CN107304370A - A kind of recapitalization generating oil hydrogenation process - Google Patents

A kind of recapitalization generating oil hydrogenation process Download PDF

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Publication number
CN107304370A
CN107304370A CN201610252810.5A CN201610252810A CN107304370A CN 107304370 A CN107304370 A CN 107304370A CN 201610252810 A CN201610252810 A CN 201610252810A CN 107304370 A CN107304370 A CN 107304370A
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China
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hydrogenation
reactor
oil
reformer
hydrogenation reactor
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Chinese (zh)
Inventor
崔国英
关明华
方向晨
徐大海
樊宏青
牛世坤
李扬
丁贺
陈�光
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to CN201610252810.5A priority Critical patent/CN107304370A/en
Publication of CN107304370A publication Critical patent/CN107304370A/en
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    • 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
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • C10G45/10—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 characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of recapitalization generating oil hydrogenation process, reformed oil is subjected to hydrotreating before depentanizer is entered, hydrotreating uses liquid-phase hydrogenatin treatment technology, the pipeline of the reformed pre-hydrogenated reactor outlet heat exchanger of connection and hydrogenation reactor entrance is set, gone into operation initial stage in hydrogenation reactor, naphtha after the pre- hydrogenation unit of reformer is refined introduces hydrogenation reactor, through after a period of time, stop the naphtha introducing after refining again, reformed oil is introduced into hydrogenation reactor, normal hydrofining reaction process is carried out.The inventive method can ensure that, at the initial stage of going into operation, reaction product quality is stablized qualified.

Description

A kind of recapitalization generating oil hydrogenation process
Technical field
The present invention relates to a kind of recapitalization generating oil hydrogenation process, specifically by reformed oil post-processing unit It is incorporated into reformer, is particularly suitable for producing the reformer of aromatic hydrocarbons.
Background technology
Catalytic reforming（Catalytic Reforming）It is one of petroleum refining significant process.It is in higher temperature, low Press and face under hydrogen state, in the presence of noble metal catalyst, naphtha is transformed into the reformed oil rich in aromatic hydrocarbons Process.Reformed oil can be directly used as the blend component of motor petrol, and benzene, toluene and diformazan can be also produced through Aromatics Extractive Project Benzene, while the hydrogen of by-product.
Since being gone into operation from first set hydroforming process device in 1940, catalytic reforming process is so far after nearly more than 70 years Development course, with the demand of market and human lives to fuel and aromatic hydrocarbons, many countries are all continuous to catalytic reforming process R and D are carried out.
In recent years, continuing to develop with reforming catalyst and catalytic reforming process, in addition new-type heat exchanger, many streams connection The introducing of the high-efficiency appliance such as heating furnace is closed, technological process is improved, reduce the pressure drop for facing hydrogen system, catalytic reforming faces hydrogen Pressure is greatly reduced；In reduction energy consumption simultaneously, product yield has also obtained further raising.But because reformer is anti- The reduction of pressure is answered, reaction severity is further improved, causes ethylenic unsaturation hydrocarbon content in reformed oil to increase, sternly Ghost image rings follow-up aromatic extraction unit stable operation and product quality.Therefore, reformed oil is before Aromatics Extractive Project part is entered Need to be pre-processed, to ensure that olefin(e) centent therein meets requirement of the extraction unit to raw material.At this stage, reformed oil Deolefination mainly has two methods, clay-filtered technique and hydrofining technology.Due to there is refining effect in clay-filtered technique The problems such as difference, fast deactivation rate and serious environmental pollution, process for refining it has been hydrogenated gradually and has been replaced.
In recent years, the related of technology of alkene is reported in external existing selective hydrogenation and removing reformed oil（Method State IFP Arofining techniques）.Using the benzene fraction of reformed oil as raw material, using noble metal catalyst, comparing mitigation Under conditions of removing raw material in alkene.The domestic oily selective hydrogenation and olefin hydrocarbon removal technology of catalytic reforming generation is also opened in oil refining enterprise Beginning is progressively applied.
