CN105586078B - A kind of heavy oil coking method - Google Patents
A kind of heavy oil coking method Download PDFInfo
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- CN105586078B CN105586078B CN201410563195.0A CN201410563195A CN105586078B CN 105586078 B CN105586078 B CN 105586078B CN 201410563195 A CN201410563195 A CN 201410563195A CN 105586078 B CN105586078 B CN 105586078B
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Abstract
The invention provides a kind of heavy oil coking method, this method includes temperature being atomized for 50 400 DEG C of coking heavy oil raw material, then the deoxidation smoke contacts that the coking heavy oil raw material of state will be atomized with temperature is 490 750 DEG C, the coking heavy oil raw material of the atomization state is set to reach coking temperature and carry out pyrogenetic reaction, then coke coarse powder, coke fines and oil gas are isolated from pyrogenetic reaction product, then the oil gas is subjected to fraction seperation.The heavy oil coking method that the present invention is provided can not only reduce the coking even completely avoided in heating furnace tube and improve liquid yield, and can also save by the flue gas carry out desulfurization, denitrogenation and dedusting the step of, there is no a large amount of decoking wastewater problems that delayed coking is produced, great prospects for commercial application.
Description
Technical field
The present invention relates to a kind of heavy oil coking method.
Background technology
Current crude oil heaviness, in poor quality, higher-priced trend are more and more obvious, need of the whole world to lightweight and clean fuel oil
Rapid growth is sought, along with environmental requirement is increasingly strict so that heavy oil deep processing technology turns into petroleum refining industry of the world today
The emphasis of development.Particularly inferior heavy oil density is big, viscosity is high, content of beary metal is high, sulfur content is high, nitrogen content is high, colloid and
The features such as asphalt content is high, the processing (the especially secondary operation of heavy oil) to crude oil brings bigger difficulty.Carry at present
High heavy oil conversion level, the earned value techniques of increase light-end products yield still rely primarily on coking, RFCC and residual oil and added
The techniques such as hydrogen processing.Wherein, coking is the primary means of inferior heavy oil (particularly residual oil) conversion based on de- charcoal technique.And
Delay coking process has that de- charcoal is thorough, flow is simple, technology maturation, relatively low plant investment the features such as, it has also become processing of heavy oil
One of important process.
Delayed coking is a kind of heat processing technique of depth thermal cracking, can convert heavy oils into for coking dry gas, liquefied gas,
The products such as coker gasoline, coker gas oil, wax tailings, coke.Generally the yield of coker gasoline, coker gas oil and wax tailings
Sum is as the liquid yield of delayed coking, and liquid yield is the most important technical-economic index of coking process.Conventional delay
Coking process main flow is：It (is usually 490- that heavy oil, which is rapidly heated in heating furnace radiating furnace tube and is warming up to coking temperature,
515 DEG C or so) after, enter coke drum from the bottom of coke drum, pyrogenetic reaction is carried out in coke drum, the coke of generation stays in Jiao
In charcoal tower, the oil gas of generation from top of coke tower escape into fractionating column in be fractionated, obtain cooking gas (including coking vapour
Oil), coker gas oil, wax tailings and bottom of towe recycle oil.Wherein, coke drum is generally two, and two coke drums are used in turn, its
In one be full of coke after devoked, hot logistics switches to the progress pyrogenetic reaction of another coke drum, and the tower full of coke adopts
Cut and devoked with waterpower.
Current processing heavy oil tends in poor quality, the increase of carbon residue, asphalitine and tenor etc., to delayed coking unit
Operation bring challenge, not only product distribution is deteriorated, liquid yield reduction, and coking of the raw material in heating furnace tube enter
One step is aggravated, and directly influences the long-term operation of device.Grasped in addition, the decoking process of delayed coking coke drum belongs to interval
Make, its program is more, and time-consuming, can also produce large amount of sewage, not only adds the energy consumption and running cost of device, also environment is made
Into immense pressure.
In order to improve the liquid yield of delayed coking and extend the on-stream time of delayed coking, petroleum refining researcher research
The technology related to developing.
