CN1104238A - Refining method and its configuration - Google Patents
Refining method and its configuration Download PDFInfo
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- CN1104238A CN1104238A CN94115788A CN94115788A CN1104238A CN 1104238 A CN1104238 A CN 1104238A CN 94115788 A CN94115788 A CN 94115788A CN 94115788 A CN94115788 A CN 94115788A CN 1104238 A CN1104238 A CN 1104238A
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- 238000007670 refining Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004821 distillation Methods 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims description 197
- 239000007788 liquid Substances 0.000 claims description 89
- 239000000047 product Substances 0.000 claims description 84
- 229910052739 hydrogen Inorganic materials 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 46
- 238000000926 separation method Methods 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000007791 liquid phase Substances 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 33
- 239000003350 kerosene Substances 0.000 claims description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 238000001833 catalytic reforming Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 238000005204 segregation Methods 0.000 claims 1
- 239000010779 crude oil Substances 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 69
- 239000003915 liquefied petroleum gas Substances 0.000 description 25
- 238000005194 fractionation Methods 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 239000002912 waste gas Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005457 optimization Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YUMYYTORLYHUFW-MSKIIMLESA-N n-[(2s)-1-[[(e,3s)-1-(benzenesulfonyl)-5-phenylpent-1-en-3-yl]amino]-4-methyl-1-oxopentan-2-yl]morpholine-4-carboxamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC=1C=CC=CC=1)\C=C\S(=O)(=O)C=1C=CC=CC=1)C(=O)N1CCOCC1 YUMYYTORLYHUFW-MSKIIMLESA-N 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
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- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
Abstract
The present invention relates to a refinery for hydrotreating of petroleum fractions, and more particularly, a refining method and a refinery configuration comprising a step for distillation of a crude oil to separate a residue and a distillate and a step for hydrotreating the distillate at once in a single hydrotreating unit. If compared to the conventional wherein crude oil is distilled into several fractions and hydrotreating is carried out on each fraction independently, the present invention can simplify a refinery configuration and achieves compact plant with low capital investment cost, even for a small scale refinery.
Description
The present invention relates to a kind of from crude oil, the separate cut of gas oil, kerosene, heavy naphtha, light naphthar LPG and lightweight gas and the method for refining and the refinery configuration of hydrotreatment thereof.
Fig. 8 illustrates a kind of method for refining of routine.Crude oil is offered atmospheric distillation plant 1 pre-treatment, for example dehydrogenation and desalination.In atmospheric distillation plant 1, crude distillation becomes lightweight gas, LPG(liquefied petroleum gas (LPG)), the cut of light naphthar, heavy naphtha, kerosene, gas oil and residual oil.Lightweight gas (waste gas) from atmospheric distillation plant is made amination treatment together with the waste gas from other technologies in amine treatment unit 2, to remove sour gas contained in the waste gas.The gas of handling is as the inflammable gas of refining.Sour gas is sent to sulfur recovery unit 3 and reclaims sulphur.The LPG cut is processing treatment in LPG treatment unit 4, to reduce impurity and to be processed into the LPG product.Light naphtha fraction desulfurization in light naphthar treatment unit 5, and mix in the high-octane rating reformate.Heavy naphtha is sent to heavy naphtha hydrotreater 6, so that in the presence of catalyzer, do hydrotreatment, then, be sent to catalyzer reformer 7 and carry out isomerization and aromizing processing, and be processed into the high-octane rating reformate, be suitable for the fusion of high-octane rating reformate.Kerosene is sent to kerosene treatment unit 8 so that remove mercaptan contained in the kerosene.Gas oil fraction is sent to gas oil hydrotreater 9, carries out hydrotreatment in the presence of catalyzer, and is processed to gas oil product after removing impurity.The pressure naphtha that produces in this process (unstable petroleum naphtha) is sent atmospheric distillation plant 1 back to.From the residual oil of atmospheric distillation plant 1 blending compound as heavy fuel oil (HFO), or in vacuum distillation plant further processing treatment become vacuum gas oil.
Prior art is not noted the refining ability; Crude oil is separated into several fractions in water distilling apparatus, then every kind of cut hydrotreatment or processing respectively.
Therefore, conventional refinery provides quite complicated configuration, and requires big cost of investment.
Especially for the small-scale refinery, compacted location figure and the low cost of investment that seek development and have low cost of investment in addition, also can be applied to refinery on a small scale.
According to method for refining of the present invention, crude oil is separated into residual oil and overhead product, and this overhead product carries out hydrotreatment together in single hydrotreater.
The product of hydrotreatment acquisition is distilled into the cut of gas oil, kerosene, heavy naphtha, light naphthar, LPG and lightweight gas.Preferably isolating heavy naphtha is supplied with catalytic reforming unit, thereby further change into the high-octane rating reformate therein, reclaiming purity from the catalyzer reformer simultaneously is 75% or greater than 75% hydrogen, and with its as a supplement hydrogen offer the hydrogen treatment unit.
