CN101376828A - Hydrofinishing method for coker gasoline - Google Patents

Hydrofinishing method for coker gasoline Download PDF

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Publication number
CN101376828A
CN101376828A CNA2007100126832A CN200710012683A CN101376828A CN 101376828 A CN101376828 A CN 101376828A CN A2007100126832 A CNA2007100126832 A CN A2007100126832A CN 200710012683 A CN200710012683 A CN 200710012683A CN 101376828 A CN101376828 A CN 101376828A
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Prior art keywords
reactor
coker gasoline
hydrogenation
raw material
surge tank
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王震
王晓璐
肖云鹏
刘继华
李扬
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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 CNA2007100126832A priority Critical patent/CN101376828A/en
Publication of CN101376828A publication Critical patent/CN101376828A/en
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Abstract

The invention discloses a hydrogenation refining method of coking kerosene. A diene-removing reactor is additionally arranged in front of the reactor of a coking kerosene hydrogenation device for selectively removing the diene and less olefin in an oil product under a lower reaction temperature; the coking kerosene directly enters the hydrogenation device for treatment without through the storage tank of the oil product; an automatic backwashing filter and a circulating oil line are additionally added. The measures can be adopted to effectively delay the pressure drop of the reactor from rising and ensure the running period of the hydrogenation device.