For example, CN1599784A discloses a kind of delayed coking method for producing anisotropy free-flowing shot coke,
This method includes with oxidant contacting vacuum residuum feed at a temperature of about 150-325 DEG C, subsequently into heating stove heat
To the temperature needed for coking, the shot coke that anisotropy is flowed freely then is generated in coke drum.Although this method can be with
Obtain shot coke, and eliminate coke cleaning step, but be due to vacuum residuum feed needed before heating furnace is entered first with
Oxidation reaction and condensation reaction occur for oxidant contact, therefore can be further exacerbated by the coking of heating furnace tube, so as to influence
Continuous production, the technique is difficult to industrialize.
CN101619237A and CN101619238A disclose the technique for being combined delayed coking with vacuum distillation process,
The liquid yield of delayed coking unit is improved, the property of weight wax tailings is improved.But, this method, which still needs, to be postponed
Coking raw material is directly heated in heating furnace tube to coking temperature, therefore, exacerbates the coking of boiler tube, so that can shortening device
On-stream time.
In addition, the coking in order to slow down delayed coker unit furnace boiler tube, petroleum refining researcher researches and develops
Related technology.Research shows, diluent, free radical inhibitors, arene coking are added into delayed coking raw material
Inhibitor, anti-coking agent etc. can suppress the coking of heating furnace tube to a certain extent, extend on-stream time, but mode of heating
Indirect heating manner (by heating-furnace tube wall heat exchange) is generally belonged to, the thermal efficiency is low, therefore boiler tube green coke problem
It can not be able to effectively solve, and liquid yield is lifted without essence, and coke drum decoking environmental issue is still protruded.
In summary, liquid can be improved again by needing a kind of coking behavior that can either improve heating furnace tube of exploitation badly at present
The heavy oil coking method of body yield.
During fluid catalytic cracking (FCC), feedstock oil with catalyst split by the Rapid contact progress catalysis in riser
Change causes it to inactivate in reaction, the coke laydown that reaction is generated to catalyst, and the catalyst of green coke inactivation enters again after stripping
Raw device carries out coke burning regeneration.The flue-gas temperature that regeneration is produced may be up to 700 DEG C or so, the energy that it is taken away in catalytic cracking unit
Amount can account for a quarter of full device energy consumption or so.The efficiency of regenerated flue gas energy regenerating also directly influences package unit
Energy consumption.
In addition, the energy reclaiming method of regeneration fume from catalytic cracking is still using flue gas turbine expander and waste heat recovery pot at present
The method that stove combination is reclaimed.The energy-conserving action of flue gas turbine expander is mainly expanded by high-temperature flue gas does manual work, for generating electricity or driving
Catalyst cracking device；Pre- thimble-tube boiler is then that water is changed into water using flue gas institute's liberated heat using heat exchange principle to steam
Vapour.Kinetic energy and heat energy are converted and shifted by this method, and energy loss is larger.In addition, catalytic cracking catalyst regenerates cigarette
Contain substantial amounts of CO, SO in gasXAnd NOXDeng pollutant and catalyst dust, these pollutants must carry out desulphurization and denitration, dedirt
Processing can be discharged, however, these complex disposal process, and it is high to invest the cost of operation.
The content of the invention
The invention aims to overcome existing delayed coking method can not be while realizing improves heating furnace tube
Coking behavior and the defect for improving liquid yield, and a kind of new heavy oil coking method is provided.
Specifically, the heavy oil coking method that the present invention is provided includes carrying out temperature for 50-400 DEG C of coking heavy oil raw material
Atomization, the deoxidation smoke contacts that then will be atomized the coking heavy oil raw material of state with temperature is 490-750 DEG C make the atomization state
Coking heavy oil raw material reaches coking temperature and carries out pyrogenetic reaction, and coke coarse powder, Jiao are then isolated from pyrogenetic reaction product
Charcoal fine powder and oil gas, then the oil gas is subjected to fraction seperation.