In addition, also atmospheric residue may be offered vacuum distillation plant, so that distillation, to obtain vacuum gas oil and in single hydrotreater, this vacuum gas oil and air distillation product to be carried out hydrotreatment together.
Preferred gas/liquid of the hydrotreater of this method for refining and downward flow type reactor, gas/liquid countercurrent reactor and gas/liquid also flow a kind of among the up-flow reactor.The hydrotreater of comparative optimization is gas/liquid and flows down flow reactor or gas/liquid and flow up-flow reactor, is equipped with in the stage casing of this reactor and carries out the isolating equipment of gas/liquid.
In addition, in this method for refining, will return the reactor inlet of hydrotreater by a part of product oil that hydrotreatment obtains.
Preferred hydroprocessing condition is following listed: pressure is 20-80kg/cm
2G, comparative optimization 30-70kg/cm
2G.Temperature is 300-400 ℃, and comparative optimization is 320-380 ℃.Hydrogen is 50-200N1/1 with the ratio of oil, comparative optimization 70-150N1/1.LHSV is 0.1-5h
-1 r, comparative optimization is 1-4h
-1 r
Refinery configuration of the present invention comprises and a kind of crude distillation is become the atmospheric distillation plant of residual oil and distillate and a kind of to make the hydrotreater of hydrotreatment from the distillate of atmospheric distillation plant.
Refinery configuration of the present invention can comprise that the product that will obtain by hydrotreatment is distilled into the fractionation section of following cut: gas oil, kerosene, heavy naphtha, light naphthar, LPG and lightweight gas in hydrotreater.Refinery configuration of the present invention also comprises a kind of catalytic reforming unit and a kind of by product hydrogen supply line that will be offered hydrotreater by the hydrogen that catalytic reforming unit reclaims that heavy naphtha fraction is changed into the high-octane rating reformate.In addition, refinery configuration of the present invention can comprise a kind of vacuum distillation plant and a kind of vacuum gas oil supply line that is suitable for vacuum gas oil is offered the hydrotreater that is suitable for hydrotreatment normal pressure distillate that is suitable for long residuum is distilled into vacuum gas oil.
In refinery configuration of the present invention, preferred hydrotreater is selected from gas/liquid and flows up-flow reactor, and gas/liquid countercurrent reactor and gas/liquid also flow down a kind of in the flow reactor.This gas/liquid also flows down flow reactor and gas/liquid and flow the stage casing that up-flow reactor is preferably in this reactor gas/liquid separation is housed.
In addition, this refinery configuration can comprise a kind of product oil return line pipeline that will be back to the hydrotreater inlet at the portioned product oil that hydrotreater obtains.
Refinery configuration of the present invention has following advantage:
According to this refinery configuration, crude oil is to be distilled into residual oil and distillate under normal pressure, and whole distillates are done hydrotreatment together in single hydrotreater.The present invention can simplify refinery configuration greatly.Compare with the refinery configuration (wherein crude distillation becomes several fractions and every kind of cut is distinguished hydrotreatment) of routine, refinery configuration of the present invention has advantage compact to design, that cost of investment is low.
Wherein every kind of cut ordinary method of carrying out hydrotreatment respectively needs maintenance, for example to each hydrotreater supply catalyzer respectively, therefore, needs the various additional facilities that are applicable to maintenance.On the other hand, in refinery configuration of the present invention (wherein with distillate hydrotreatment together in single hydrogenation unit), maintenance also can once be carried out, and the additional facilities that is used to maintain is also simplified widely.So also can reduce maintenance work, and the refinery is operated effectively.
Except be applicable to crude distillation become residual oil and distillate atmospheric distillation plant and be suitable for this distillate is all done the hydrotreater of hydrotreatment, refinery configuration of the present invention can comprise that a kind of product that is suitable for obtaining in hydrotreater is separated into the fractionation section of following cut: gas oil, kerosene, heavy naphtha, light naphthar, LPG and lightweight gas; A kind of catalyzer reformer that is suitable for heavy naphtha fraction is changed into the high-octane rating reformate; Offer the by product hydrogen supply line of hydrotreater with a kind of hydrogen that is suitable for to retrieve by catalytic reforming unit.Therefore, above-mentioned cut and a large amount of gasoline components might be produced, and the by product hydrogen hydrogen as a supplement in the hydrotreater can be utilized.
In addition, refinery configuration of the present invention can comprise and a kind ofly is suitable for that long residuum is distilled into vacuum gas oil and offers the vacuum gas oil supply line that hydrotreater is used for hydrotreatment normal pressure distillate.Thereby the charging of hydrotreater increases, that is, the quantity of the overhead product product of added value has increased.
