CN102533328A - Inferior gasoline fraction hydrotreatment process method - Google Patents
Inferior gasoline fraction hydrotreatment process method Download PDFInfo
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- CN102533328A CN102533328A CN2010106152476A CN201010615247A CN102533328A CN 102533328 A CN102533328 A CN 102533328A CN 2010106152476 A CN2010106152476 A CN 2010106152476A CN 201010615247 A CN201010615247 A CN 201010615247A CN 102533328 A CN102533328 A CN 102533328A
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Abstract
The invention discloses an inferior gasoline fraction hydrotreatment process method, which comprises the following steps of: (1) directly mixing an inferior gasoline fraction and recycle oil-recycle hydrogen heated by a heating furnace in a step (3), making the temperature of the mixture reach alkadiene removal reaction temperature, and introducing the mixture into a hydrogenation pretreatment reactor; (2) directly mixing reaction effluent of the hydrogenation pretreatment reactor and the recycle oil-recycle hydrogen heated by the heating furnace in the step (3), making the mixture reach temperature required by the inlet of a hydrotreatment reactor, and introducing the mixture into the hydrotreatment reactor; and (3) introducing reaction effluent of the hydrotreatment reactor into a separation system, separating out hot recycle oil without temperature reduction, separating out the hydrogenated gasoline fraction and gas phase through temperature reduction, taking the gas phase as recycle hydrogen, mixing the hot recycle oil and the recycle gas, heating the mixture in the heating furnace, and feeding to the step (1) and the step (2) for recycle. Compared with the prior art, the method can effectively solve the problem of coking of an inferior gasoline fraction hydrotreatment device.
Description
Technical field
The present invention relates to a kind of inferior patrol cut fraction hydrogenation treatment process method, particularly improve the inferior patrol cut fraction hydrogenation treatment unit method in fortune cycle.
Background technology
Along with crude oil constantly becomes improving constantly of heavy and the level of crude oil processing; The status that is processed in the oil refining process of heavy oil product becomes more and more important; Delay coking process is simple because of technology, investment is low, more and more becomes the important means that oil refining enterprise is handled residual oil, improved yield of light oil.The main liquid product coking distillate of delay coking process comprises coking naphtha and coker gas oil.Because foreign matter contents such as coking distillate unsaturated hydrocarbons, sulphur, nitrogen are all higher; And stability is poor; Be difficult to charging as subsequent processing; Must can be used as feed ethylene, synthetic ammonia material after improving its stability and removing impurity widely, reform and expect and chemical industry light oil use and vehicle fuel etc. through unifining.
Catalytic cracking also is one of important means of heavy oil and residual oil deep processing, be that with the key distinction of delayed coking the raw material that catalytic cracking is handled is better than processing raw material of delayed coking, or raw material carries out hydrogenation pre-treatment etc.Similar with delayed coking, the product that catalytic cracking process obtains such as gasoline fraction, diesel oil distillate etc. have unsaturated hydrocarbons content height, contain impurity such as a certain amount of sulphur, nitrogen simultaneously.
In the industrial production, the gasoline fraction that also has some thermal cracking process to obtain also has above-mentioned similar character.Gasoline fractions such as above-mentioned coker, catalytically cracked gasoline cut, pyrolysis gasoline cut are second-rate, are referred to as the inferior patrol cut in this patent.
Industrial application shows, one of subject matter that perplexs the running of inferior patrol cut fraction hydrogenation device for a long time is to raise and compelled the shut-down in the hydrogenation catalyst bed lamination difference SP, and its major cause is due to the polyreaction that causes of the diolefine in the raw oil.Materials such as the rare hydrocarbon in the raw material, two rare hydrocarbon are when temperature is higher; Be prone to take place Diels-Alder cyclization and polyreaction formation macromolecular organic compound; And further condensation green coke; These green coke reactions mainly concentrate on positions such as high-temperature heat-exchanging, process furnace and reactor head, cause production unit to need frequent shutdowns to handle, and cause to ordinary production to have a strong impact on.