China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops to be carried out using noble metal catalyst The oily selective hydrogenation and olefin hydrocarbon removal technology of catalytic reforming generation（FHDO）.The technology is from 2003 first in Maoming Petrochemical branch company Since being applied successfully on benzene fraction hydrogenation and olefin hydrocarbon removal device, realized in succession in the BTX cuts of Yanshan Mountain branch company, Chang Ling branch company Commercial Application, also successfully realizes commercial Application in 2009 on the full cut of Zhenghai refinery reformed oil.Current reformation generation Oily selective hydrogenation and olefin hydrocarbon removal commercial plant, provided with the dynamic equipment such as raw material pump, make-up hydrogen compressor, circulating hydrogen compressor, device hydrogen Gas circulate operation, is a set of independent unit, and it is higher to there is energy consumption, and the problem of investment and operating cost are higher have impact on enterprise Economic benefit.
CN103666544A discloses a kind of recapitalization generating oil hydrogenation processing method.This method is in liquid-phase hydrogenatin treatment conditions Under, reformed oil is contacted with the catalyst with catalytic hydrogenation in hydrogenation reactor, weight is taken full advantage of Alkene in dissolved hydrogen in whole generation oil, removing reformed oil, while also eliminating for recycle hydrogen and its recycle unit Demand.Although this method technological process is simpler, still need newly-built a set of hydrogenation plant, operating cost with this method ratio Also it is of a relatively high.
CN102911721A discloses a kind of method of reformed oil liquid phase circulation selective hydrogenation and olefin hydrocarbon removal.In pipeline Middle progress hydrogen saturation, forms a kind of liquid phase mixture of raw material/hydrogenation products/hydrogen, under hydroconversion condition, liquid phase mixture point Section enters multistage conventional hydro reactor；Segmentation enters beds area and reacted, the reaction come out from reactor bottom Product section circulation afterwards is mixed with fresh feed, and follow-up separator is partly discharged from reaction system.This method technique stream Journey is different with this method, is to be fed from reactor top, and is also a set of independent hydrogenation plant, investment and operating cost phase To also higher.
In the technology of recapitalization generating oil hydrogenation processing, hydrogenation plant goes into operation initial stage, due to reaction condition and catalyst The state that performance is not up to needed for reaction, therefore hydrogenation products are typically up to less than quality index, to follow-up aromatic extraction unit Normal Influence of production it is larger.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of recapitalization generating oil hydrogenation process, by hydrotreating Device is optimized with reformer and combined, and can not only be met olefin(e) centent after recapitalization generating oil hydrogenation and be met extracting requirement, And investment, energy consumption, operating cost are greatly lowered compared with existing apparatus, are gone into operation while solving hydrogenation plant caused by initial stage The problem of product quality is not up to standard.
The recapitalization generating oil hydrogenation process of the present invention includes following content：Reformed oil is being entered into depentanizer Carry out hydrotreating before, hydrotreating uses liquid-phase hydrogenatin treatment technology, including reformed oil after temperature raising with hydrogen Mixed dissolution, subsequently into hydrogenation reactor, in hydrogenation reactor, reformed oil remains at least partly in liquid phase state, Hydrobon catalyst is used in hydrogenation reactor, hydrofining reaction effluent is directly entered depentanizer and carried out at fractionation Reason；The pipeline that naphtha of the pre- hydrogenation unit of reformer after refined is introduced to hydrogenation reactor is set, opened in hydrogenation reactor Work initial stage, naphtha introduces hydrogenation reactor after hydrofinishing, after 5 minutes~24 hours, after preferably 1~10 hour, then Stop introducing the refined rear naphtha of pre- hydrogenation unit, reformed oil is introduced into hydrogenation reactor, normal hydrofinishing is carried out Course of reaction.