The gas/liquid countercurrent reactor is being used as under the situation of hydrotreater, distillate is offered middle portion between last catalyst bed and following catalyst bed, and distillate is separated into gas phase (more lower boiling cut) and liquid phase (cut of higher) there.Contain a large amount of sulphur compounds, the high boiling fraction that is difficult to hydrogenating desulfurization flows downward, so as with the hydrogen counter current contact.On the other hand, upwards flow and hydrogen and stream than being easier to the hydrogenant low boiler cut.Thereby, might have the different boiling several fractions and carry out efficient hydrogen treatment containing with all kinds sulfide with different desulphurization reactions.
In this case, hydrotreater wherein is gas/liquid and flows down flow reactor or gas/liquid and flow up-flow reactor, be equipped with in the middle part of this reactor and be suitable for the isolating gas/liquid separation of gas/liquid, overhead product is extracted out from the stage casing of reactor, so that it is separated into gas phase and liquid phase.One of gas phase and liquid phase can be resupplied reactor is for further processing.Therefore might contain total overhead product hydrogenation effectively of several fractions with different boiling and various types of sulfide, and satisfy technical requirements neatly for the various products of each cut with different desulphurization reactions.
In addition, refinery configuration of the present invention can comprise that also a kind of a part of product oil that is suitable for obtaining by hydrotreatment is back to the product oil return line pipeline of the reactor inlet of hydrotreater.Therefore, might repeat hydrotreatment to a certain concrete cut if necessary, the further hydrotreatment easily of this concrete cut.
Fig. 1 is the process flow sheet of an embodiment of explanation refinery configuration of the present invention.
First embodiment of Fig. 2 explanation preferred hydrotreater in refinery configuration of the present invention.
Second embodiment of Fig. 3 explanation preferred hydrotreater in refinery configuration of the present invention.
Fig. 4 illustrates the 3rd embodiment of preferred hydrotreater in the refinery configuration of the present invention.
The 4th embodiment of Fig. 5 explanation preferred hydrotreater in refinery configuration of the present invention.
The 5th embodiment of the preferred hydrotreater of Fig. 6 explanation in refinery configuration of the present invention.
The 6th embodiment of Fig. 7 explanation preferred hydrotreater in configuration of the present invention.
Fig. 8 is the process flow sheet of the conventional refinery configuration of explanation.
Fig. 1 illustrates method for refining of the present invention.To offer crude unit (atmospheric distillation plant) 11 through the crude oil of pre-treatment (for example dehydrogenation and desalination) according to this method for refining, crude oil is distilled into overhead product and the residual oil that contains gas oil, kerosene, petroleum naphtha, LPG and lightweight gas under normal pressure in this device.
To offer hydrotreater 12 from all overhead products of crude unit 11, being allowed to condition at the catalyzer existence contacts with hydrogen down, so that hydrotreatment, will be distilled into the cut of gas oil, kerosene, heavy naphtha, light naphthar, LPG and lightweight gas (waste gas) by the product that hydrotreatment obtains.
Preferred hydrotreater 12 is selected from gas/liquid and flows down flow reactor, gas/liquid countercurrent reactor, gas/liquid and flow up-flow reactor and the reactor of gas/liquid separation is housed in the reactor stage casing.The hydrogen that is used for hydrotreater can be the hydrogen that reclaims from catalytic reforming unit 7, and the heavy naphtha of hydrotreatment changes into the high-octane rating reformate in device 7.The hydrogen of this recovery preferably has 75% or greater than the purity more than 75%, comparative optimization 80% or greater than 80% purity.
According to the present invention, crude oil is distilled under normal pressure, be separated into residual oil and overhead product, and with the hydrotreatment together in single hydrogenation unit of all overhead products.Become several fractions with crude separation wherein, then the conventional refinery configuration of every kind of cut fraction hydrogenation processing or individual curing is compared, method for refining of the present invention can be simplified refinery configuration, and realizes compact plant and low cost of investment, is particularly useful for refinery on a small scale.
According to the present invention, crude oil is distilled into residual oil and overhead product under normal pressure.The overhead product of gained can be used as and a kind ofly comprises the overhead product (gas oil, kerosene, petroleum naphtha, LPG and lightweight gas) of except that long residuum all cuts or as several isolating cuts.For example, have and in air distillation, to obtain gas oil fraction and kerosene and light ends respectively.
Also can from the overhead product that requires hydrotreatment, obtain a kind of cut that does not require hydrotreatment respectively.If lightweight gas does not need hydrotreatment, for example, the heavy gas that overhead product can be separated into lightweight gas and LGP and will in hydrotreater, handle.If in atmospheric distillation plant, obtain containing the overhead product of lightweight gas, should before being offered hydrotreater, remove overhead product lightweight gas as far as possible.
