CN105694951A - Method for removing trace of coke powder in coker diesel - Google Patents

Method for removing trace of coke powder in coker diesel Download PDF

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Publication number
CN105694951A
CN105694951A CN201610251832.XA CN201610251832A CN105694951A CN 105694951 A CN105694951 A CN 105694951A CN 201610251832 A CN201610251832 A CN 201610251832A CN 105694951 A CN105694951 A CN 105694951A
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CN
China
Prior art keywords
coke powder
gas oil
coker gas
trace
magnetic
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Pending
Application number
CN201610251832.XA
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Chinese (zh)
Inventor
陈英
陈东
王敏
陈勇
王路辉
王玉华
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Zhejiang Ocean University ZJOU
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Zhejiang Ocean University ZJOU
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Priority to CN201610251832.XA priority Critical patent/CN105694951A/en
Publication of CN105694951A publication Critical patent/CN105694951A/en
Pending legal-status Critical Current

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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
    • C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • 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
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (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 method for removing a trace of coke powder in coker diesel. A magnetic flocculant Fe3O4-EC is added to the coker diesel, in the adding process, the temperature of the coker diesel is controlled to be 250 DEG C or below, stirring is conducted, and settling separation is conducted under the effect of a magnetic field. According to the method, the magnetic flocculant Fe3O4-EC is adopted, and under the effect of the magnetic field, a trace of coke powder precipitates in the coker diesel are removed. Through a test, the removal rate of the coke powder in the obtained coker diesel is 99%, and repeated use can be achieved.

