CN102435605A - Method for preferring delayed coking heating furnace outlet temperature - Google Patents
Method for preferring delayed coking heating furnace outlet temperature Download PDFInfo
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- CN102435605A CN102435605A CN201110277535XA CN201110277535A CN102435605A CN 102435605 A CN102435605 A CN 102435605A CN 201110277535X A CN201110277535X A CN 201110277535XA CN 201110277535 A CN201110277535 A CN 201110277535A CN 102435605 A CN102435605 A CN 102435605A
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Abstract
The invention relates to a method for preferring the delayed coking heating furnace outlet temperature, which comprises the following steps of: on a heat effect test instrument, taking a series of standard oil samples with the same distilling ranges as raw materials, running in a set of simulation test and evaluation system with a pressure simulation industrial delayed coking device in the same condition to obtain a proper operation temperature range without adhesive coke or shot coke, measuring the heat effects of the standard oil samples in a heat analysis instrument, corresponding the proper temperatures to the heat effects one by one, and building a standard oil sample reference system; comparing the heat effects of the tested oil samples with the reference system to obtain an oil sample test furnace outlet temperature; and performing a coking simulation test at the oil sample test furnace outlet temperature and subjecting to generating general coke but not the adhesive coke or the shot coke at the oil sample test furnace outlet temperature. The test process is simple, the quantification treatment is easily carried out, the series of the standard oil samples with the heat effects are built, and a reference standard is provided for confirming the heavy oil or heavy mixed oil heating furnace outlet temperature.
Description
Technical field:
The present invention relates to a kind of method of preferred delay coking heating furnace outlet temperature.
Background technology:
Hot-working in petroleum refining technology [Cheng Zhiguang (1994). mink cell focus process technology, Sinopec publishing house .], be meant the effect that utilizes heat, be oil plant chemically reactive and reach the process of processing purpose.Its major technique means are different from technologies such as catalysis processing and solvent processing.Because it is the effect that utilizes heat, thus bigger to the adaptability of raw material, can handle distillate, also can handle asphaltum oil, can handle the few raw material of impurity (sulphur, nitrogen, oxygen, heavy metal, bituminous matter), also can handle the many raw materials of impurity.In technological process, need not use auxiliary material like catalyzer or solvent and so on.Compare with catalysis processing and solvent processing etc., hot worked energy consumption and processing charges are low, investment is generally also low.The product of hot-working gained, its quality is often not ideal enough, must reach the demand of market and use through subsequent treatment.Hot worked main technique method is following three kinds:
(1) with the vacuum distillate is raw material, produces the thermal cracking of gasoline, diesel oil and fuel oil.
(2) with vacuum residuum be raw material, produce the coking of gasoline, diesel oil, distillate and coke.
(3) be raw material with long residuum or vacuum residuum, producing with fuel oil is main viscosity breaking.Along with the poor qualityization of world's tradition petroleum resources and the progressively processing of non-traditional resource such as heaviness and oil sands bitumen, a large amount of residual oil and various unmanageable asphaltum oil have been produced.Because delay coking process is strong to the hungry adaptability of raw material, little, the technology maturation of investment; As in the heat processing technique important one; Therefore under this situation to the heavy charge lighting, to the voluminous raw material of industry or transport fuel oil, important effect is arranged.Also therefore in the share of world's heavy oil residue processing at present, occupy about 50～60%.
Mink cell focus [Qu Guohua (2008). delay coking process and engineering, Sinopec publishing house .] be the potpourri that many relative molecular masses are big, molecular structure is different hydro carbons and non-hydrocarbons compound are formed.Their thermal response behavior had both met the universal law of monomer hydro carbons and non-hydrocarbons thermal response, but its characteristics are arranged.Because its reaction intersects each other, makes it more complicated.All in all, the free chain reaction course is also followed in the thermal transition of mink cell focus, is characterized in liquid phase reactor.In gas phase, after being split into free radical, hydrocarbon and non-hydrocarbon molecule scatter rapidly immediately, and also far apart mutually; And in liquid phase; It is much tight that molecule is wanted; The free radical that generates can be surrounded by contiguous free radical and other molecules, is easy to collision each other chain reaction is ended, thereby correspondingly reduce the speed of chain reaction; Cause under the same conditions than gas-phase reaction produce more condensation product and less decomposition product [Ma Er markon work, Xu Yifang etc. translate. petrochemical process theoretical foundation. petroleum industry publishing house].In a word, the various components of mink cell focus are reacted along cracking and condensation both direction when thermal transition all the time.Under the total constant situation of total hydrocarbon atom, removing in its product has the distillate lighter than raw material gentle external, and inevitable heavier than raw material in addition simultaneously product is until coke.