According to the present invention, overhead product cut that will obtain with single cut or the overhead product cut that needs hydrotreatment are incorporated in the single hydrogenation hydrotreater and with it and carry out hydrotreatment together.Also the cut that does not need hydrogen to handle that obtains can be offered hydrotreater in air distillation.Hydrotreatment is preferably carried out under following condition: its pressure is 20-80kg/cm
2G, comparative optimization are 30-70kg/cm
2G.Temperature is 300-400 ℃, and comparative optimization is 320-380 ℃.H
2The ratio of/oil is 50-200N1/1, and comparative optimization is 70-150N1/1.LHSV is 0.1-5h
-1 r, comparative optimization is 1-4h
-1 rHydrogen source can be hydrogenous any gas, preferably has 60% or 60% above purity.
Any catalyzer with hydrotreatment ability all is suitable as the catalyzer of hydrotreatment.For example, use CoMo, N usually
1Mo, CoMoP and WN
1Mo.
Fig. 2 has illustrated as the gas/liquid of first embodiment of hydrotreater and has flowed down flow reactor.This hydrotreater comprises reactor 21, the gas/liquid separation 25 that hydrogenation catalyst 20 is housed, and as the main fractionation section of forming 23.For hydrotreatment and this device fractionation of use, to comprise for example gas oil and kerosene and the top that offers reactor 20 together than the overhead product and the hydrogen of light ends, and allow the gas/liquid mixture be downward through, and make overhead product hydrotreatment under preset temperature and predetermined pressure.Product flows out from the bottom of reactor 21 and offers gas/liquid separation 25, and product is separated into gas phase (unreacted hydrogen, reacted gas reach other) and liquid phase (product oil) in separator 25.Liquid phase is offered fractionation section 23, simultaneously with gas phase remove cracked gas for example behind the hydrogen sulfide recirculation return reactor 21.The liquid phase of supplying with fractionation section 23 is distilled into the cut of gas oil, kerosene, petroleum naphtha, LPG and lightweight gas.By the way, if necessary, gas oil fraction can be turned back to reactor 21 again, so that repeated hydrogenation is handled.
Fig. 3 illustrates second embodiment of hydrotreater, and this hydrotreater is to have the gas/liquid of middle gas/liquid separation and flow up-flow reactor.According to the same way as of the described hydrotreater of Fig. 2, the hydrotreater of second embodiment comprises: the reactor 21 arranged with multilayer of hydrogenation catalyst 20 wherein, middle gas/liquid separation 22, gas/liquid separation 25 and fractionation section.In order to use this hydrotreater that overhead product is carried out hydrotreatment, with the bottom of overhead product and hydrogen supply response device 21, and overhead product and hydrogen are flowed downward so that under preset temperature and predetermined pressure the hydrotreatment overhead product.Will be from gas/liquid separation 22 in the middle of the logistics supply of lower floor's catalyst bed, it is separated into gas phase and liquid phase in separator 22.This gas phase is the catalyst bed by the upper strata and discharge and will cool down from reactor head further, and warp let-off gas/liquid separation 25 makes it be separated into waste gas and product oil then.To be sent to the fractionation section respectively or together from the liquid phase of middle gas/liquid separation 22 with from the logistics of gas/liquid separation 25, be separated into the cut of gas oil, kerosene, petroleum naphtha, LPG and waste gas there.
Fig. 4 illustrates the 3rd embodiment of hydrotreater, and this hydrotreater is to have the isolating gas/liquid of middle gas/liquid and flow down flow reactor.According to the identical mode of the described hydrotreater of Fig. 2, the 3rd embodiment of hydrotreater comprises: have reactor 21, middle gas/liquid separation 22, the gas/liquid separation 25 of the hydrogenation catalyst of arranging with multilayer 20, and a fractionation plant.
In order to use this device to carry out hydrotreatment, the top with overhead product and hydrogen supply response device 21 makes them flow downward at inside reactor simultaneously, the hydrotreatment under preset temperature and predetermined pressure of this overhead product.The gas/liquid mixture flows out from upper strata catalyst bed bottom and is sent to middle gas/liquid separation 22, and this mixture separation becomes gas phase and liquid phase there.To and be sent to gas/liquid separation 25 from the cooling of the gas phase of middle gas/liquid separation 22, it is separated into liquid phase and waste gas there.To in middle gas/liquid separation 22, isolating liquid phase flow by lower floor's catalyst bed further hydrotreatment downwards with additional hydrogen.The effluent of autoreactor 21 bottoms and be sent to the fractionation section respectively or together from the effluent of gas/liquid separation 25 in the future, they are separated into gas oil, kerosene, petroleum naphtha, LPG and other materials there.
Fig. 5 illustrates the 4th embodiment of hydrotreater, and it is the gas/liquid countercurrent reactor.The hydrotreater of the 4th embodiment comprises reactor 21, heat exchanger 24, the gas/liquid separation 25 with hydrogenation catalyst 20 of arranging with multilayer, hydrogen sulfide stripping device 26, loop compression device 27 and fractionation plant.