Discovery of the present inventor after further investigation, existing heavy oil coking method is generally included heavy oil first
Coking raw material is heated to coking temperature in the radiant heating area of heating furnace, afterwards again by the heavy oil delay coke of the liquid after heating
Change raw material and carry out pyrogenetic reaction from coking tower bottom injection coking tower, pyrogenetic reaction product is finally subjected to fraction seperation.So
And, (exchanged heat using this indirectly heat by boiler tube tube wall) mode and directly by coking heavy oil raw material one-time heating to Jiao
Change temperature and coking heavy oil raw material and carry out the mode of coking in liquid form and be not only easily caused knot in heating furnace tube
Jiao, and liquid yield is relatively low.
And the heavy oil coking method that provides of the present invention dexterously using the higher deoxidation flue gas of temperature as heat carrier to heavy oil
Coking raw material is exchanged heat and and then so that the coking heavy oil raw material reaches coking temperature and occurs pyrogenetic reaction, so that not only
The coking even completely avoided in heating furnace tube can be reduced and liquid yield is improved, and can also save and taken off flue gas
The step of sulphur, denitrogenation and dedusting.Concrete principle is as follows：On the one hand, the method provided using the present invention carries out coking heavy oil reaction
When, coking heavy oil equipment is only needed first by coking heavy oil raw material preheating to 50-400 DEG C, without as existing coking heavy oil
Coking heavy oil raw material is equally heated to coking temperature (being usually 490-515 DEG C) by equipment, and the thermal source of pyrogenetic reaction passes through deoxidation
Flue gas is carried along into, and the deoxidation flue gas contacts with the coking heavy oil raw material after preheating and reaches coking temperature, therefore, it is possible to aobvious
Write the coking of reduction heating furnace tube；On the other hand, before pyrogenetic reaction is carried out, first coking heavy oil raw material is atomized,
The coking heavy oil raw material and deoxidation flue gas of unit volume so can be significantly increased by coking heavy oil stock dispersion into fine oil droplets
Between contact area so that the heat-transfer capability of whole pyrogenetic reaction process can not only be caused greatly to strengthen, green coke amount reduce,
Liquid yield increase, and generation coke be with certain particle size be distributed can fluidized particles, easily fluidisation conveying eliminates clear
Burnt step, has saved expense and time cost, and production process does not devoke waste water, reduces process step and the place of follow-up waste water
Manage difficulty.
A preferred embodiment of the invention, when the fraction seperation of the oil gas is carried out in knockout tower, and institute
Stating heavy oil coking method also includes feedstock oil introducing the fractionation from the raw material oil-in for being arranged on the fractionating column side-lower
In tower, the feedstock oil is introduced after being mixed with the bottom of towe withdrawing oil of fractionating column at the fractionation column bottom as coking heavy oil raw material
When being atomized in the spraying coking tower, coking heavy oil raw material can be preheated directly in fractionating column, without volume
Outer setting heating furnace is preheated to it, therefore, it is possible to avoid the coking problem in heating furnace tube completely, and due to preheating
Temperature it is relatively low, therefore the coking heavy oil raw material also unobvious coking in conveyance conduit, the operation cycle can be able to substantially
Extension.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
The structural representation for the coking heavy oil equipment that Fig. 1 provides for a kind of embodiment of the present invention；
The structural representation for the spraying coking tower that Fig. 2 provides for a kind of embodiment of the present invention；
The structural representation for the coke gasification reaction device that Fig. 3 provides for a kind of embodiment of the present invention；
The part-structure schematic diagram for the coking heavy oil equipment that Fig. 4 provides for a kind of embodiment of the present invention.
Description of reference numerals
B- coke gasification reaction devices；B27- gas distributors；B28- fluidizes state solid；B29- solids add mouth；B31- solids go out
Material mouth；C- spraying coking towers；C20- chev(e)ron baffles；C21- tops straight tube reaction zone；C22- bottoms cone collecting region；C18- mists
Change nozzle；C19- side outlets；C24- hot-wind inlets；C25- feed(raw material)inlets；C30- gas distribution grids；D- cyclone separators；e-
Fractionating column；E1- raw materials oil-in；E11- coking dry gas is exported；E12- liquefied gas is exported；E13- coker gasolines are exported；E14- is burnt
Change diesel oil outlet；E15- wax tailings are exported；K- coke coarse powder collecting tanks；M- coke fines collecting tanks；G- pumps；H- air-introduced machines；
3- flue gases；Deoxidation flue gases of the 4- after deoxidation；The mixture of 6- oil gas and coke fines；The stripped vapors of 7- first；The vapour of 9- second
Carry steam；10- oil gas；16- bottom of towe withdrawing oils；17- coking raw materials.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, in the case where not making opposite explanation, the noun of locality used such as " upper and lower, left and right " is typically referred to
The direction of the coking heavy oil equipment of the present invention under operating conditions, that is, the direction shown in accompanying drawing.In Fig. 1 into Fig. 4, arrow
The direction of head represents logistics direction.