Specifically in the delay coking process flow process, this reaction member of coke drum is approximate to be a thermal insulation system.Reaction raw materials through the heating furnace heating gets into the energy generation thermal response of coke drum bottom by self through water back fast, generates gas, distillate and coke.When delay coking process was handled different feeds at present, the furnace outlet temperature was more or less the same, and coke cat head place temperature controlling is by chilling logistics control, and " actual temperature " in the coke drum can only " be estimated " shortage relevant detection means.In actual process, the structure of different material is formed different, and it is bigger that carbon residue differs, and it is bigger that cracking activity differs.If the furnace outlet temperature is not adjusted with feed properties, the thermal response temperature in coke drum can differ greatly with the difference of raw material.This just causes the coking temperature to differ greatly, and then influences the coking characteristic, thereby causes the generation of shot coke (temperature is too high) or sticking burnt (temperature is on the low side, and reaction not exclusively).This long-term operation to device is disadvantageous, also influences product simultaneously and distributes.Mostly be in the refinery that at present experience judges during practical operation, lack effectively quantitative data and support with theoretical.
At present at biomass flash pyrolysis [Mette Stenseng. " Investigation of biomass pyrolysis by thermogravimetric analysis and differential scanning calorimetry " .Journal of Analytical and Applied Pyrolysis Volumes 58-59; 1April 2001, Pages 765-780] also there is the situation of similar estimation reaction needs heat in the aspect.But aspect petroleum refining, do not utilize thermal effect to solve the documents and materials of similar problem.
With regard to thermal process reactor, thermal cracking is thermonegative reaction, but charing green coke process is heat release.The delayed coking coking yield difference of different material is bigger, and the big more exothermic effect of coking yield is big more; Cracking performance is good more, and coking yield is low more, and then heat absorption is big more, and heat release is more little, thereby different raw materials thermal conversion processes institute energy requirement is different.The needed coking temperature of the coking raw material that coking yield is big is low, and the raw material coking coking temperature that cracking conversion rate is high is just high.Therefore, available heat analytical approach research different material thermal effect, and then judge suitable heating heater outlet temperature scope according to the thermal effect reference value of standard series oil sample.At present can quantity research in pyrolytic process [Antonio J.Lopez-Peinado; Peter J.J.Tromp; Jacob A.Moulijn; Quantitative heat effects associated with pyrolysis of coals, ranging from anthracite to lignite, Fuel 68 (1989) 999-1004.; J.Rah, Heat of wood pyrolysis, Fuel 82 (2003) 81-91.] to use more testing tool be DSC (differential scanning calorimeter) in the aspect.Its heat-supplying mode has two kinds: non-isothermal test (linear temperature increase process) and isothermal test.The non-isothermal test often is used to study oil pyrolysis [Mustafa Versan KOK; Ozgen Karacan; Pyrolysis analysis and kinetics of crude oils; Journal of Thermal Analysis 52 (1998) 781-788.], the burning processes such as [Mustafa Versan Kok, Characterization ofmedium and heavy crude oils using thermal analysis techniques, Fuel Processing Technology 92 (2011) 1026-1031]; The isothermal test then mainly is used in the reaction heat [Dai Xiaoqing etc. of gentle temperature of reaction condition; ISOTHERMAL DSC method research RFI uses epoxy resin cure dynamics, compound substance journal, 25 (4) 2008] test.And according to specimen character, this method of the reaction type of research can also be selected carrier gas of different nature and pressure condition for use: inert atmosphere (helium, nitrogen), reducing atmosphere (hydrogen), oxidizing atmosphere (oxygen).But (for example temperature, pressure [William S.-L. Mok because test condition; Michael J.Antal; Jr.; Effects of pressure on biomass Pyrolysis.II.Heas of reaction of cellulose pyrolysis, [J] Thermochimica Acta, 68 (1983) 165-186], properties of samples) bigger to resulting thermal effect data influence in the course of reaction.Therefore experiment condition comprises that the boiling range of specimen should be in equal state in hot analytic process.
The means of observation coke pattern detect for the polarizing microscope optical texture.The main foundation of wherein analyzing is the optical texture of coke polishing section.Thermal response institute coke is under polarisation; Usually [M.Siskin; S.R.Kelemen, M.L..Gorbaty, et al.Chemical Approach to Control Morphology of Coke Produced in Delayed Coking [J] Energy&Fuels; 2006,20:2117-2124] comprise mosaic type optical texture (diameter is between 1-10 μ m) and basin type optical texture (diameter is greater than 10 μ m).The material carbon that be prone to generate shot coke changes into that mosaic type structure accounts for major part in the burnt polarization optical structure, and the ratio of basin type optical texture then is in the great majority in common Jiao's the optical texture.The scope of basin type or mosaic optical texture is big more, and the order degree of coke is big more, and corresponding coke quality is high more.
