CN1132903C - Heavy hydrocarbon hydroprocessing technique - Google Patents
Heavy hydrocarbon hydroprocessing technique Download PDFInfo
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- CN1132903C CN1132903C CN 01106025 CN01106025A CN1132903C CN 1132903 C CN1132903 C CN 1132903C CN 01106025 CN01106025 CN 01106025 CN 01106025 A CN01106025 A CN 01106025A CN 1132903 C CN1132903 C CN 1132903C
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Abstract
The present invention discloses a heavy hydrocarbon hydrotreating technology. Raw oil and hydrogen are respectively heated, and after the temperature reaches the temperature required by a reaction, the raw oil is supplied into a reactor or a reaction bed layer from a first reactor or from the top of the reaction bed layer in a downward flow form to contact a catalyst; the hydrogen is supplied into the reactor from a last reactor or from the bottom of the reaction bed layer in an upward flow form to pass through a catalyst bed layer, and the two phases contact in a counter flow mode to complete the hydrogenation reaction. After the reaction is completed, liquid-phase fluid is discharged from the last reactor or from the bottom of the reaction bed layer, and gas-phase fluid is discharged from the first reactor or from the top of the reaction bed layer. The adopted technology can improve reaction effects and further reduce the hydrogen consumption and the energy consumption of a device.
Description
The present invention relates to a kind of hydroprocessing process of heavy hydrocarbon, specifically a kind of improvement of heavy hydrocarbon fixed bed hydrogenation technology.
Increasingly stringent along with heaviness day by day, poor qualityization and the environmental legislation of crude oil, hydrogenation technique becomes one of main method in the refining of petroleum day by day, it not only can slough detrimental impurity such as metal in the oil, sulphur, nitrogen in a large number, the low boiling component that can also make heavily, residue oil fraction is cracked into high value.
At present, more employing fixed-bed reactor in heavy, the Residue Hydrotreating Technology, the catalyzer of difference in functionality are divided in different reactors or the different bed, and packing sequence is: the general Hydrodemetalation catalyst of filling earlier, the Hydrobon catalyst that recharges loads hydrodenitrogenation catalyst at last.The simple process flow of this technology is: stock oil mixes before the charging process furnace with hydrogen, enters process furnace jointly, with temperature be heated to reaction temperature required after, enter reactor by the top of reactor.Stock oil and hydrogen with downward stream mode and stream successively by Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst bed and hydrogenation reaction takes place.After reaction finished, the hydrogenation resultant entered high pressure hot separator, tells gas-phase product and liquid product, and wherein gas-phase product enters cold high pressure separator again and isolates hydrogen-rich gas, and liquid product then enters thermal low-pressure separators again and isolates hydrogenation heavy oil.Hydrogen-rich gas Returning reactor after purifying continues to use, and hydrogenation heavy oil removes atmospheric fractional tower or directly go the further lighting of catalytic cracking unit.
In general, sulphur content in oil and the most of petroleum fractions is more much higher than nitrogen content, and hydrogenating desulfurization is easier than hydrodenitrification usually, therefore in the said fixing bed hydroprocessing technology, the hydrogen sulfide that hydrogenation reaction generates also can be with reactant flow successively by above-mentioned beds, hydrogenating desulfurization and hydrodenitrification to stock oil produce restraining effect, especially to hydrodenitrification, document ((English) applied catalysis A.General154 (1997) 7-15) just points out that the existence of hydrogen sulfide can bring two kinds of bad influences to hydrotreatment, and promptly (1) is to the restraining effect of the part or all of function of hydrotreating catalyst; (2) blocking catalyst hole or reactor are played a driving role.Cause the operational condition that hydrodenitrification need be harsher than other hydrotreatment processes, shortened the work-ing life of hydrodenitrogenation catalyst.In addition, the concurrent flow of reaction feed makes the hydrogen dividing potential drop height of easy hydro-upgrading part (hydrodemetallation (HDM), partial hydrogenation desulfurization), and the hydrogen branch of difficult hydro-upgrading part (partial hydrogenation desulfurization, hydrodenitrification, removal of ccr by hydrotreating, hydrocracking) forces down, and causes the low reaction rate of whole hydrogenation reaction.Moreover hydrogenation reaction is thermopositive reaction, and the concurrent flow of charging makes the temperature of reaction rising gradient of industrial adiabatic hydrogenator big, has promptly increased the cold hydrogen amount of device, has also increased the cracking reaction and the coking reaction of stock oil, improves the hydrogen consumption of device.The preheating temperature of stock oil also improves constantly with the inactivation of catalyzer simultaneously, increases the energy consumption of device logistics heating.