It is 50-400 DEG C that the heavy oil coking method that the present invention is provided, which is included temperature, be preferably 300-400 coking heavy oil
Raw material is atomized, the deoxidation smoke contacts that then will be atomized the coking heavy oil raw material of state with temperature is 490-750 DEG C, is made described
The coking heavy oil raw material of atomization state reaches coking temperature and carries out pyrogenetic reaction, then isolates coke from pyrogenetic reaction product
Coarse powder, coke fines and oil gas, then the oil gas is subjected to fraction seperation.
The present invention is not particularly limited to the condition of the atomization, as long as enabling to the coking heavy oil stock dispersion
As droplet, it is preferable that the condition of the atomization makes the droplet size of the coking heavy oil raw material of obtained atomization state be
20-500 μm, the contact area between the coking heavy oil raw material of unit volume and thermal medium flue gas can be so significantly improved, is increased
Big heat and mass ability, and further improve liquid yield.In addition, the atomization can be carried out using existing various methods,
It is for instance possible to use making the coking heavy oil raw material be carried out by way of atomizer.The interior bore of the atomizer is big
The small droplet size that can be obtained as needed is suitably selected, if for example, the as described above, atomization state that to make to obtain
The droplet size of coking heavy oil raw material is 20-500 μm, then the interior bore of the atomizer can be 0.5-50mm.
The present invention is not particularly limited to the source of the deoxidation flue gas, can be existing temperature be 490-750 DEG C,
Preferably 495-720 DEG C, more preferably 500-700 DEG C and coking heavy oil raw material can be heated to coking temperature as thermal source
Various depleted gas, for example, can be coke powder and/or coking dry gas burn generation flue gas deoxidation after gas,
It can also be that catalytic cracking catalyst is carried out into regeneration to burn the gas after the regenerated flue gas deoxidation of generation, be preferably to split catalysis
Change catalyst to carry out regenerating the gas produced after the regenerated flue gas deoxidation for burning generation.Specific group of the catalytic cracking catalyst
Divide and the concrete mode and condition of coke burning regeneration are known to the skilled person, therefore not to repeat here.The deoxidation flue gas
In oxygen content be preferably more preferably 0.03-2 volumes % below 2 volume %, so can prevent coking heavy oil raw material from existing
Burning, the possibility of blast occur in coking, so as to ensure the security used.The mode of the deoxidation can be according to existing
The various methods having are carried out, for example, by the regenerated flue gas and the coke coarse powder and/or coke fines can aoxidize also
(oxygen in regenerated flue gas generates CO or CO with coke gasification reaction for original reaction2And a small amount of water).Wherein, the redox reaction
Condition include reaction temperature can be 450-750 DEG C, reaction pressure can be 0-0.15MPa, the reaction time can be 0.1-
5min.In the present invention, the pressure refers both to gauge pressure.
The deoxidation flue gas primarily serves the effect of thermal medium, by the coking heavy oil raw material and deoxidation flue gas of the atomization state
After contact, the temperature of the coking heavy oil raw material can be increased to by coking temperature by heat exchange action.The deoxidation cigarette
The temperature of gas is 490-750 DEG C, more preferably preferably 495-720 DEG C, 500-700 DEG C.In addition, the consumption of the deoxidation flue gas
As long as enabling to the temperature of the coking heavy oil raw material of the atomization state to rise to coking temperature (to be usually 490-515 DEG C, be preferably
495-505 DEG C), this those skilled in the art can be known, therefore not to repeat here.