Summary of the invention:
The objective of the invention is to deficiency, a kind of method of preferred delay coking heating furnace outlet temperature is provided to prior art.Solve the problem of the no quantitative data foundation of present delay coking heating furnace outlet temperature adjustment.Set up standard oil sample thermal effect series, reference standard is provided for confirming mink cell focus or heavy mixing oil plant furnace outlet temperature.
The objective of the invention is to test through following technical scheme:
On the thermal effect tester, be standard raw materials with the same oil sample of a series of boiling ranges at first, in a cover band pressing mold is intended the simulation evaluation system of commercial delayed coker, move, draw suitable coking operation temperature range with identical experiment condition.Its criterion is that institute's coke is common Jiao under the preference temperature.The test result that is reflected in polarizing microscope is to occur the crystal face reflection in the sample polarisation photo, shows that carbonization crystallization pyrogenetic reaction is for complete; The average optical diameter of movement shows that greater than 10 μ m the probability that shot coke occurs is very little, and institute's coke is mainly common Jiao.
Again above-mentioned standard oil sample system is measured thermal effect in thermal analyzer, separately suitable coking temperature and thermal effect is corresponding one by one, set up oil sample canonical reference system; Through the thermal effect of test oil sample and the comparison of reference frame, confirm the suitable heater outlet temperature scope of test oil sample, temperature range then must meet the nonoverlapping principle of each oil sample.
Through recommending to carry out the coking simulated experiment under the heater outlet temperature condition that obtains, the burnt appearance that obtains is carried out polarized light microscopy and is observed, and can occur light and grey dark-part in the photo usually at last.Because crystal has anisotropic properties, under polarized light, have reflection, light is to having in the burnt appearance due to the same layer structure polarisation reflection of image-stone China ink in the picture, is representing the crystal growth situation.And grey dark-part is not have crystal structure, but is mingled in together, has formed the thing that mingles of macroscopical isotropy, therefore under polarisation, is shown as gloomy.
In sum, the invention has the advantages that:
1. test process is simple, is easy to quantification and handles.
2. be directed against the deficiency of prior art, a kind of method of preferred delay coking heating furnace outlet temperature.Solve the problem of the no quantitative data foundation of present delay coking heating furnace outlet temperature adjustment.Set up standard oil sample thermal effect series, reference standard is provided for confirming mink cell focus or heavy mixing oil plant furnace outlet temperature.
Description of drawings:
The test result of Fig. 1 embodiment of the invention one
Fig. 2 embodiment one burnt kind polarisation photo
Wherein: the polarisation photo of Fig. 2 a burnt appearance during greater than 500 ℃; Burnt appearance polarisation picture under Fig. 2 b reacts in the time of 496 ℃;
The test result of Fig. 3 embodiment of the invention two
Fig. 4 embodiment two burnt kind polarisation photos
Wherein: the polarisation photo of Fig. 4 a burnt appearance during greater than 499 ℃; Burnt appearance polarisation picture under Fig. 4 b reacts in the time of 493 ℃;
Embodiment:
Because the standard oil sample is more in the system of canonical reference described in the claim, only use wherein grand celebration vacuum residuum, Liaohe River vacuum residuum, Venezuela's vacuum residuum in the following example as explanation.
Embodiment 1:
Choosing boiling range is the standard oil sample greater than 500 ℃ grand celebration vacuum residuum, Liaohe River vacuum residuum, Venezuela's vacuum residuum, in room temperature to 1000 ℃ process under the nitrogen protection 10k/min linear temperature increase condition, and the test thermal effect, test pressure is 0.2MPa.Utilize the best carbonization coking temperature range of 460～520 ℃ of each residual oil of pilot scale delayed coking analogue means test.The test oil sample is a Kelamayi vacuum residuum.The result is as shown in Figure 1.
The suitable heater outlet temperature that obtains Kelamayi vacuum residuum is about 495.5 ± 2.5 ℃; In this temperature and high 5 ℃ of do simulation coking experiments; The polarisation that obtains burnt appearance photo such as Fig. 2: occur coccoid particle studded structure in the time of＞500 ℃ in the product, the polarizing microscope photo is Fig. 2 a.Picture shows the wide area optical texture (bright place) that does not have in the burnt appearance greater than 10 μ m, in the burnt appearance crystallization less, become to disperse zyklopisch.Show that reaction velocity is very fast under this temperature, form shot coke easily.And the burnt appearance polarisation picture Fig. 2 b under the reaction shows in the time of 495/496 ℃, and diameter occurs greater than the wide area structure of 10 μ m.The graininess bead does not occur yet in the actual burnt appearance.The temperature of utilizing said method to draw is suitable for the coking of this test oil sample.