In the inventive method, hydrogenation reactor is arranged on again between contact tower and depentanizer of reformer, if weight Contain dechlorination tank in engagement positions, be then arranged between dechlorination tank and depentanizer.Contact tower again（Or dechlorination tank）The reformation of discharge Generation oil carries out fully dissolving in air and liquid mixer after heat exchanger, with hydrogen and mixed, subsequently into hydrogenation reactor.Plus Hydrogen reactor is entered in reactor using downflow operation mode, i.e. reaction mass from hydrogenation reactor top carries out the de- alkene of hydrogenation Hydrocarbon reaction, after refined oil is by depentanizer, can be directly entered extraction unit.Hydrogenation reactor can also be using up flow type operation Mode, i.e. reaction mass enter from hydrogenation reactor bottom carries out hydrogenation and olefin hydrocarbon removal reaction in reactor.Can be in contact tower again （Or dechlorination tank）The pipeline directly connected is set between depentanizer, when needing to carry out maintenance disposal for hydrogenation reaction device Hydrogenation plant can be isolated with reformer system.Hydrogenation reactor uses liquid phase reactor state, i.e., at reaction conditions, extremely Small part reformed oil is liquid phase state, preferably 80%（Weight）Most preferably more than 90% reformed oil is liquid phase shape above State.Naphtha after the pre- hydrogenation unit of reformer is refined is introduced after hydrogenation reactor, and effluent is recycled back to reformation by pipeline The pre- hydrogenation unit of device, can also be recycled back to reformer reforming reactor entrance.After the pre- hydrogenation unit of reformer is refined Naphtha can also introduce depentanizer after introducing hydrogenation reactor, and pre- hydrogenation unit or reforming reaction are recycled back to from depentanizer Device.Pipeline and valve that can be according to needed for being set recycle scheme.Naphtha after the pre- hydrogenation unit of reformer is refined is from vapour Stripper bottom or fractionation column base are drawn, and temperature is generally 100~180 DEG C.Reformer is introduced in hydrogenation reactor to be hydrogenated with advance The volume space velocity of naphtha is arbitrary after unit is refined, as long as fully wetting hydrogenation catalyst, generally 0.05 h-1~ 50.0h-1, it is preferably 0.5 h according to the ability of normal device for transporting objects-1~10.0h-1.Introduce reformer and be hydrogenated with list in advance Naphtha can dissolve hydrogen after member is refined, hydrogen can also not dissolved, preferably by hydrogen to oil volume ratio 2：1~5：1 dissolving hydrogen.
In the inventive method, air and liquid mixer is set before hydrogenation reactor is entered, for by hydrogen and reformed oil Progress is sufficiently mixed dissolving.Air and liquid mixer can be static mixer or dynamic mixer.Static mixer can be selected from SV In type static mixer, SK types static mixer, SX types static mixer, SH types static mixer, SL type static mixers One or several kinds combination, dynamic mixer can be a kind of or several in mixing pump, overcritical blender, mixer Plant combination.
Reformed oil in the inventive method can be the full cut of reformed oil, can also pass through reformed oil Benzene fraction or BTX cuts.
In the inventive method, hydroprocessing operations condition and catalyst are also close with prior art.As reaction pressure For the MPa of 0.5 MPa ~ 6.0, the MPa of preferably 1.2 MPa ~ 3.0, reaction pressure is according to contact tower again（Or dechlorination tank）Pressure It is determined that, regulation is typically not required to, can also suitably be adjusted as needed；Reaction temperature be 100 DEG C ~ 200 DEG C, preferably 120 ℃~170℃；Volume space velocity is 1.0 h-1~10. 0h-1, preferably 2.0 h-1~6.0 h-1；Hydrogen oil body before into air and liquid mixer Product is than being 0 ~ 20：1（Due to the hydrogen containing dissolving in reformed oil, therefore it can be 0 to introduce the hydrogen of air and liquid mixer）, Preferably 2：1~5：1.In the inventive method, hydrogen to oil volume ratio can be reduced substantially compared with existing conventional method.Above-mentioned reaction It is liquid phase state that condition, which ensure that reformed oil at least keeps more than 80%,.