In order to improve the deficiency of above-mentioned heavy, residue fixed-bed hydrogenation technique, the purpose of this invention is to provide a kind of heavy hydrocarbon hydroprocessing technique, improve reaction effect, further reduce the hydrogen consumption and the energy consumption of device.
Different with above-mentioned existing mink cell focus hydrogenation technique, the present invention heats stock oil and hydrogen respectively, after temperature reached the required temperature of reaction, stock oil was contacted with catalyzer by first reactor or streamed reactor or the reaction bed of entering below the reaction bed top; Hydrogen is the streamed reactor that enters more than the bottom by last reactor or reaction bed then, and by beds, hydrogenation reaction is finished in the two phase countercurrent flow contact.Liquid phase fluid was discharged by the bottom of last reactor or reaction bed after reaction was finished, and gaseous fluid is then discharged by the top of first reactor or reaction bed.
Because the gas-liquid two-phase counter-current flow has the gas-liquid separation effect, hydrogen can carry out reactor with the light ends oil of gasification, therefore the liquid-phase hydrogenatin resultant can directly enter thermal low-pressure separators, tell hydrogen-depleted gas body and hydrogenation heavy oil, the hydrogen-depleted gas body goes the cold low separator to continue to separate, and hydrogenation heavy oil then removes atmospheric fractional tower or directly goes the further lighting of catalytic cracking unit.The gas-phase product of being discharged by reactor head is because of mainly containing light hydrocarbons, isolate hydrogen-rich gas and light ends so can directly enter cold high pressure separator, hydrogen-rich gas Returning reactor after purifying continues to use, and light ends then goes the cold low separator to continue to separate.
When practical application is of the present invention, whether sneak into hydrogen before can according to stock oil character and reactor is temperature required deciding stock oil to advance process furnace, be used for suppressing the coking of stock oil at process furnace.If need sneak into hydrogen, the amounts of hydrogen of then sneaking into accounts for the 5-10V% that enters the total hydrogen amount of reactor.
Technology of the present invention mainly is applicable to residue fixed-bed hydrogenation technique, and other technology such as expanded bed, moving bed process also can be used the solution of the present invention certainly.
In general, catalyzer in the described reactor all is to carry out the layering filling according to character of himself and function, promptly since first reactor or reaction bed top to the bottom of last reactor or reaction bed, load Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly, even can use with a kind of catalyzer.But consider that from reaction kinetics and thermodynamic (al) angle the reaction of hydrogenating desulfurization is easy than hydrodenitrification, even load with a kind of catalyzer, hydrogenating desulfurization and hydrodenitrification reacting phase ratio also will take place in the front portion of catalyzer.
Described heavy, residue fixed-bed hydroprocessing condition is generally: temperature of reaction 340-427 ℃, and preferably 360-410 ℃; Reaction pressure is 8.0-20.0MPa, and that best is 8.0-15.0MPa; Hydrogen to oil volume ratio is 500-2000, and that best is 700-1500; Volume space velocity is 0.1-1.0h during liquid
-1, that best is 0.2-0.8h
-1The weight that is adopted, residual oil hydrocatalyst be meant have weight, the single catalyst or the series catalyst of residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous refractory inorganic oxide such as aluminum oxide or crystalline silicate such as zeolite, the oxide compound of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. is an active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.