Existing inferior patrol heats up in a steamer in the hydrogen addition technology; A general reactor drum or two tandem reactors of adopting, reaction temperature in generally at the hydrogenation activity of competence exertion catalyzer more than 220 ℃, take off the impurity reaction to reach effective hydrogenation; Add the bigger temperature rise (can produce the temperature rise about 140 ℃) that hydrogenation reaction produces like the coker hydrogenation; Be easy to make the diolefine generation coking reaction in the raw material, the blocking catalyst bed increases reactor pressure decrease; Device running period is shortened in the processing of need stopping work when serious greatly.In general, reaction high temperature elute need with the raw material heat exchange to reclaim and to utilize heat, in interchanger and process furnace, the diolefine in the coking naphtha raw material etc. also is easy to coking, the initial stage can be reduced heat exchange efficiency, the later stage processing of need stopping work.Along with the device prolongation of runtime, quality product descends and can only compensate through improving reactor inlet temperature, causes the aggravation of beds top diolefine condensation green coke, causes reacting system pressure to fall rising, influences the long-term operation of device.Though interchanger and furnace outlet temperature of charge are also not really high, heat exchanger wall and furnace wall temperature are very high; Stove hall temperature like common hydrogenation unit process furnace can reach 500 ℃; High can reach more than 600 ℃, and therefore, the coking problem of interchanger and process furnace is very serious.Sometimes the green coke material can get in the reactor drum with following of material in interchanger and the process furnace, is deposited on reactor catalyst bed top, has further accelerated the obstruction speed of reactor catalyst bed.
How effectively eliminating the coking problem of inferior patrol cut in hydrotreater, is to improve inferior patrol to heat up in a steamer the hydrogenation unit key point of running period.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, and described is that hydrogenation and removing diolefine under more shallow hydroconversion condition is to guarantee less loss of octane number with the pre-sulfide catalyst series connection of two different activities and variable grain diameter.Because two kinds of catalyzer can be put into a reactor drum or two reactor drums, can not guarantee that catalyzer reacts under lower temperature of reaction, therefore can not delay raw material and generate oil heat exchanger shell side and heating furnace tube coking degree.
US4,113,603 reports use two sections hydrofinishing process to handle diolefine and sulfide in the pyrolysis gasoline, and the catalyzer of first section nickeliferous-tungsten of use is removed mercaptan, and second section is used precious metals palladium catalyst to remove diolefine, and technology is comparatively complicated.Because the not anti-sulphur of noble metal catalyst, and temperature of reaction is very low, is inappropriate for coking naphtha hydrogenation technique process.
CN1084547A has introduced a kind of hydrodesulfurizationof of naphtha dechlorination dearsenification and the saturated process for purification of aromatic hydrocarbons.Though can aromatic hydrocarbons be reduced to less than below 1%, because dearomatization catalyst is nickel or noble metal catalyst,, must adopt two-stage method technology for preventing the catalyzer sulfur poisoning, flow process is complicated, and operational condition is comparatively harsh.
CN200710012091.0 discloses a kind of method that improves running period of hydrogenation plant for poor petroleum naphtha; Before process furnace, set up a reactor drum; Inferior naphtha at first carries out selectivity diene hydrogenation reaction under lower temperature of reaction, and then carrying out hydrogenation reaction through main reactor, to remove sulphur, nitrogen impurity and alkene saturated.The charging of first reactor drum of this method need be warming up to required temperature in interchanger; Though first reactor inlet temperature is lower; But the very high (temperature of second reactor outlet material of the heat transfer tube wall temperature of interchanger; Generally can reach more than 300 ℃), therefore still there is the problem of interchanger coking.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of inferior patrol cut fraction hydrogenation treatment process method, and the inventive method can effectively solve the coking problem of hydrotreater, prolongs the running period of hydrotreater.
Inferior patrol cut fraction hydrogenation treatment process method of the present invention comprises the steps:
(1) the inferior patrol cut directly mixes with the turning oil-recycle hydrogen of the middle part of step (3) through the process furnace heating, and the temperature of mixture reaches the dialkene removal temperature of reaction, gets into hydrogenation pretreatment reaction device and takes off two rare hydrocarbon reactions;
(2) hydrogenation pretreatment reaction device reaction effluent directly mixes with the turning oil-recycle hydrogen of the middle part of step (3) through the process furnace heating; It is temperature required that the mixture temperature reaches the hydrotreating reactor inlet, and the entering hydrotreating reactor carries out hydrogenation and takes off the impurity reaction;
(3) the hydrotreating reactor reaction effluent gets into separation system; At first isolate the turning oil of heat without cooling; Gasoline fraction and the gas phase after the hydrotreatment isolated in cooling then; Gas phase is mainly hydrogen as recycle hydrogen, and the turning oil of heat mixes with recycle hydrogen to pass through to deliver to respectively in step (1) neutralization procedure (2) after process furnace heats and recycles.