In the inventive method, the Hydrobon catalyst used can be commodity Hydrobon catalyst, such as with noble metal Or the Hydrobon catalyst that reduced state nickel is active component, such catalyst, can be mutually with higher hydrogenation activity Hydrogenation reaction is carried out at relatively low temperature.It is preferred to use the Hydrobon catalyst using middle noble metal as active component, such as Fushun The HDO-18 catalyst of Petroleum Chemical Engineering Institute's development and production.Noble metal hydrogenation catalyst for refining is general using aluminum oxide as carrier, Using Pt and/or Pd as active component, the content of active component by weight in the catalyst be not less than 0.1%, generally 0.1%~ 1.5%.For the Hydrobon catalyst using reduced state nickel as active component, typically using aluminum oxide or modified aluminas as carrier, Using nickel oxide as active component（The 15%~70% of catalyst weight, preferably 25%~45% are accounted in terms of nickel oxide weight）, Reduction activation is being carried out to catalyst using preceding, nickel oxide reduction-state is being converted into, to improve catalyst hydrogenation activity.Counterweight For whole generation oil distillate raw material, using the Hydrobon catalyst reformed oil bromine index can be made to be less than 100mgBr/ 100g, and aromatic hydrocarbons loss is less than 0.5%, meets the charging index request of follow-up aromatic extraction unit.
Catalytic reforming uses noble metal catalyst, and the impurity such as sulphur, nitrogen is the poisonous substance of such catalyst, therefore catalytic reforming is former Material needs to remove sulphur, nitrogen by pre- hydrogenation, therefore catalytic reforming complexes include the pre- hydrogenation plant of reformer feed.This Shen Please the organic knot of the hydrotreater of the pre- hydrogenation plant of reformer feed and reformed oil is coordinated, made at recapitalization generating oil hydrogenation Reason device is rapidly achieved optimal use state, it is to avoid the initial production subsequent operational problems off quality brought.
The inventive method takes full advantage of and connect again on the premise of pressure needed for meeting system pressure balance and hydrogenation reaction Tower top hydrogen is touched as raw hydrogen, is sufficiently mixed with bottom of towe feedstock oil in air and liquid mixer from reactor top and enters liquid phase Hydrogenation and olefin hydrocarbon removal reactor, simplifies technological process, reduces cost of investment.Simultaneously when hydrogenation plant goes into operation, one is first introduced The refined naphtha of section time pre- hydrogenation unit, the optimal shape for making hydrogenation reactor and hydrogenation catalyst be rapidly achieved needed for reaction State, does not result in device and goes into operation the problem of initial stage, hydrogenation reaction product did not reached index.This method makes this process have more Good flexibility, will not influence the normal operation of subsequent extraction device because of this process.
Brief description of the drawings
Fig. 1 is a kind of idiographic flow schematic diagram of the inventive method.Wherein：1- reformation stabilizer base oils, 2- heat exchangers, 3- is again Contact tower, 4- valves, 5- contacts tower top hydrogen-rich gas, 6- heat exchangers, 7- air and liquid mixers, 8- hydrogenation reactors, 9- de- penta again Alkane tower, 10- depentanizers bottom pump, 11- depentanizers bottom reboiler, 12- depentanizer base oils, 13- pentane admixtures, 14- valves Door, the pre- hydrogenation unit stripper column bottoms pump of 15- reformers, the pre- hydrogenation unit stripper of 16- reformers.
Embodiment
The inventive method is described in detail with specific embodiment below in conjunction with the accompanying drawings.
New device for using the inventive method, as shown in Figure 1：Before hydrogenation reactor 8 goes into operation, by reformer The bottom of towe oil part of pre- hydrogenation unit stripper 16 introduces hydrogenation reactor 8, and now the effluent of hydrogenation reactor 8 is recycled back to weight The pre- hydrogenation unit stripper 16 of engagement positions.After suitable time, stop introducing the bottom of towe oil of pre- hydrogenation unit stripper 16, will The reformed oil of the discharge of contact tower 3 is reformed again after exchanging heat and dissolving hydrogen, hydrogenation reactor 8 is introduced, completion went into operation Journey.This flexible technological process avoids the initial production that goes into operation unqualified stationary phase.