The present invention is applicable to normal slag and the hydrocracking that subtracts slag, is particularly useful for the residual hydrocracking of high metal, high-sulfur, high nitrogen-containing, also is suitable for light, heavy distillate fixed bed hydrogenation modifying process that all are used for hydrogenating desulfurization, hydrodenitrification.
Compared with prior art, the characteristics of the mobile fixed-bed process of fluid countercurrent current of the present invention have: the agitaion that the countercurrent flow of (1) hydrogen produces liquid phase fluid has increased biphase and has effectively mixed, and has increased their velocity of diffusion, has improved speed of response.(2) the gas phase light ends that generates of cracking reaction and the hydrogen back-mixing at upper reaches get on, and the stock oil that reverse and feeding temperature are lower than temperature of reaction conducts heat, and has promptly reduced self temperature, improves the stock oil temperature again.As a result, not only suppress the further cracked degree of gas phase light ends, reduce the hydrogen consumption, and the preheating temperature that can also reduce stock oil cuts down the consumption of energy.Dirty liquid phase fluid, though the temperature of reaction of bearing is more and more higher, but the hydrogen lower than temperature of reaction because of itself and feeding temperature reacts, again reverse heat transfer can take place, and the hydrogen dividing potential drop is also more and more higher, the result, its temperature rising amplitude is little, be difficult for causing the reactor temperature runaway, can significantly reduce the generation of hydro carbons coking reaction again, and reduced the cold hydrogen amount of device.(3) fluid countercurrent current of the present invention flows, concentration of hydrogen sulfide in the reactor is raise successively by hydrodenitrogenation catalyst to Hydrodemetalation catalyst, reduce the restraining effect of hydrogen sulfide greatly, also help heavy metals such as Ni, V and generate sulfide and deposit hydrodenitrification and hydrogenating desulfurization.(4) fluid countercurrent current of the present invention flows the hydrogen dividing potential drop in the reactor is reduced successively by hydrodenitrogenation catalyst to Hydrodemetalation catalyst, helps difficulty and removes the removing of impurity such as sulphur, nitrogen (hydrogenation and removing of unsaturated nuclear nitrogen and sulphur must be hydrogenated into earlier after the saturated rings could hydrogenolysis).
Fig. 1 is that to adopt counter-current process schematic flow sheet, Fig. 2 in the embodiment of the invention be the existing co-current flow fixed bed process flow diagram of fluid.
The present invention is described in detail below in conjunction with drawings and Examples.
The schematic flow sheet of counter-current process described in embodiment of the invention particular case is as follows: residual oil raw material 1 enter process furnace 3 be heated to temperature required after, heated stream streamed top by reactor below 4 enters fixed bed hydrogenation reactor 5.Hydrogen 2 enters process furnace 7, be heated to temperature required after, enter fixed bed hydrogenation reactor 5 by reactor lower part through pipeline is streamed more than 8.Reacted liquid product 6 is discharged from reactor bottom and is directly entered thermal low-pressure separators 12 separation, and the liquid-phase hydrogenatin heavy oil 13 after the separation goes out device, goes the further lighting of downstream unit.And gas-phase product 11 enters cold low separator 17.Directly entering cold high pressure separator 15 after reacted gas-phase product 9 is discharged by reactor head separates.Capable of circulation time reactor after isolated rich hydrogen hydrogen 10 is purified, isolated light oil 14 then enters cold low separator 17 further to be separated.The cold low separator 17 isolated gas-phase products 16 body recovery system of can degassing, light oil 18 goes out device.
