim 4 or 5, it is characterized in that, consisting of of described Hydrobon catalyst: the weight of catalyzer of take is benchmark, and group VIB metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15wt% with oxide compound; Its character is as follows: specific surface is 100～650m
2/ g, pore volume is 0.15～0.8ml/g.
7. according to processing method claimed in claim 1, it is characterized in that, the processing condition of described the first reactor are: 280 ℃～400 ℃ of temperature of reaction, reaction pressure 3.0MPa～10.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio 100～1000; The processing condition of second reaction zone are: 300 ℃～420 ℃ of temperature of reaction, reaction pressure 3.0MPa～10.0MPa, volume space velocity 1.0h during liquid
-1～6.0h
-1; The processing condition of depriving hydrogen sulphide reactor are: 280 ℃～400 ℃ of temperature of reaction, reaction pressure 3.0MPa～10.0MPa, volume space velocity 0.5h during liquid
-1～6.0h
-1.
8. according to processing method claimed in claim 7, it is characterized in that, the processing condition of described the first reactor are, 300 ℃～380 ℃ of temperature of reaction, reaction pressure 4.0MPa～8.0MPa, volume space velocity 1.5h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio 400～800; The processing condition of second reaction zone are, 320 ℃～400 ℃ of temperature of reaction, reaction pressure 4.0MPa～8.0MPa, volume space velocity 1.5h during liquid
-1～4.0h
-1; The processing condition of depriving hydrogen sulphide reactor are, 300 ℃～380 ℃ of temperature of reaction, reaction pressure 4.0MPa～8.0MPa, volume space velocity 1.0h during liquid
-1～3.0h
-1.
9. according to processing method claimed in claim 1, it is characterized in that, the adsorption desulfurize hydrogen catalyst using in described depriving hydrogen sulphide reactor be take alkaline-earth metal as active ingredient, carrier is natural inorganic clay or gac, wherein the content of alkaline earth metal compound is 50wt%～90wt%, and natural inorganic clay or gac content are 10wt%～50wt%.
10. according to processing method claimed in claim 1, it is characterized in that, the gas liquid mixer described in step (3) is selected static mixer or dynamic mixer.
11. according to processing method claimed in claim 10, it is characterized in that, described static mixer is SV type, SL type, SH type, SX type, SK type, ISG type or SMV type static mixer; Described dynamic mixer is star gear shape mixing tank, sound gear ring shape mixing tank, crescent moon trough mixer or ball-and-socket type mixing tank.
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| CN103773475B (en) * | 2012-10-24 | 2015-09-02 | 中国石油化工股份有限公司 | A kind of gas phase, Solution-Phase Combinatorial hydrogenation method |
| CN103773471B (en) * | 2012-10-24 | 2015-08-12 | 中国石油化工股份有限公司 | A kind of gas phase, liquid phase Unionfining technological process |
| CN103789016B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Combined distillate oil hydroprocessing method |
| CN103789030B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Hydrocracking method of low-sulfur raw materials |
| CN104927910B (en) * | 2014-03-21 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of diesel oil hydro-upgrading method and a kind of hydrogenation reaction device |
| CN106147841B (en) * | 2015-04-22 | 2017-11-14 | 中国石化工程建设有限公司 | A kind of Heavy oil hydrogenation method |
| CN109679682B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Hydrogen dissolving equipment and hydrogen dissolving method |
| CN109679690B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation system and liquid-phase hydrogenation method |
| CN109679684B (en) * | 2017-10-19 | 2020-09-11 | 中国石油化工股份有限公司 | Liquid phase hydrogenation reaction system and method |
| CN114433058B (en) * | 2020-10-31 | 2023-11-07 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst composition |
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| CN1670134A (en) * | 2005-04-25 | 2005-09-21 | 石油大学(北京) | Method for refining catalytic gasoline |
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| US7569136B2 (en) * | 1997-06-24 | 2009-08-04 | Ackerson Michael D | Control system method and apparatus for two phase hydroprocessing |
| CN100443571C (en) * | 2005-09-28 | 2008-12-17 | 中国石油化工股份有限公司 | Diesel fraction deep desulfurization and decoloring hydrogenation |
| CN1986748B (en) * | 2005-12-23 | 2010-04-14 | 中国石油化工股份有限公司 | Diesel oil fraction overhydrogenating modification process |
| US8999141B2 (en) * | 2008-06-30 | 2015-04-07 | Uop Llc | Three-phase hydroprocessing without a recycle gas compressor |
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| CN1670134A (en) * | 2005-04-25 | 2005-09-21 | 石油大学(北京) | Method for refining catalytic gasoline |
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