Embodiment 2:
Residual Oil and respective cycle oil mixes oil plant (the actual charging of simulation heating stove) under identical condition, recycle ratio 0.15, and recycle oil boiling range＞480 ℃, test pressure is 0.2MPa.Can find out the fine said method that meets of the raw material that has added recycle oil ability as the same from Fig. 3 as a result.Test result such as Fig. 3: the suitable heater outlet temperature that obtains Kelamayi vacuum residuum is 493 ± 2.5 ℃; In this temperature and high 5 ℃ of do simulation coking experiments respectively; The polarisation that obtains burnt appearance photo such as Fig. 4: same＞as coccoid particle studded structure to occur in the product 498 ℃ the time; The polarizing microscope photo shows that at 493 ± 2.5 ℃ of time reactions burnt appearance polarisation picture Fig. 4 b down diameter occurs greater than 10 μ m wide area structures equally for Fig. 4 a.The graininess bead does not occur yet in the actual burnt appearance.The temperature of utilizing said method to draw is suitable for the coking of this test oil sample.
Claims (5)
1. the method for a preferred delay coking heating furnace outlet temperature is characterized in that:
At first on the thermal effect tester; With the same standard oil sample of a series of boiling ranges is raw material; With identical experiment condition, in the simulation evaluation system of a cover band pressing mold plan commercial delayed coker, move, draw the suitable operating temperature range that does not contain sticking Jiao or shot coke; The test result that is reflected at polarizing microscope is to occur the crystal face reflection in the sample polarisation photo, shows that carbonization crystallization pyrogenetic reaction is for complete; The average optical diameter of movement shows that greater than 10 μ m the probability that shot coke occurs is very little;
Again above-mentioned standard oil sample system is measured thermal effect in thermal analyzer, separately preference temperature and thermal effect is corresponding one by one, set up standard oil sample reference frame; Through the thermal effect and the reference system of contrastive test oil sample, draw the suitable heater outlet temperature scope of test oil sample;
Through under the heater outlet temperature condition of recommending to obtain, carrying out the coking simulated experiment, the burnt appearance that obtains is carried out polarized light microscopy and is observed at last, and light is being represented the crystal growth situation for having in the burnt appearance due to the same layer structure polarisation reflection of image-stone China ink in the picture; Grey dark-part is crystal structure and isotropic thing that mingles in the picture.
2. the method for a kind of preferred delay coking heating furnace outlet temperature according to claim 1 is characterized by: the pressure test conditions of said thermal effect tester is absolute pressure 0-0.2MPa; The temperature test condition is the non-isothermal process of room temperature to 1000 degree centigrade; All test conditions when different specimen are tested should be in equal state.
3. the method for a kind of preferred delay coking heating furnace outlet temperature according to claim 1, the boiling range that it is characterized by test oil sample and institute accepted standard oil sample should be the same.
4. the method for a kind of preferred delay coking heating furnace outlet temperature according to claim 1, it is characterized by the standard oil sample that adopts is serial oil sample, its thermal effect and heater outlet temperature corresponding relation are canonical reference system.
5. the method for a kind of preferred delay coking heating furnace outlet temperature according to claim 1; It is characterized by that the said accuracy of judging for the heater outlet temperature that is fit to does not generate sticking Jiao to generate common Jiao under this temperature range or shot coke is as the criterion, temperature range then must meet the nonoverlapping principle of each oil sample.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105716992A (en) * | 2016-02-19 | 2016-06-29 | 中国石油大学(华东) | Measuring method for gasification rates of heavy oil at outlet temperature of heating furnace |
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| US20030102250A1 (en) * | 2001-12-04 | 2003-06-05 | Michael Siskin | Delayed coking process for producing anisotropic free-flowing shot coke |
| CN101302435A (en) * | 2008-06-20 | 2008-11-12 | 中国石油大学(华东) | Improved method of delay coking process |
| CN101776547A (en) * | 2010-01-20 | 2010-07-14 | 中国科学院山西煤炭化学研究所 | Method for easily and quickly evaluating needle coke |
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| US20030102250A1 (en) * | 2001-12-04 | 2003-06-05 | Michael Siskin | Delayed coking process for producing anisotropic free-flowing shot coke |
| CN101302435A (en) * | 2008-06-20 | 2008-11-12 | 中国石油大学(华东) | Improved method of delay coking process |
| CN101776547A (en) * | 2010-01-20 | 2010-07-14 | 中国科学院山西煤炭化学研究所 | Method for easily and quickly evaluating needle coke |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105716992A (en) * | 2016-02-19 | 2016-06-29 | 中国石油大学(华东) | Measuring method for gasification rates of heavy oil at outlet temperature of heating furnace |
| CN105716992B (en) * | 2016-02-19 | 2018-05-15 | 中国石油大学(华东) | A kind of assay method of mink cell focus rate of gasification at a temperature of furnace outlet |
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Application publication date: 20120502 |