It is as follows to be used for the co-current flow fixed bed bed process schematic flow sheet of correlated existing fluid particular case in the embodiment of the invention: stock oil 1 at first mixes with hydrogen 2, enter process furnace 3 afterwards jointly, mixing raw material in process furnace 3, be heated to temperature required after, heated stream is streamed below 4 to enter fixed bed hydrogenation reactor 5 by reactor head.Reactor operating condition is identical with fluid counter-current flow fixed-bed process.Reaction product 6 enters high pressure hot separator 7S separates, and the liquid product 8S after the separation enters thermal low-pressure separators 12 further to be separated, and gas-phase product 9 then enters cold high pressure separator 15 further to be separated.Cold high pressure separator 15 isolated light oil 14 enter cold low separator 17 with thermal low-pressure separators 12 isolating gas phases 11 further to be separated, and isolated hydrogen-rich gas 10 loops back reactor after then can purifying.The cold low separator 17 isolated gas-phase products 16 body recovery system of can degassing, light oil 18 goes out device.The isolated heavy oil 13 of thermal low-pressure separators goes out the further lighting of device that device goes to the downstream.
The main impurity removal performance of investigating fluid countercurrent current mobile fixed-bed process and existing fluid and flowing down current flow fixed bed technology of this test, detailed process is referring to Fig. 1 and Fig. 2.The hydrogenation catalyst that residue fixed-bed device in this test uses is heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.Wherein Hydrodemetalation catalyst is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Filling ratio between each catalyzer is:
CEN-2∶FZC-16∶CEN-4∶CEN-5∶CEN-6∶ZTS-01∶ZTS-02∶ZTS-03∶ZTN-01＝1∶1.25∶1.5∶2.62∶7.8∶6.63∶0.69∶0.87∶11(V/V)。
Residue fixed-bed hydrogenation reaction is all carried out in this test on the long run test device.Operational condition and reaction result see Table-1.
Table-1
| | 1 | 2 | 3 | |||
| Reaction conditions | And stream | Adverse current | And stream | Adverse current | And stream | Adverse current |
| Temperature of reaction, ℃ | 370 | 380 | 385 | |||
| Air speed, h -1 | 0.25 | 0.30 | 0.30 | |||
| Hydrogen pressure, MPa | 10.0 | 12.0 | 12.0 | |||
| Hydrogen-oil ratio | 800 | 800 | 1000 | |||
| Generate oily impurity removal percentage, % | ||||||
| HDS | 84.74 | 86.43 | 86.12 | 88.76 | 88.20 | 89.97 |
| HDN | 56.97 | 60.12 | 58.11 | 63.56 | 62.11 | 66.36 |
| HD(Ni+V) | 86.13 | 86.11 | 88.21 | 88.30 | 89.32 | 89.64 |
Continuous table-1
| Embodiment | 4 | 5 | 6 | |||
| Reaction conditions | And stream | Adverse current | And stream | Adverse current | And stream | Adverse current |
| Temperature of reaction, ℃ | 390 | 400 | 41O | |||
| Air speed, h -1 | 0.35 | 0.35 | 0.35 | |||
| Hydrogen pressure, Mpa | 14.0 | 15.0 | 15.0 | |||
| Hydrogen-oil ratio | 1000 | 1200 | 1500 | |||
| Generate oily impurity removal percentage, % | ||||||
| HDS | 89.03 | 90.67 | 90.33 | 91.86 | 91.63 | 92.55 |
| HDN | 63.23 | 69.97 | 67.62 | 73.36 | 70.62 | 78.36 |
| HD(Ni+V) | 90.31 | 90.37 | 91.11 | 91.23 | 92.32 | 92.64 |
Embodiment 7
This test is main to be investigated fluid countercurrent current mobile fixed bed hydrogenation technology and existing fluid and flows down current flow fixed bed process catalyst deactivation rate.Catalyzer is with embodiment 1～6, and temperature of reaction is 390 ℃, and air speed is 0.35h
-1, hydrogen pressure is 14.0MPa, and hydrogen-oil ratio is 1000, and device turned round 3600 hours.Test-results sees Table-2.