Description

A kind of hydrofinishing method for coker gasoline
Technical field
The invention belongs to the hydroprocessing technique technology.Specifically, be coker gasoline cut fraction hydrogenation process for refining technology.
Background technology
At present, the crude oil heaviness of refinery processing, the trend of poor qualityization are obvious day by day, and along with The development in society and economy, the demand that light ends oil is particularly cleaned light ends oil progressively increases, and inferior, heavy feed stock need be converted into cleaning light ends oil production.Delayed coking is the important means that realizes inferior heavy oil, residual oil lighting, has obtained widespread use at each refinery.
The product of delayed coker produces normally is cut into coker gasoline, coker gas oil and wax tailings in fractionating system, and the final boiling point of coker gasoline is generally about 180 ℃.The coker gasoline cut is general to adopt following several modes to handle: direct mediation charging as the pre-hydrogenation unit of catalytic reforming; After hydrotreatment as the mediation charging of the pre-hydrogenation unit of catalytic reforming; Raw material as preparing ethylene by steam cracking after hydrotreatment dispatches from the factory; After hydrotreatment as the charging of molecular sieve dewaxing unit.Because sulphur, nitrogen, alkene, the diene content height of coker gasoline, stability is very poor, adopts all necessary step through hydrotreatment of which kind of mode.
Industry coker gasoline hydrogenation unit exists to some extent because of lift velocity falls in pressure and causes device unplanned shutdown problem often soon in operation process, and its reason mainly contains the following aspects:
(1) coker gasoline advances tank stores usually and resupplies hydrogenation unit, is subjected to the influence of head tank secluding air effect, very fast generation oxidizing reaction behind the diolefine ingress of air;
(2) diolefine character is comparatively active, just can polymerization reaction take place under lower temperature, even stop up pipeline and Tube Sheet of Heat Exchanger layer before and after the process furnace, cause system pressure drop sharply to increase.
(3) in traditional coker gasoline hydrogenation technique, most of coker gasoline raw material is vaporized under hydrogenation conditions, and a small amount of unvaporized colloid class material is easy to be deposited on the catalyzer top, and then the coking and blocking beds;
(4) delayed coking unit generally uses and contains silicon defoaming agent, and silica flour is carried by coker gasoline as impurity and enters hydrogenation system.Trickle silicon powder particle can not be removed by automatic backwashing filter, is deposited on the top of reactor bed, has further aggravated the fast rise of bed pressure drop, and silicon powder deposit causes catalyst activity reduction in catalyzer micropore inside simultaneously.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, and described is that hydrogenation and removing diolefine under more shallow hydroconversion condition is to guarantee less loss of octane number with the pre-sulfide catalyst series connection of two different activities and variable grain diameter.Because two kinds of catalyzer can be put into a reactor or two reactors, can not guarantee that catalyzer reacts under lower temperature of reaction, therefore can not delay raw material and generate oil heat exchanger shell side and heating furnace tube coking degree.
USP4343693 discloses a kind of method that removes impurity such as sulfonate, silicone oil from feed stream.Described feed stream is the oil fuel that comprises C5~C10 hydro carbons.This patent use cheap and effectively silicon oxide and bauxitic clay be sorbent material, can reduce running cost.CN 1478862A discloses a kind of method that removes silicoorganic compound from distillate.Described is that material passes through the adsorbent bed of salic and silicon oxide, adsorbing and removing silicon compound under suitable temperature, and this method flow is longer, and desorbing agent regeneration needs to use caustic alkali, causes unnecessary environmental pollution.Above-mentioned desilication method is unsuitable for the petroleum naphtha hydrogenation device.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of hydrofinishing method for coker gasoline, can delay coker gasoline hydrogenation unit system pressure drop to greatest extent and rise, guarantee the running period of hydrogenation unit.
Hydrofinishing method for coker gasoline provided by the invention comprises following content: before outlet of the coker gasoline of delayed coking unit fractionating system and hydrogenation unit raw material surge tank automatic backwashing filter is set; Coker gasoline directly enters hydrogenation device for treatment without oil product storage tank by the raw material surge tank; Hydrogenation unit raw material surge tank increases volume and nitrogen-sealed is set; The dialkene removal reactor is set before the hydrogenation unit reactor; The turning oil line of setting from oil export at the bottom of the separation column to the raw material surge tank guarantees the stable of hydrogenation unit feed rate.By taking these processing, coker gasoline enters hydrofining reactor, can delay hydrofining reactor pressure and fall rising, guarantees the running period of hydrogenation unit.
Some concrete technology contents are as follows in the hydrofinishing method for coker gasoline of the present invention:
1, the delayed coking unit fractionating system cuts out coker gasoline, carries out the first time through automatic backwashing filter earlier and filters, and removes particle diameter〉25 μ m solid particulates.Oil product after the filtration is without storage tank, and the automatic backwashing filter that directly enters hydrogenation unit by pipeline carries out the filtration second time, incoming stock again surge tank.The surge tank nitrogen-sealed prevents the stock oil ingress of air.The volume of surge tank is generally more than or equal to the volume of hydrofining reactor.
2, coker gasoline is adjusted to suitable temperature of reaction through the heat exchange facility, enters the hydrogenation dialkene removal reactor again and reacts.The heat exchange facility is one group (platform) or several groups of (platform) interchanger, and the by-pass that can adjust flow is set, to adjust temperature of reaction.
3, the operational condition of dialkene removal reactor is:
Working pressure: 2.0~8.0MPa;
Reactor inlet temperature: 100~250 ℃;
Average reaction temperature: 110~300 ℃;