Description

The minimizing technology of trace coke powder in a kind of coker gas oil
Technical field
The present invention relates to the minimizing technology of trace coke powder in a kind of coker gas oil。
Background technology
Delayed coking is that (and high-acid crude oils) such as the low value poor residuum of petroleum refining enterprise, sump oil and greasy filth is heated cracking, condensation, thus being changed into the secondary operations technique of the products such as the liquefied gas of high value, gasoline, diesel oil, wax oil and the side-product such as dry gas, petroleum coke。Due to delay coking process raw material wide accommodation, light oil yield is high, invest and operating cost is low, it has also become the Main Means of current petroleum refining enterprise residual oil particularly poor residuum processing。In coking distillate (coker gasoline, coker gas oil, wax tailings), the content of heteroatoms such as alkene and sulfur, nitrogen, silicon is high, and stability is poor, it is impossible to use directly as product。For making coking distillate meet end product standard, it is necessary to carry out following process (hydrofinishing, catalytic cracking etc.)。And coking distillate is typically different degree and carries coke powder。These coke powders enter after following process device, deposit at catalyst surface, make beds Pressure Drop raise, the phenomenon such as beds is built bridge, bias current, ultimately result in catalysqt deactivation。When coke powder enters high pressure heat exchanger, easily making high pressure heat exchanger fouling and clogging, affect heat transfer effect, cleaning of must stopping work time serious, thus shortening the on-stream time of whole device。Therefore the coke powder in elimination coking distillate seems particularly significant。
Automatic backwashing filter is to remove the core methed of coke powder in coking distillate at present, although production needs substantially can be met, but have disadvantages that: switching is frequently, often automatically stop transport because of pressure reduction super large, and device acquisition expenses and maintenance cost are high, the coke powder particle diameter of less than 20 μm is little, density is low, is very difficult to remove, and conventional high-accuracy filter is easy to blocking。The research application in elimination coking distillate coke powder of the mini-hydrocyclone separation technology receives publicity in recent years。Li Zhimings etc. devise the liquid-solid mini-hydrocyclone separation device of 25mm, import coke powder mean particle size be 25 μm, flow be 0.86m3/h, split ratio be 5% time, separation efficiency is more than 92%, and cut diameter is 6 μm, it is adaptable to containing the isolation of purified of coke powder coking oil product。Make mini-hydrocyclone separation technology obtain efficient, stable operational effect in coking distillate decoking powder, also need flow process in mini-hydrocyclone separation device is carried out big quantity research。
The general grain diameter of coke powder in coking distillate is little, substantially belongs to micron and submicron even nano-scale particle；It addition, general coke powder is little with the density contrast of distillate, it is typical that the density contrast of the solid particle in tar and tar is only 30～70Kg/m3, different coking plant oil divide the coke powder carried distinct, and coke powder density is typically in 1500Kg/m3Below。Above two major features is the main cause affecting filtering technique and cyclone technique at present in coking distillate decoking pink collar territory respectively。
Summary of the invention
Present invention aim to overcome that said method cannot remove the technical problem of trace coke powder, it is provided that the minimizing technology of trace coke powder in a kind of coker gas oil, adopted flocculation and magnetic sedimentation method to remove the trace coke powder of coking distillate。
The purpose of the present invention implements by the following technical programs:
The minimizing technology of trace coke powder in a kind of coker gas oil, adds magnetic flocculant Fe in coker gas oil3O4-EC, adition process controls the temperature of coker gas oil below 250 DEG C, stirring, more settlement separate under the effect in magnetic field。
Preferably, the addition of described magnetic flocculant is the 0.1% of coker gas oil quality。
Preferably, adition process controls the temperature of coker gas oil is 60 DEG C
Preferably, stirring 20min。
Preferably, magnetic field intensity is 0.1～0.3T。
It is further preferred that will added with magnetic flocculant Fe3O4The coker gas oil of-EC is placed on Magnet, stands 10min,。
The magnetic flocculant Fe that the inventive method adopts3O4The preparation method of-EC is as follows:
The ethyl cellulose with flocculation demulsification performance is connected on the Fe3O4 microparticle surfaces with superparamagnetism, obtains oil loving magnetic flocculant, i.e. Fe3O4-EC。In order to make Fe3O4Can be bonded by chemical combination with EC, need to Fe3O4Carry out surface treatment, EC is carried out bromination process。Specifically comprise the following steps that
1. preparation Fe3O4:
Weigh Iron(III) chloride hexahydrate 27.72g, green vitriol 47.11g be dissolved in 800ml deionized water, add 225ml ammonia (concentration is 25%), the pH making aqueous solution is about 9.5, it is thus achieved that ferric hydroxide precipitate。Aging 12 hours of ferric hydroxide precipitate, then precipitate 3 times with deionized water wash under magnetic field, removes non-magnetic iron compound and anion such as sulfate ion, chloride ion etc., filters precipitation, vacuum drying 12 hours at 40 DEG C, obtains Fe3O4。
2.Fe3O4/Si(OH)4