The reformed oil handled by the inventive method, product can reach following property：Refined oil bromine index is less than 100mgBr/100g, aromatic hydrocarbons loss 0.5%.Other properties meet requirement of the extraction device to feedstock oil.
The advantage of the invention is that：Technological process is simple, easy to operate, invests less.For having weighed for oil refining enterprise Engagement positions, only need to increase a hydrogenation and olefin hydrocarbon removal reactor and a gas again in reformer between contact tower and depentanizer Liquid mixer both may be used, it is not necessary to independent newly-built a set of hydrogenation and olefin hydrocarbon removal device, and investment and operating cost can be greatly lowered.This hair Bright method technological process is simple, and operating condition more relaxes, and exploitativeness is strong, and clay-filtered unit or hydrogenation can be substituted completely Refined unit；And without the dynamic equipment such as make-up hydrogen compressor, circulating hydrogen compressor.If using existing process method, needed newly-built Hydrogenation plant and corollary equipment, and investment and operating cost are higher.Increase again contact tower bottom simultaneously to reformed pre-hydrogenated reaction Device outlet heat exchanger returns to air and liquid mixer circular route, goes into operation initial stage, and the naphtha after reformed pre-hydrogenated introduces hydrogenation dress Put, reaction system can be made to rapidly enter optimum response state, it is ensured that product quality directly meets extracting and required, it is to avoid just Phase product unqualified stationary phase.
The following examples illustrate the present invention further.
Experiment, using the hydrotreating catalyst that catalyst is commercial Application, is Fushun Petrochemical Research Institute's development and production HDO-18 hydrogenation catalysts, its physicochemical property index is shown in Table 1.
Embodiment 1
By the newly-built reformer of application scheme.Reformed oil raw material passes through stabilizer, again contact tower and tower top hydrogen partial After being sufficiently mixed dissolving in SV type static mixers, into hydrogenation and olefin hydrocarbon removal reactor, reaction condition is：Reaction pressure 1.5MPa ﹑ volume space velocities 3.7h-1, 142 DEG C of reaction temperature.Hydrogenation plant is carried out using method of the present invention and carries out the place that goes into operation Reason, when hydrogenation plant goes into operation, first introduces the naphtha of reformed pre-hydrogenated unit stripping tower bottom（130 DEG C of temperature, volume space velocity 0.5h-1）, after 5 hours, switch to normal operating process（Reformed oil enters hydrogenation reactor, the stone of stripping tower bottom Cerebrol is not re-introduced into hydrogenation reactor）.Raw material oil nature and product property are listed in table 2.
From table 2, use the technology can make the bromine index of reformed oil be reduced to 100mgBr/100g with Under, and aromatic hydrocarbons loss 0.5%, and whole start-up process product quality also keeps stable.
Comparative example 1
According to the scheme of embodiment 1, simply when going into operation, reformed oil is directly entered hydrogenation reactor.In start-up process, Reaction product has the requirement that can not touch the mark in about 30 hours.
Embodiment 2
The use of the clay-filtered technological transformation of reformed oil is herein described method.Reformed oil raw material 2 is by stable After tower, again contact tower and tower top hydrogen partial are sufficiently mixed dissolving in SH type static mixers, into hydrogenation and olefin hydrocarbon removal reaction Device, reaction condition is：Reaction pressure 1.6MPa ﹑ volume space velocities 4.0h-1, 155 DEG C of reaction temperature.Using method of the present invention Carry out hydrogenation plant and carry out the processing that goes into operation, reformed oil first introduces Clay Refining Unit and introduced after clay-filtered when going into operation Depentanizer, the naphtha of reformed pre-hydrogenated unit stripping tower bottom（130 DEG C of temperature, volume space velocity 1.0h-1）Introduce hydrogenation reaction Device, after 30 minutes, switches to normal operating process（Reformed oil enters hydrogenation reactor, the stone brain of stripping tower bottom Oil is not re-introduced into hydrogenation reactor）.Raw material oil nature and product property are listed in table 2.