Table-2
| Runtime, hour | 100 | 3600 | ||
| And stream | Adverse current | And stream | Adverse current | |
| Generate oily impurity removal percentage, % | ||||
| HDS | 89.03 | 90.67 | 85.12 | 87.63 |
| HDN | 63.23 | 69.97 | 55.30 | 69.13 |
| HD(Ni+V) | 90.31 | 90.37 | 86.45 | 88.05 |
Claims (6)
1, a kind of heavy hydrocarbon hydroprocessing technique is characterized in that comprising: after stock oil and hydrogen were heated to the required temperature of reaction, stock oil was contacted with catalyzer by first reactor or the streamed reactor that enters below the reaction bed top; Hydrogen is the streamed reactor that enters more than the bottom by last reactor or reaction bed then, pass through beds, hydrogenation reaction is finished in the two phase countercurrent flow contact, liquid phase fluid was discharged by the bottom of last reactor or reaction bed after reaction was finished, and gaseous fluid is then discharged by the top of first reactor or reaction bed; Wherein hydrogenation conditions is: temperature of reaction 340-427 ℃, and reaction pressure 8.0-20.0MPa, hydrogen to oil volume ratio is 500-2000, volume space velocity is 0.1-1.0h during liquid
-1
2,, it is characterized in that described liquid-phase hydrogenatin resultant directly enters thermal low-pressure separators, tells hydrogen-depleted gas body and hydrogenation heavy oil according to the described heavy hydrocarbon hydroprocessing technique of claim 1.
3, according to the described heavy hydrocarbon hydroprocessing technique of claim 1, it is characterized in that the gas-phase product that discharges at described first reactor or reaction bed top directly enters cold high pressure separator and isolates hydrogen-rich gas and light ends, hydrogen-rich gas Returning reactor after purifying continues to use, and light ends then goes the cold low separator to continue to separate.
4, according to the described heavy hydrocarbon hydroprocessing technique of claim 1, the filling that it is characterized in that catalyzer in described reactor or the reaction bed is in proper order: begun to load Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst successively to the bottom of last reactor or reaction bed by first reactor or reaction bed top.
5, according to the described heavy hydrocarbon hydroprocessing technique of claim 1, it is characterized in that the described heavy hydrocarbon hydrogenation reaction condition of answering is: temperature of reaction 360-410 ℃, reaction pressure 8.0-15.0Mpa, hydrogen to oil volume ratio is 700-1500, volume space velocity is 0.2-0.8h during liquid
-1
6, according to the described heavy hydrocarbon hydroprocessing technique of claim 1, it is characterized in that described catalyzer is is carrier with porous refractory inorganic oxide or crystalline silicate, is the hydrogenation catalyst of active metal component with group vib and/or VIII family metal component.
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| CN 01106025 CN1132903C (en) | 2001-01-05 | 2001-01-05 | Heavy hydrocarbon hydroprocessing technique |
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| CN 01106025 CN1132903C (en) | 2001-01-05 | 2001-01-05 | Heavy hydrocarbon hydroprocessing technique |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373082A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | Counter flow hydrogenation method of catalytic-cracked heavy oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8313705B2 (en) | 2008-06-23 | 2012-11-20 | Uop Llc | System and process for reacting a petroleum fraction |
| CN102634367A (en) * | 2008-08-11 | 2012-08-15 | 中国石油化工集团公司 | Double-phase hydrogenating method |
| CN101768468B (en) * | 2008-12-31 | 2013-11-06 | 中国石油化工股份有限公司 | Hydrogenation method for residual oil |
| CN102465031B (en) * | 2010-11-04 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
| CN103789022B (en) * | 2012-11-03 | 2015-07-22 | 中国石油化工股份有限公司 | Hydrogenation process |
| CN105586084B (en) * | 2014-10-23 | 2017-04-26 | 中国石油化工股份有限公司 | Catalytic hydrogenation method for inferior wax oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373082A (en) * | 2010-08-12 | 2012-03-14 | 中国石油化工股份有限公司 | Counter flow hydrogenation method of catalytic-cracked heavy oil |
| CN102373082B (en) * | 2010-08-12 | 2013-12-25 | 中国石油化工股份有限公司 | Counter flow hydrogenation method of catalytic-cracked heavy oil |
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