Take Fe3O417.26g, with in ultrasonic cell disrupte machine ultrasonic disperse to 1000ml deionized water, 75ml sodium silicate is slowly added dropwise in above-mentioned solution, and adds the sulfur acid for adjusting pH of 0.3mol/L to about 9.5。At 40 DEG C, stir 3 hours post-heating to 95 DEG C constant temperature 1 hour, make sodium silicate hydrolytic precipitation on Fe3O4。With deionized water wash solid matter 3 times under magnetic field, gained solid is continued in water vapour hydrolysis 1 hour, finally solid is placed on 105 DEG C and dries and can obtain Fe in 1 hour3O4/Si(OH)4。
3.Fe3O4/Si(OH)4Surface amination:
By 17gFe3O4/Si(OH)4It is dispersed in the toluene of 100ml (ultrasonic disperse 10 minutes), then is slowly added dropwise 45ml dimethylformamide, boiling reflux 4 hours, replace magnetic with toluene and ethanol after cooling to room temperature and wash 3 times, and put into vacuum desiccator and dry to obtain the Fe of surface amination3O4/Si(OH)4。
4. prepared by bromination ethyl cellulose:
Weigh 8g ethyl cellulose to be dissolved in 200ml oxolane, add 0.8ml pyridine solution, called after mixed liquor A。By 2-bromo isobutyl acylbromide (98%) 1.2ml with oxolane constant volume to 10ml, by mixed liquor called after B。B mixed liquor is slowly added dropwise in A (temperature of A controls at 0 DEG C)。Stirring reaction 3 hours at 40 DEG C, then reaction 24 hour is stirred at room temperature, replace washed product 3 times with deionized water and oxolane, obtain white solid bromination ethyl cellulose。
5. synthesis Fe3O4-EC:
The Fe of 6g ammonification is dissolved with the oxolane of 300ml3O4/Si(OH)4With the bromination ethyl cellulose of 1g, add 2ml pyridine, be stirred at room temperature reaction 48 hours, wash with oxolane magnetic after terminating, vacuum drying cabinet is drying to obtain Fe3O4-EC。
The method have the benefit that
The inventive method adopts has magnetic flocculant Fe3O4-EC, under the influence of a magnetic field, makes the coke powder precipitation of trace in coker gas oil remove。After tested, after the inventive method, in gained coker gas oil, the clearance of coke powder is 99%, and can recycle。
In order to further illustrate the essence of the present invention, the coker gas oil after adopting the inventive method is carried out experimental analysis。
The content analysis of coke powder in coker gas oil: the microporous filter membrane utilizing aperture to be 0.22 μm is filtered, acquisition coke powder weight of weighing。
Experimental result:
Coke powder clearance in coker gas oil during table 1 difference magnetic flocculant consumption
Temperature 60 C, stirs 20min, settles 10min
Table 2 magnetic flocculant recycling situation (coker gas oil)
Can being obtained by above-mentioned contrast experiment's data, the optimum condition of the inventive method is: temperature 60 C, flocculant usage 0.1%, stirring 20min, sedimentation 10min。
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention
Embodiment 1:
The collection of coker gas oil: from certain oil plant, its coke powder content is 230mg/L, coke powder granule average out to 35 μm, and the true density of coke powder granule is 1450Kg/m3, coker gas oil density 835Kg/m3。
Magnetic flocculant Fe3O4The preparation of-EC:
1. preparation Fe3O4:
Weigh Iron(III) chloride hexahydrate 27.72g, green vitriol 47.11g be dissolved in 800ml deionized water, add 225ml ammonia (concentration is 25%), the pH making aqueous solution is about 9.5, it is thus achieved that ferric hydroxide precipitate。Aging 12 hours of ferric hydroxide precipitate, then precipitate 3 times with deionized water wash under magnetic field, removes non-magnetic iron compound and anion such as sulfate ion, chloride ion etc., filters precipitation, vacuum drying 12 hours at 40 DEG C, obtains Fe3O4。
2.Fe3O4/Si(OH)4
Take Fe3O417.26g, with in ultrasonic cell disrupte machine ultrasonic disperse to 1000ml deionized water, 75ml sodium silicate is slowly added dropwise in above-mentioned solution, and adds the sulfur acid for adjusting pH of 0.3mol/L to about 9.5。At 40 DEG C, stir 3 hours post-heating to 95 DEG C constant temperature 1 hour, make sodium silicate hydrolytic precipitation on Fe3O4。With deionized water wash solid matter 3 times under magnetic field, gained solid is continued in water vapour hydrolysis 1 hour, finally solid is placed on 105 DEG C and dries and can obtain Fe in 1 hour3O4/Si(OH)4。
3.Fe3O4/Si(OH)4Surface amination:
By 17gFe3O4/Si(OH)4It is dispersed in the toluene of 100ml (ultrasonic disperse 10 minutes), then is slowly added dropwise 45ml dimethylformamide, boiling reflux 4 hours, replace magnetic with toluene and ethanol after cooling to room temperature and wash 3 times, and put into vacuum desiccator and dry to obtain the Fe of surface amination3O4/Si(OH)4。
4. prepared by bromination ethyl cellulose:
Weigh 8g ethyl cellulose to be dissolved in 200ml oxolane, add 0.8ml pyridine solution, called after mixed liquor A。By 2-bromo isobutyl acylbromide (98%) 1.2ml with oxolane constant volume to 10ml, by mixed liquor called after B。B mixed liquor is slowly added dropwise in A (temperature of A controls at 0 DEG C)。Stirring reaction 3 hours at 40 DEG C, then reaction 24 hour is stirred at room temperature, replace washed product 3 times with deionized water and oxolane, obtain white solid bromination ethyl cellulose。
5. synthesis Fe3O4-EC:
The Fe of 6g ammonification is dissolved with the oxolane of 300ml3O4/Si(OH)4With the bromination ethyl cellulose of 1g, add 2ml pyridine, be stirred at room temperature reaction 48 hours, wash with oxolane magnetic after terminating, vacuum drying cabinet is drying to obtain Fe3O4-EC。
The method removing trace coke powder: add the 200ml coker gas oil gathered at 500ml beaker, control temperature, add a certain amount of magnetic flocculant Fe3O4-EC, stirs 30min more settlement separate under the action of a magnetic field (beaker is placed on Magnet, stands 10min)。The optimum condition of inventive method is: temperature 60 C, flocculant usage 0.1%, stirring 20min, sedimentation 10min。
The foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature carries out equivalent replacement。All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention。