From table 3, use the technology can make the bromine index of reformed oil be reduced to 100mgBr/100g with Under, and aromatic hydrocarbons loss 0.5%, and also quality keeps stable to whole start-up process product quality.
Comparative example 2
According to the scheme of embodiment 2, simply when going into operation, reformed oil is directly entered hydrogenation reactor.In start-up process, Reaction product has the requirement that can not touch the mark in about 30 hours.
The physicochemical property index of the catalyst of table 1
The raw material oil nature of 2 embodiment of table 1 and result of the test
The raw material oil nature of 3 embodiment of table 2 and result of the test

Claims (10)

1. a kind of recapitalization generating oil hydrogenation process, including following content：By reformed oil before depentanizer is entered Hydrotreating is carried out, hydrotreating uses liquid-phase hydrogenatin treatment technology, including reformed oil to be mixed after temperature raising with hydrogen Dissolving, subsequently into hydrogenation reactor, in hydrogenation reactor, reformed oil remains at least partly in liquid phase state, hydrogenation Hydrobon catalyst is used in reactor, hydrofining reaction effluent is directly entered depentanizer and carries out fractionation processing；Its It is characterised by：The pipeline that naphtha of the pre- hydrogenation unit of reformer after refined is introduced to hydrogenation reactor is set, it is anti-in hydrogenation Device is answered to go into operation initial stage, naphtha introduces hydrogenation reactor, after 5 minutes~24 hours, preferably 1~10 hour after hydrofinishing Afterwards, then stop introducing pre- hydrogenation unit it is refined after naphtha, reformed oil is introduced into hydrogenation reactor, is normally hydrogenated with Refining reaction process.
2. in accordance with the method for claim 1, it is characterised in that：Hydrogenation reactor be arranged on reformer contact tower again and Between depentanizer.
3. in accordance with the method for claim 1, it is characterised in that：Contain dechlorination tank in reformer, hydrogenation reactor is set Between dechlorination tank and depentanizer.
4. according to the method described in Claims 2 or 3, it is characterised in that：Between contact tower again or dechlorination tank and depentanizer The pipeline directly connected is set, can be by hydrogenation plant and reformer when needing repair and dispose for hydrogenation reaction device Isolation of system.
5. in accordance with the method for claim 1, it is characterised in that：Hydrogenation reactor uses liquid phase reactor state, i.e., in reaction Under the conditions of, at least part reformed oil is liquid phase state, and preferably more than 80% reformed oil is liquid phase state.
6. in accordance with the method for claim 1, it is characterised in that：Naphtha after the pre- hydrogenation unit of reformer is refined is introduced After hydrogenation reactor, effluent is recycled back to the pre- hydrogenation unit of reformer by pipeline.
7. in accordance with the method for claim 1, it is characterised in that：Air and liquid mixer is set before hydrogenation reactor is entered, used In hydrogen and reformed oil progress are sufficiently mixed into dissolving, air and liquid mixer is static mixer or dynamic mixer.
8. in accordance with the method for claim 1, it is characterised in that：Hydrotreating reaction pressure is the MPa of 0.5 MPa ~ 6.0, most It is well the MPa of 1.2 MPa ~ 3.0；Reaction temperature is 100 DEG C ~ 200 DEG C, preferably 120 DEG C ~ 170 DEG C；Volume space velocity is 1.0 h-1 ~10. 0h-1, preferably 2.0 h-1~6.0 h-1；The hydrogen to oil volume ratio for introducing hydrogen is 0 ~ 20：1, preferably 2：1~5：1.
9. in accordance with the method for claim 1, it is characterised in that：The hydrofinishing processing catalyst used is used with your middle gold Belong to the hydrotreating catalyst for active component, noble metal hydrogenation handles catalyst using aluminum oxide as carrier, using Pt and/or Pd as Active component, the content of active component by weight in the catalyst is not less than 0.2%, generally 0.2%~0.5%.
10. in accordance with the method for claim 1, it is characterised in that：Naphtha after the pre- hydrogenation unit of reformer is refined from Stripper bottom or fractionation column base are drawn.
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