In order to carry out hydrotreatment,, supply with hydrogen from the bottom of reactor 21 simultaneously with the middle portion of overhead product supply between the catalyst bed of the upper and lower with this device.The overhead product of middle portion is separated into comprises gas phase and comprise having the liquid phase that high boiling point heats up in a steamer with low boiler cut.Liquid phase flows downward and flows through lower floor's catalyst bed, and by with the hydrogen counter current contact by hydrotreatment.Flow through the upper strata catalyst bed on gas phase and hydrogen and the flow direction.The gas phase of the hydrotreatment of discharging from reactor head contains more lower boiling cut, unreacted hydrogen and reacted gas.They are sent to heat exchanger 24, so that gas/liquid separation 25 is sent in cooling then, are separated into liquid phase (having lower boiling cut) and gas phase.Be sent to fractionation section 23 respectively or together from the liquid phase of gas/liquid separation 25 discharges and the effluent of discharging from reactor 21 bottoms, there, they are separated into the cut of gas oil, kerosene, petroleum naphtha, LPG and waste gas (lightweight gas).Isolating gas phase is sent to hydrogen sulfide stripping device 26 in gas/liquid separation 25, and this device is equipped with for example absorption of pressure swing (PSA) device.After from gas phase, removing hydrogen sulfide, with this gas phase with loop compression device 27 compression and be back to reactor 21 as hydrogen circulation gas.
The hydrotreater of the 4th embodiment is separated into gas phase (having more lower boiling cut) and liquid phase (cut with higher) with overhead product.The high boiling fraction that is difficult to desulfurization that contains a large amount of sulphur compounds flows downward and the hydrogen counter current contact, so that effectively hydrogenation is flowed than being easier to hydrogenant low boiler cut and hydrogen and flowing to go up, simultaneously so that hydrogenation.Therefore, this class hydrotreater effectively hydrogenation comprises several overhead products with cut of different boiling cut and differential responses, to be fit to the desulfurization of sulfide.
Fig. 6 illustrates a kind of hydrotreater, and it is a kind of being suitable for further refining the gas/liquid with middle gas/liquid separation of low weight cut and flow down flow reactor.With the top of overhead product and hydrogen supply response device 21, and in the catalyst bed of upper strata, handle at first.Gas/liquid separation 22 in the middle of will being introduced into from the logistics of upper strata catalyst bed bottom, it is separated into gas phase and liquid phase there.Liquid phase is made product oil.For further hydrotreatment, with lower floor's catalyst bed of gas phase supply response device 21.To cool off from the logistics of lower floor catalyst bed bottom, and be introduced into gas/liquid separation 25, there, it is separated into gas phase and liquid phase.Usually gas phase is reclaimed and act as a fuel or, simultaneously liquid phase is made product oil as the hydrogen of hydrotreatment.To be sent to the fractionation section respectively or together from the liquid phase effluent of middle gas/liquid separation 22 with from the liquid phase effluent of gas/liquid separation 25.
Fig. 7 illustrates a kind of low weight cut of effectively refining, and is used as the gas/liquid of hydrotreater and flows down flow reactor.Overhead product is separated into gas phase and liquid phase in gas/liquid separation 25A, this separator is contained in the upstream of the reactor 21 with many catalyst beds 20.With the top of gas phase supply response device, simultaneously liquid phase is supplied with the middle part between the catalyst bed of the upper and lower.The gas/liquid mixture of autoreactor bottom is introduced into the first gas/liquid separation 25B in the future, and there, it is separated into gas phase and liquid phase.The isolating gas phase of a part is back to reactor head (representing with discontinuous straight line) in Fig. 7, simultaneously,, and supplies with the second gas/liquid separation 25C the cooling of another part gas phase.Will be from the liquid phase cools of the first gas/liquid separation 25B, and with also to send the fractionation section, come from the liquid phase of second gas/liquid separation or be sent to the fractionation section respectively.The also liquid cooling of autoreactor 21 in the future, and it is supplied with gas/liquid separation, it is separated into waste gas and product oil there.
As mentioned above, by carrying out hydrotreatment and fractionation, the described hydrotreater 12 of available Fig. 1 obtains the cut of gas oil, heavy naphtha, light naphthar, LPG and waste gas.
Waste gas offers amine treatment unit 2, produces fuel gas by removing sour gas.This sour gas is sent to sulfur recovery unit 3, to reclaim sulphur.
In fact, LPG is used as the LPG product.
Light naphthar can directly be admixed in the high-octane rating reformate or if desired must be through reforming or the desulfurization processing.
Heavy naphtha is sent to catalyzer reformer 7, and in device 7, heavy naphtha is through isomerization and aromizing, and is admixed in the high-octane rating reformate.To be sent to hydrotreater 12 at the by product hydrogen in the catalytic reforming unit 7, and, simultaneously the LPG by product will be back to hydrotreater 12 or mix with the LPG that obtains from hydrotreater 12 so that as the hydrogen of hydrotreater.In fact, kerosene can be used as the kerosene product.In fact, gas oil can be used as gas oil product.