Volume space velocity: 2.0~15.0h -1
Hydrogen to oil volume ratio: 200~1000.
Control dialkene removal reactor generates oily diene value<0.2g-I/100g.
4, use conventional Hydrobon catalyst in the dialkene removal reactor, or use the Hydrobon catalyst after the regeneration, or use the dialkene removal special-purpose catalyst.The use of generally not regenerating of used dialkene removal catalyzer.
5, the dialkene removal reactor is provided with pipeline in parallel, and more catalyst changeout of too high time excision reactor falls in pressure, and hydrogenation unit uses pipeline in parallel to continue to produce the processing of need not stopping work.More required time of catalyst changeout shorter, to the not obviously influence of back master's hydrofining reactor.
6, the reaction heat of coker gasoline hydrogenation is very big, after raw material directly supplies hydrogenation unit, for preventing the quiet run of delayed coker produces influence of fluctuations hydrogenation unit, increases the space of surge tank, uses nitrogen-sealed.And set up turning oil line from oil export at the bottom of the separation column to the raw material surge tank, the coker gasoline behind the hydrogenation partly circulates, to adjust the material flow instability problem of coker instability generation.
The present invention has following several advantages:
1, coker gasoline is removed mechanical impurity through the automatic backwashing filter two-stage filtration.
2, coker gasoline is without the tank field, and the raw material surge tank is provided with nitrogen-sealed, avoids the stock oil ingress of air to greatest extent.
3, under suitable operational condition, remove diolefine, prevent diolefine polymerization reaction take place blocking pipeline, help the reactive system quiet run of coker gasoline hydrogenation unit simultaneously.
4, too high time excision reactor falls in the dialkene removal reactor pressure, and device uses pipeline in parallel to continue to produce, and need not stop work, and main hydrofining reactor is not had obvious influence.
5, avoided the detrimentally affect of silica flour that coker gasoline carries to system pressure drop and coker gasoline activity of hydrocatalyst.
6, increase the surge tank space, the turning oil line is set, prevent the influence of delayed coker operation fluctuation hydrogenation unit.
7, prolong the operational cycle of coker gasoline hydrogenation unit to greatest extent, improve economic benefit of enterprises.
Description of drawings
Fig. 1 is a coker gasoline hydrogenation technique schematic flow sheet of the present invention.
Wherein: 1 is coker gasoline, and 2,3 is automatic backwashing filter, 4 raw material surge tanks, 5 is the hydrogenation fresh feed pump, and 6 is interchanger, and 7 is the dialkene removal reactor, 8 is process furnace, and 9 is hydrofining reactor, and 10 is high-pressure separator, 11 is new hydrogen, and 12 is recycle hydrogen, and 13 is light pressure separator, 14 is stripping tower, 15 is separation column, and 16 is hydrogenated gasoline, and 17 is the hydrogenated gasoline circular route.
Embodiment
Further specify technical process of the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, coker gasoline 1 filters through 2,3 two automatic backwashing filters, incoming stock surge tank 4, mix with recycle hydrogen and new hydrogen through hydrogenation fresh feed pump 5, enter dialkene removal reactor 7 through interchanger 6 heat exchange to suitable temperature of reaction, at working pressure 2.0~8.0MPa, 100~250 ℃ of reactor inlet temperatures, 110~300 ℃ of average reaction temperature, volume space velocity 2.0~15.0h -1, hydrogen to oil volume ratio 200 ~ 1000 processing condition under carry out dialkene removal reaction.Reaction product enters hydrofining reactor 9 through process furnace 8, carries out hydrofining reaction under conventional coker gasoline hydroconversion condition.Reaction product enters high-pressure separator 10 and carries out gas-liquid separation behind interchanger, air-cooler, water recirculator, gaseous product recycles behind circulating hydrogen compressor, and product liquid enters light pressure separator 13 and carries out gas-liquid separation once more.Low branch liquid product enters stripping tower 14 and carries out full cut stripping, enters in the separation column 15 again, obtains hydrogenated gasoline 16 at the bottom of the fractionation Tata.When coking was unstable, hydrogenated gasoline 16 can loop back charging surge tank 4 by circular route 17 parts, to guarantee the steady running of hydrogenation unit.
The dialkene removal catalyzer that the present invention uses can be selected the new agent or the regenerator of conventional Hydrobon catalyst, or the dialkene removal special-purpose catalyst.Conventional Hydrobon catalyst can be the common Hydrobon catalyst in this area, FH-5, FH-5A, FH-98, FH-40A, catalyzer such as FH-40B, FH-40C as Fushun Petrochemical Research Institute's development and production, also can be other similar catalyzer, preferred FH-5 catalyzer and FH-98 catalyzer.The SHT catalyzer of dialkene removal special-purpose catalyst such as Fushun Petrochemical Research Institute's development and production.The catalyzer of dialkene removal reaction inactivation generally is not suitable for regeneration and uses, the catalyzer after therefore preferred other unifining process regeneration.Conventional Hydrobon catalyst is an active metal component with among W, Mo, Ni, the Co one or more generally, and active metallic content counts 10%~40% with oxide weight.The dialkene removal special-purpose catalyst is an active metal component with among W, Mo, Ni, the Co one or more generally, and active metallic content counts 10%~30% with oxide weight, and carrier is siliceous aluminum oxide.
The following examples will be elaborated to the inventive method, but the present invention is not subjected to the restriction of embodiment.
Embodiment 1
Stock oil character sees Table 1, and the dialkene removal reactor operating condition sees Table 2, and dialkene removal reactor hydrogenated products character sees Table 3.
Table 1 stock oil character
Figure A200710012683D00091
Table 2 dialkene removal reactor operating condition
Table 3 dialkene removal reactor product character
Embodiment 2
Stock oil character sees Table 4, and the dialkene removal reactor operating condition sees Table 5, and dialkene removal reactor hydrogenated products character sees Table 6.
Table 4 stock oil character
Figure A200710012683D00101
Table 5 dialkene removal reactor operating condition
Figure A200710012683D00102
Table 6 dialkene removal reactor product character