In the inventive method step (1), turning oil is that over point is 350～480 ℃ the hydrorefined petroleum fractions of process, like the vacuum distillate after the unifining, lubricant base, hydrocracking tail oil (being the hydrogen cracking unconverted oil) etc. after the unifining.Mix preceding inferior patrol feedstock temperature with turning oil-recycle hydrogen and can in cryogenic heat exchanger, heat exchange be warming up to 70～120 ℃; Then with the heating after turning oil-recycle hydrogen be mixed to the required temperature of hydrogenation pretreatment reaction; The required temperature of hydrogenation pretreatment reaction is generally 120～210 ℃ according to the performance of catalyzer.The temperature of the turning oil-recycle hydrogen after the heating is confirmed as required, is generally 350～520 ℃, is preferably 370～490 ℃.The consumption of turning oil suits to adjust according to the temperature of reaction needs.In the hydrogenation pretreatment reaction device, hydrogen and raw material (the not containing turning oil) volume ratio (hereinafter to be referred as hydrogen-oil ratio, down together) under standard state is 50: 1～300: 1.The volume space velocity during liquid of hydrogenation pretreatment reaction (in the inferior patrol feedstock, down with) is generally 2～15h
-1, reaction pressure identical with hydrotreating reactor pressure (not considering the pressure-losses).When turning oil-recycle hydrogen and raw materials mix, be preferably under the abundant agitation condition and mix, avoid non-uniform temperature.
In the inventive method step (2), the hydrotreatment temperature of reaction is generally 220～360 ℃, and hydrogen-oil ratio is 200: 1～800: 1, and reaction pressure is 1～10MPa, and volume space velocity is 1～5h during liquid stock
-1Concrete processing condition can require concrete definite according to raw material oil and quality product.
In the inventive method, the catalyzer that uses in step (1) and step (2) reactor drum can be a hydrogenation catalyst conventional in this area; It generally is carrier with the aluminum oxide; With among W, Mo, Ni, the Co one or more is active ingredient, and when catalyzer used, active ingredient was generally sulphided state.The catalyst activity component concentration (in the oxide compound of active ingredient) that uses in preferred steps (2) hydrotreating reactor is higher than the catalyzer that uses in step (1) the hydrogenation pretreatment reaction device, and is most preferably high 5～20 percentage points.Catalyzer can use suitable commercial catalyst, also can prepare by prior art.
In the inventive method, in the step (3), separation system can be confirmed by the conventional knowledge in this area, is generally reaction effluent and carries out gas-liquid separation without the direct gas-liquid separator that gets into of cooling, and liquid phase mainly is a turning oil, recycles after the heating.Gas phase is separated through the laggard stepping promoting the circulation of qi liquid of cooling, and this moment, isolated gas phase was mainly hydrogen, as looping back hydrogenation unit after the recycle hydrogen heating; This moment, isolated liquid phase was mainly the gasoline fraction behind the hydrogenation, can after suitable processing, discharge as product.
In the inventive method, hydrogen make-up required in the hydrogenation reaction system can add in the reactive system at arbitrary steps, as adding in the hydrogenation pretreatment reaction device, also can add in the hydrotreating reactor, also can add in the recycle hydrogen.
Compared with prior art, the inventive method has the following advantages:
(1) the hydrogenation preprocessing process can remove the two rare hydrocarbon that are easy to coking, when having solved following process in process furnace or reactor drum the problem of coking.
(2) cancellation high-temperature heat-exchanging directly mixes raw material with thermal cycling oil, because temperature is even; Mixing time is very short; Solve the coking problem when adopting heat-exchange equipment, avoided in the interchanger coking electrodeposition substance or got in the reactor drum depositing, improved Btu utilization efficient simultaneously.
(3) process furnace reacting by heating raw material has not further reduced the problem of the generation of rare hydrocarbon coking in the raw material.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with preferred embodiment the present invention is further specified, should be appreciated that preferred embodiment described herein only is used for explanation and explains the present invention, and be not used in qualification the present invention.Embodiment adopts laboratory miniature constant temperature fixed-bed reactor, and turning oil is the vacuum distillate after the unifining.