Residual oil from crude unit 11 bottoms can be used as the blending compound use of heavy fuel oil or further processing in vacuum distillation plant, to obtain vacuum gas oil.At least a portion vacuum gas oil with from normal pressure overhead product hydrotreatment in hydrotreater 12 of crude unit 11.
Comparing embodiment: conventional method for refining
According to the conventional refinery configuration of Fig. 8 explanation, crude oil is distilled in atmospheric distillation plant, be separated into several fractions, and every kind of cut supplied with hydrotreater do hydrotreatment.Every kind of cut has characteristic as described below.
This crude oil is to have 0.8618 proportion and 1.818%(weight) the Arabic lightweight or heavy (the 50 vol/50 vol) crude oil of sulphur concentration.
The distillation characteristics and the productive rate of every kind of cut of table 1 explanation
Under following condition, every kind of cut carries out the hydrotreatment reaction test:
Catalyzer: the commercially available catalyzer (producing) that contains CoMo by Syokubai-Kasei Kogyo.
Reactor: interior diameter 8mm * long 6000mm
The catalytic amount of filling: 96cc
Type of reactor: and flow down streaming
Hydrogen purity: 70%.
The condition of table 2 explanation hydrotreatment reaction and the reaction result of every kind of cut.
Embodiment 1: light naphthar to the order cut of gas oil (1) is all done hydrotreatment
Light naphthar to gas oil (had C
5-360 ℃ of true boiling points) order cut is as raw material, once carries out hydrotreatment by adopting the reactor the same with comparing embodiment 1.Reaction conditions is following listed:
Pressure: 40kg/cm
2G
Temperature: 330 ℃
H
2/ oil ratio: 100Nm
3/ kilolitre
LHVS：3.11/h
r
Under these conditions, all order cuts are done hydrotreatment together, the product after the hydrotreatment is distilled into light naphthar, heavy naphtha, kerosene and gas oil fraction.Measure the sulphur content of every kind of product.
Sulphur content is following listed:
Light naphthar: 0.1ppm(weight)
Heavy naphtha: 0.3ppm(weight)
Kerosene: 0.001%(weight)
Gas oil: 0.20%(weight)
This presentation of results is compared with the hydrotreatment of a cut of a conventional cut, and this total hydrotreatment can produce gratifying result.Judge by this result, we can say that the present invention can simplify refinery configuration to a great extent, and do not reduce the hydrotreatment effect that obtains with prior art.
Embodiment 2: light naphthar to the order cut of gas oil (2) is carried out total hydrotreatment
Except LHSV is 1.21/h
rWith catalyst levels be outside the 250cc, under the condition identical, light naphthar to the order cut of gas oil is carried out total hydrotreatment with embodiment 1.Measure the sulphur content of every kind of product.
This result as follows is gratifying.
Light naphthar :≤0.1ppm(weight)
Heavy naphtha :≤0.1ppm(weight)
Kerosene: 0.0003%(weight)
Gas oil: 0.05%(weight)
Embodiment 3: adopt the gas/liquid countercurrent reactor to carry out total hydrotreatment
Adopt the illustrated gas/liquid countercurrent reactor of Fig. 5 as reactor, the raw material (light naphthar is to the order cut of gas oil) as embodiment 1 is carried out hydrotreatment.Catalyst bed in the reactor is divided into secondary: upper strata catalyst bed and lower floor's catalyst bed.For total hydrotreatment,, supply with hydrogen from reactor bottom simultaneously under the following reaction conditions raw material (order cut) being offered the middle part between upper strata catalyst bed and lower floor's catalyst bed.
Catalytic amount in the upper bed: 40cc
Catalytic amount in lower floor's bed: 60cc
Pressure: 40kg/cm
2G
Temperature: 330 ℃
H
2/ oil ratio: 100Nm
3/ l
LHSV：3.1 1/h
r
Product after the hydrotreatment is offered the fractionation section distill under normal pressure, so that be separated into light naphthar, heavy naphtha, kerosene and gas oil fraction.Measure the sulphur content of each product.
This result is as follows:
Light naphthar :≤0.1ppm(weight)
Heavy naphtha :≤0.1ppm(weight)
Kerosene: 0.001%(weight)
Gas oil: 0.15%(weight)
Embodiment 4: LPG cut to gas oil fraction is done total hydrotreatment
This processing is to carry out under the condition as embodiment 1 (except the additional LPG of use).Yet, H
2/ oil ratio and LHSV are to be basic calculation with light naphthar one until the inlet amount of gas oil (for example LPG except).
The sulphur content of every kind of product is following listed:
Light naphthar :≤0.1ppm(weight)
Heavy naphtha :≤0.1ppm(weight)
Kerosene: 0.001%(weight)
Gas oil: 0.22%(weight)
Claims (21)
1, a kind of method for refining is characterised in that to comprise:
(a) by using air distillation, with crude separation become residual oil and overhead product and
(b) in single hydrotreater, together this overhead product is all carried out hydrotreatment.