Claims (8)

1, the invention discloses a kind of hydrofinishing method for coker gasoline, comprise following content: before outlet of the coker gasoline of delayed coking unit fractionating system and hydrogenation unit raw material surge tank, automatic backwashing filter is set; Coker gasoline directly enters hydrogenation device for treatment without oil product storage tank by the raw material surge tank; Hydrogenation unit raw material surge tank increases volume and nitrogen-sealed is set; The dialkene removal reactor is set before the hydrogenation unit reactor; The turning oil line of setting from oil export at the bottom of the separation column to the raw material surge tank guarantees the stable of hydrogenation unit feed rate.
2, in accordance with the method for claim 1, it is characterized in that described coker gasoline filters through two cover automatic backwashing filters of delayed coking unit and hydrogenation unit, removes particle diameter〉25 μ m solid particulates.
3, in accordance with the method for claim 1, it is characterized in that described hydrogenation unit raw material surge tank volume 〉=hydrofining reactor volume.
4, in accordance with the method for claim 1, the operational condition that it is characterized in that described dialkene removal reactor is:
Working pressure: 2.0~8.0MPa;
Reactor inlet temperature: 100~250 ℃;
Average reaction temperature: 110~300 ℃;
Volume space velocity: 2.0~15.0h -1
Hydrogen to oil volume ratio: 200~1000.
5, according to claim 1 or 4 described methods, it is characterized in that described coker gasoline adjusts to suitable temperature of reaction through the heat exchange facility, enter hydrogenator again and carry out hydrofining reaction, described heat exchange facility is one group or several groups of interchanger, and the by-pass of adjusting flow is set.
6, in accordance with the method for claim 1, it is characterized in that described dialkene removal reactor is provided with pipeline in parallel.
7, in accordance with the method for claim 1, it is characterized in that the conventional Hydrobon catalyst of filling in the described dialkene removal reactor, or filling regeneration Hydrobon catalyst, or filling dialkene removal special-purpose catalyst.
8, in accordance with the method for claim 7, it is characterized in that described conventional Hydrobon catalyst is an active metal component with among W, Mo, Ni and the Co one or more, active metallic content counts 10%~40% with oxide weight.
CNA2007100126832A 2007-08-27 2007-08-27 Hydrofinishing method for coker gasoline Pending CN101376828A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101818075A (en) * 2010-04-29 2010-09-01 华南理工大学 Method for reducing re-contact process energy consumption of catalytic reforming device
CN102732303A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732309A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732308A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732307A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrofining method and decoking tank
CN102732310A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732305A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN103611362A (en) * 2013-12-13 2014-03-05 海南汉地阳光石油化工有限公司 Filter device and petroleum hydrogenation system
CN103789020A (en) * 2012-11-03 2014-05-14 中国石油化工股份有限公司 Hydrogenation method of coker gasoline
CN103789018A (en) * 2012-11-03 2014-05-14 中国石油化工股份有限公司 Hydroprocessing method of coker gasoline
CN110129093A (en) * 2019-05-21 2019-08-16 山东京博石油化工有限公司 A kind of pre-hydrotreating reaction system
CN111495436A (en) * 2020-04-17 2020-08-07 中国石油化工股份有限公司 Sulfurizing method of hydrogenation catalyst

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101818075B (en) * 2010-04-29 2013-06-12 华南理工大学 Method for reducing re-contact process energy consumption of catalytic reforming device
CN101818075A (en) * 2010-04-29 2010-09-01 华南理工大学 Method for reducing re-contact process energy consumption of catalytic reforming device
CN102732303B (en) * 2011-04-15 2014-07-23 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732309B (en) * 2011-04-15 2014-07-23 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732307A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrofining method and decoking tank
CN102732310A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732305A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732309A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732308A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732310B (en) * 2011-04-15 2014-08-20 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732303A (en) * 2011-04-15 2012-10-17 中国石油化工股份有限公司 Device and method for hydrogenation reaction of naphtha
CN102732307B (en) * 2011-04-15 2014-06-25 中国石油化工股份有限公司 Naphtha hydrofining method and decoking tank
CN102732308B (en) * 2011-04-15 2014-06-25 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN102732305B (en) * 2011-04-15 2014-06-25 中国石油化工股份有限公司 Naphtha hydrogenation method and decoking tank
CN103789020B (en) * 2012-11-03 2015-10-21 中国石油化工股份有限公司 A kind of method of hydrotreating of coker gasoline
CN103789018A (en) * 2012-11-03 2014-05-14 中国石油化工股份有限公司 Hydroprocessing method of coker gasoline
CN103789020A (en) * 2012-11-03 2014-05-14 中国石油化工股份有限公司 Hydrogenation method of coker gasoline
CN103789018B (en) * 2012-11-03 2015-07-22 中国石油化工股份有限公司 Hydroprocessing method of coker gasoline
CN103611362A (en) * 2013-12-13 2014-03-05 海南汉地阳光石油化工有限公司 Filter device and petroleum hydrogenation system
CN103611362B (en) * 2013-12-13 2016-06-08 海南汉地阳光石油化工有限公司 A kind of filtration unit and petroleum hydrogenation system
CN110129093A (en) * 2019-05-21 2019-08-16 山东京博石油化工有限公司 A kind of pre-hydrotreating reaction system
CN111495436A (en) * 2020-04-17 2020-08-07 中国石油化工股份有限公司 Sulfurizing method of hydrogenation catalyst
CN111495436B (en) * 2020-04-17 2022-08-30 中国石油化工股份有限公司 Sulfurizing method of hydrogenation catalyst

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Application publication date: 20090304