Claims (6)

1. the minimizing technology of trace coke powder in a coker gas oil, it is characterised in that: in coker gas oil, add magnetic flocculant Fe3O4-EC, adition process controls the temperature of coker gas oil below 250 DEG C, stirring, more settlement separate under the effect in magnetic field。
2. the minimizing technology of trace coke powder in coker gas oil according to claim 1, it is characterised in that: the addition of described magnetic flocculant is the 0.1% of coker gas oil quality。
3. the minimizing technology of trace coke powder in coker gas oil according to claim 1, it is characterised in that: it is 60 DEG C that adition process controls the temperature of coker gas oil。
4. the minimizing technology of trace coke powder in coker gas oil according to claim 1, it is characterised in that: stirring 20min。
5. the minimizing technology of trace coke powder in coker gas oil according to claim 1, it is characterised in that: magnetic field intensity is 0.1～0.3T。
6. the minimizing technology of trace coke powder in coker gas oil according to claim 4, it is characterised in that: will added with magnetic flocculant Fe3O4The coker gas oil of-EC is placed on Magnet, stands 10min,。
CN201610251832.XA 2016-04-20 2016-04-20 Method for removing trace of coke powder in coker diesel Pending CN105694951A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5759991A (en) * 1980-09-29 1982-04-10 Kobe Steel Ltd Removal of insoluble solid substance in formed product of coal liquefaction
CN1122608A (en) * 1993-05-05 1996-05-15 Dsm有限公司 Process for the removal of mercury
CN1184841A (en) * 1997-06-18 1998-06-17 锦州石化天元集团公司 Technology for processing tar from delayed coking process
CN101445744A (en) * 2008-12-25 2009-06-03 上海华畅环保设备发展有限公司 Method for removing coke powder in raw oil and device thereof
FR2925519A1 (en) * 2007-12-20 2009-06-26 Total France Sa Fuel oil degrading method for petroleum field, involves mixing fuel oil and vector, and applying magnetic field such that mixture is heated and separated into two sections, where one section is lighter than another

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5759991A (en) * 1980-09-29 1982-04-10 Kobe Steel Ltd Removal of insoluble solid substance in formed product of coal liquefaction
CN1122608A (en) * 1993-05-05 1996-05-15 Dsm有限公司 Process for the removal of mercury
CN1184841A (en) * 1997-06-18 1998-06-17 锦州石化天元集团公司 Technology for processing tar from delayed coking process
FR2925519A1 (en) * 2007-12-20 2009-06-26 Total France Sa Fuel oil degrading method for petroleum field, involves mixing fuel oil and vector, and applying magnetic field such that mixture is heated and separated into two sections, where one section is lighter than another
CN101445744A (en) * 2008-12-25 2009-06-03 上海华畅环保设备发展有限公司 Method for removing coke powder in raw oil and device thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JUNXIA PENG ET AL: "Synthesis of Interfacially Active and Magnetically Responsive Nanoparticles for Multiphase Separation Applications", 《ADVANCED FUNCTIONAL MATERIALS》 *
李志明 等: "焦化油品微旋流脱焦粉实验研究", 《石油学报（石油加工）》 *
董培林 等: "《三次采出液处理技术及应用》", 31 October 2010 *

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Application publication date: 20160622