2, according to the method for refining of claim 1, wherein will be distilled into gas oil, kerosene, heavy naphtha, light naphthar, LPG and gas oil fraction by the product that hydrotreatment obtains.
3, according to the method for refining of claim 2, wherein described heavy naphtha fraction is offered catalytic reforming unit, so that be translated into the high-octane rating reformate, will by the catalyzer reformer retrieve have purity be 75% and＞75% hydrogen offer described hydrotreater.
4, according to the method for refining of claim 1, wherein said long residuum offer vacuum distillation plant so as the distillation, obtain vacuum gas oil, and with this vacuum gas oil with the hydrotreatment in described hydrotreater of described normal pressure overhead product.
5, according to the method for refining of one of claim 1-4, wherein said hydrotreater is selected from gas/liquid and flows down flow reactor, gas/liquid countercurrent reactor and gas/liquid and flow one of up-flow reactor.
6, according to the method for refining of claim 5 each described gas/liquid and flow down flow reactor and described gas/liquid and flow up-flow reactor gas/liquid separation is housed wherein, be used for carrying out gas/liquid and separate in the middle part of described reactor.
7, according to the method for refining of one of claim 1-6, wherein will be back to the Reactor inlet of described hydrotreater by the product that described hydrotreatment obtains.
8, according to the method for refining of one of claim 1-7, the condition of wherein said hydrotreatment is as described below: pressure is 20-80kg/cm
2G, temperature is 300-400 ℃, H
2/ oil ratio is 50-200N1/1, and LHSV is 0.1-5h
-1 r
9, according to the method for refining of one of claim 1-7, the condition of wherein said hydrotreatment is as described below: pressure is 30-70kg/cm
2G, temperature is 320-380 ℃, H
2/ oil ratio is that 70-150N1/1 and LHSV are 1-4h
r -1
10, according to the method for refining of claim 1, wherein described overhead product and hydrogen are incorporated into gas/liquid that hydrogenation catalyst is housed and the top that flows down flow reactor, so that the described overhead product of hydrogen treatment, to be incorporated into gas/liquid separation by the effluent that described reactor bottom is discharged, so that be separated into gas phase and liquid phase, described gas phase is recycled into described reactor, simultaneously with described liquid phase distillation, obtain product oil, its part is looped back reactor.
11, according to the method for refining of claim 1, wherein said hydrotreater is gas/liquid and flows down flow reactor, its hydrogenation catalyst bed is divided into secondary at least, upper strata catalyst bed and lower floor's catalyst bed, overhead product is supplied with the top of described reactor with hydrogen, so that the described overhead product of hydrogen treatment, overhead product is discharged from the bottom of described upper strata catalyst bed and is sent to gas/liquid separation, in this separator, overhead product is separated into gas phase and liquid phase, and any one communicated flows through described lower floor catalyst bed by further hydrotreatment.
12, according to the method for refining of claim 1, wherein said hydrotreater is gas/liquid and flows up-flow reactor, its hydrogenation catalyst bed is divided into secondary at least: upper strata catalyst bed and lower floor's catalyst bed, described overhead product is supplied with the bottom of described reactor with hydrogen, so that described overhead product is made hydrogen treatment, effluent is discharged from the top of described lower floor catalyst bed and is sent to gas/liquid separation, effluent is separated into liquid and gas there, this gas phase is supplied with the bottom of described upper strata catalyst bed, so that further hydrotreatment.
13, according to the method for refining of claim 1, wherein said hydrotreater is the gas/liquid counter-current reactor, its hydrogenation catalyst bed is divided into secondary at least: upper strata catalyst bed and lower floor's catalyst bed, described overhead product offered in the middle part between upper strata catalyst bed and the described lower floor catalyst bed use the hydrogen of supplying with at the bottom of the reactor to carry out hydrotreatment, so that obtain gas phase and obtain liquid phase from the bottom of described reactor from described reactor head.
14, according to the method for refining of claim 1, wherein said hydrotreater is gas/liquid and flows down flow reactor, its hydrogenation catalyst bed is divided into the secondary of upper strata catalyst bed and lower floor's catalyst bed at least, described overhead product is offered gas/liquid separation with hydrogen, so that separate gas phase and liquid phase, described gas phase is offered the top of described reactor, simultaneously described liquid phase is incorporated into middle part between described upper strata catalyst bed and described lower floor catalyst bed carrying out hydrotreatment, effluent is discharged from the bottom of described reactor.
15, a kind of refinery configuration is characterized in that comprising:
A kind of atmospheric distillation plant that is suitable for crude distillation is become residual oil and overhead product; With
A kind of being suitable for isolating overhead product in the described atmospheric distillation plant hydrotreater of hydrotreatment together.
16,, be equipped with wherein that the product that is used for obtaining at described hydrotreater is distilled into the cut of gas oil, kerosene, heavy naphtha, light naphthar, LPG and lightweight gas and the segregation section established according to the refinery configuration of claim 15.