Table 1 raw oil character
| The raw oil title | Coker |
| Density (20 ℃), gcm -3 | 0.7210 |
| The boiling range scope, ℃ | 40～200 |
| Sulphur content, wt% | 0.79 |
| Nitrogen content, wt% | 0.02 |
| Diolefine, g-I 2/100g | 4.8 |
| The bromine valency, gBr.100g -1 | 71.0 |
| Aromatic hydrocarbons, v% | 9.8 |
Table 2 turning oil character
| The turning oil title | The unifining vacuum distillate |
| The boiling range scope, ℃ | 390～550 |
| Sulphur content, μ g/g | ＜1 |
| Nitrogen content, μ g/g | ＜1 |
The main composition and the character of table 3 catalyzer
| Catalyzer | Hydrogenation pretreatment catalyst | Hydrotreating catalyst |
| Catalyzer is formed | ||
| MoO 3+NiO/wt％ | 12 | 20 |
| Carrier | Aluminum oxide | Aluminum oxide |
| The main character of catalyzer | ||
| Specific surface, m 2/g | 180 | 230 |
| Pore volume ml/g | 0.62 | 0.45 |
Table 4 embodiment processing condition
| Processing condition | |
| The turning oil consumption, raw material weight % | 25 |
| Turning oil-recycle hydrogen temperature after heating, ℃ | 480 |
| Pressure, MPa | 4.0 |
| Hydrogen to oil volume ratio | |
| Hydrogenation pretreatment reaction device | 80∶1 |
| Hydrotreating reactor | 600∶1 |
| Volume space velocity, h -1 | |
| Hydrogenation pretreatment reaction device | 7.0 |
| Hydrotreating reactor | 1.3 |
| Temperature, ℃ | |
| Raw material heat exchange temperature | 120 |
| The charging of hydrogenation pretreatment reaction device | 160 |
| The hydrotreating reactor charging | 310 |
Table 5 embodiment test-results
Can find out that from the embodiment data through experiment in 2000 hours, the result of the inventive method still had higher level, particularly problem of pressure drop and obtained good solution.Experimental installation is not considered exothermic heat of reaction, and in full scale plant, because hydrogenation reaction is a strong exothermal reaction, so the consumption of turning oil can reduce significantly.
Claims (10)
1. an inferior patrol cut fraction hydrogenation treatment process method is characterized in that comprising the steps:
(1) the inferior patrol cut directly mixes with the turning oil-recycle hydrogen of the middle part of step (3) through the process furnace heating, and the temperature of mixture reaches the dialkene removal temperature of reaction, gets into hydrogenation pretreatment reaction device and takes off two rare hydrocarbon reactions;
(2) hydrogenation pretreatment reaction device reaction effluent directly mixes with the turning oil-recycle hydrogen of the middle part of step (3) through the process furnace heating; It is temperature required that the mixture temperature reaches the hydrotreating reactor inlet, and the entering hydrotreating reactor carries out hydrogenation and takes off the impurity reaction;
(3) the hydrotreating reactor reaction effluent gets into separation system; At first isolate the turning oil of heat without cooling; Gasoline fraction and the gas phase after the hydrotreatment isolated in cooling then; Gas phase is mainly hydrogen as recycle hydrogen, and the turning oil of heat mixes with recycle hydrogen to pass through to deliver to respectively in step (1) neutralization procedure (2) after process furnace heats and recycles.
2. according to the described method of claim 1; It is characterized in that: in the step (1); Turning oil is that over point is 350～480 ℃ the hydrorefined petroleum fractions of process, is preferably vacuum distillate, the lubricant base after the unifining or hydrocracking tail oil after the unifining.
3. according to claim 1 or 2 described methods; It is characterized in that: in the step (1); Inferior patrol feedstock temperature heat exchange in cryogenic heat exchanger before mixing with turning oil-recycle hydrogen is warming up to 70～120 ℃, then with heating after turning oil-recycle hydrogen be mixed to the required temperature of hydrogenation pretreatment reaction.
4. according to the described method of claim 1, it is characterized in that: the temperature of hydrogenation pretreatment reaction is 120～210 ℃.
5. according to the described method of claim 1, it is characterized in that: the temperature of the turning oil-recycle hydrogen after the heating is 350～520 ℃, is preferably 370～490 ℃.
6. according to the described method of claim 1, it is characterized in that: hydrogen and the volume ratio of raw material under standard state are 50: 1～300: 1 in the hydrogenation pretreatment reaction device.
7. according to the described method of claim 1, it is characterized in that: volume space velocity is 2～15h during the liquid of hydrogenation pretreatment reaction
-1
8. according to the described method of claim 1, it is characterized in that: in the step (2), the hydrotreatment temperature of reaction is 220～360 ℃, and hydrogen-oil ratio is 200: 1～800: 1, and reaction pressure is 1～10MPa, and volume space velocity is 1～5h during liquid stock
-1
9. according to the described method of claim 1, it is characterized in that: the catalyzer that uses in step (1) and step (2) reactor drum is a carrier with the aluminum oxide, is active ingredient with among W, Mo, Ni, the Co one or more.
10. according to the described method of claim 9; It is characterized in that: the catalyst activity component concentration that uses in step (2) hydrotreating reactor is higher than and uses 5～20 percentage points of catalyzer in step (1) the hydrogenation pretreatment reaction device in the oxide compound of active ingredient.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103805243A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for prolonging running period of inferior gasoline hydrogenation device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103805243A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for prolonging running period of inferior gasoline hydrogenation device |
| CN103805243B (en) * | 2012-11-07 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of method extending inferior patrol operation period of hydrogenation device |
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Application publication date: 20120704 |