17, according to the refinery configuration of claim 16, wherein said configuration comprises that also a kind of catalytic reforming unit and a kind of being used for that described heavy naphtha fraction is changed into the high-octane rating reformate will offer the by product hydrogen supply line of described hydrotreater from the hydrogen that described catalytic reforming unit reclaims.
18, according to the refinery configuration of claim 15, wherein said configuration also comprises a kind of vacuum distillation plant and a kind of vacuum gas oil supply line that is used for described vacuum gas oil is offered described hydrotreater that is suitable for long residuum is distilled into vacuum gas oil.
19, according to the refinery configuration of one of claim 15-18, wherein said hydrotreater is selected from gas/liquid and flows down flow reactor, gas/liquid countercurrent reactor and gas/liquid and flow one of up-flow reactor.
20, according to the refinery configuration of claim 19, wherein any described gas/liquid also flows down flow reactor and described gas/liquid and flow up-flow reactor and be equipped with and be used for carrying out the isolating gas/liquid separation of gas/liquid in the stage casing of described reactor.
21, according to the refinery configuration of one of claim 15-20, wherein said configuration also comprises a kind of being used for the oil circulation product oil return line pipeline of going into the reactor inlet of described hydrotreater of a part of product that obtains at described hydrotreater.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18308593 | 1993-07-23 | ||
| JP183085/93 | 1993-07-23 | ||
| JP6019671A JPH0782573A (en) | 1993-07-23 | 1994-02-16 | Method and apparatus for treating petroleum |
| JP019671/94 | 1994-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1104238A true CN1104238A (en) | 1995-06-28 |
Family
ID=26356518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115788A Pending CN1104238A (en) | 1993-07-23 | 1994-07-22 | Refining method and its configuration |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0635555A3 (en) |
| JP (1) | JPH0782573A (en) |
| KR (1) | KR950003423A (en) |
| CN (1) | CN1104238A (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
| US6162350A (en) * | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
| US6929738B1 (en) | 1997-07-15 | 2005-08-16 | Exxonmobil Research And Engineering Company | Two stage process for hydrodesulfurizing distillates using bulk multimetallic catalyst |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| JP4050364B2 (en) | 1997-09-11 | 2008-02-20 | 日揮株式会社 | Oil processing method and oil processing apparatus |
| KR100326588B1 (en) * | 1998-12-28 | 2002-10-12 | 에스케이 주식회사 | Automated Crude Oil Analysis Using Near Infrared Spectroscopy |
| ID30551A (en) | 1999-05-13 | 2001-12-20 | Shell Int Research | HYDROCARBON CONVERSION PROCESS |
| WO2003078549A1 (en) * | 2002-03-15 | 2003-09-25 | Jgc Corporation | Method of refining petroleum and refining appratus |
| AU2004200270B2 (en) * | 2003-01-31 | 2009-11-12 | Chevron U.S.A. Inc. | High purity olefinic naphthas for the production of ethylene and propylene |
| US6890962B1 (en) | 2003-11-25 | 2005-05-10 | Chevron U.S.A. Inc. | Gas-to-liquid CO2 reduction by use of H2 as a fuel |
| JP4608341B2 (en) * | 2005-03-04 | 2011-01-12 | 出光興産株式会社 | Method for producing gasoline base material |
| JP2009040844A (en) * | 2007-08-07 | 2009-02-26 | Idemitsu Kosan Co Ltd | Method for producing reformed crude oil |
| US8932451B2 (en) | 2011-08-31 | 2015-01-13 | Exxonmobil Research And Engineering Company | Integrated crude refining with reduced coke formation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3050458A (en) * | 1957-12-13 | 1962-08-21 | Shell Oil Co | Petroleum refining process |
| NL278028A (en) * | 1961-05-05 | |||
| US3268438A (en) * | 1965-04-29 | 1966-08-23 | Chevron Res | Hydrodenitrification of oil with countercurrent hydrogen |
| US3801495A (en) * | 1972-05-19 | 1974-04-02 | Chevron Res | Integrated process combining catalytic cracking with hydrotreating |
| WO1992008772A1 (en) * | 1989-05-10 | 1992-05-29 | Davy Mckee (London) Limited | Hydrodesulphurisation process |
-
1994
- 1994-02-16 JP JP6019671A patent/JPH0782573A/en not_active Withdrawn
- 1994-07-20 EP EP94401673A patent/EP0635555A3/en not_active Withdrawn
- 1994-07-22 CN CN94115788A patent/CN1104238A/en active Pending
- 1994-07-23 KR KR1019940017885A patent/KR950003423A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0782573A (en) | 1995-03-28 |
| EP0635555A3 (en) | 1995-08-09 |
| EP0635555A2 (en) | 1995-01-25 |
| KR950003423A (en) | 1995-02-16 |
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