The present invention is not particularly limited to the condition of the pyrogenetic reaction, for example, the condition of the pyrogenetic reaction is usual
It can be 490-515 DEG C, preferably 495-505 DEG C including coking temperature；Coking pressure can for -0.01MPa to 0.1MPa, it is excellent
- 0.01MPa is elected as to 0MPa；Scorch time can be 0.01-20min, preferably 0.1-5min.
When isolating coke coarse powder, coke fines and oil gas from pyrogenetic reaction product, the coke coarse powder is due to certainly
Body gravity is larger can generally to carry out sedimentation separation, and coke fines and oil gas can be separated further by cyclone separator.
Wherein, the particle diameter typically 0.01-1mm, preferably 0.02-1mm of the coke coarse powder；The particle diameter of the coke fines can
Think 0.001-0.1mm, preferably 0.001-0.05mm.In addition, after the oil gas progress fraction seperation, coking can be obtained
Dry gas, liquefied gas, coker gasoline, coker gas oil and wax tailings.
According to a kind of embodiment of the present invention, the heavy oil coking method that the present invention is provided is as shown in Figure 1 to Figure 3
Coking heavy oil equipment in carry out, wherein, being atomized of the coking heavy oil raw material, the coking heavy oil raw material of the atomization state with it is de-
The contact of oxygen flue gas and the separation of the coke coarse powder and coke fines and oil gas are carried out in spraying coking tower c, Jiao
The separation of charcoal fine powder and oil gas is carried out in cyclone separator d, and the fraction seperation of the oil gas is carried out in fractionating column e.In addition,
The deoxidation of flue gas is carried out in coking reactor b.
Specifically, the coking heavy oil equipment includes coke gasification reaction device b, spraying coking tower c, cyclone separator d and fractionation
Tower e, the spraying coking tower c include interconnected top straight tube reaction zone c21 and bottom cone collecting region c22, are arranged on
Atomizer c18 that is at the top of the top straight tube reaction zone c21 and being connected with the feed(raw material)inlet c25 of the spraying coking tower c,
And side outlet c19；Temperature for 50-400 DEG C coking heavy oil raw material via the spraying coking tower c feed(raw material)inlet c25
It is introduced into spraying coking tower c and is atomized by the atomizer c18, flue gas 3 is taken off by the coke gasification reaction device b
Oxygen, the deoxidation flue gas 4 after deoxidation introduces spraying Jiao by the hot-wind inlet c24 at the top of the spraying coking tower c
Change in tower c and contacted with the coking heavy oil raw material for being atomized state, so that the coking heavy oil raw material of the atomization state reaches coking temperature
And the coke coarse powder in pyrogenetic reaction, pyrogenetic reaction product is carried out from the bottom cone collecting region c22 bottom collections, coke is anti-
Answer the mixtures 6 of the oil gas in product and coke fines from the side outlet c19 be introduced into the cyclone separator d in carry out oil
The separation of gas and coke fines, the oil gas 10 from the cyclone separator d, which is introduced into fractionating column e, carries out fraction seperation.
The present invention is not particularly limited to the concrete structure of the coke gasification reaction device b, as long as can be by the oxygen in flue gas
Gas is removed substantially.For example, the coke gasification reaction device b can be gas-solid fluidized bed reactor.As shown in figure 3, the coke
Fluidisation state solid b28 is filled with reactor b, it can be the coke coarse powder and/or coke fines, and the flue gas 3 is from institute
The bottom for stating coke gasification reaction device b is introduced into the coke gasification reaction device b and contacted with the fluidisation state solid b28 to carry out redox
Reaction, it is reacted after deoxidation flue gas 4 from the Base top contact of the coke gasification reaction device b.Wherein, the bar of the redox reaction
It can be 450-750 DEG C that part, which includes reaction temperature, and reaction pressure can be 0-0.15MPa, and the reaction time can be 0.1-5min.
The spraying coking tower c bottoms can be respectively from by being seated in coke coarse powder and/or coke fines in the coke gasification reaction device b
And/or the cyclone separator d bottoms.Specifically, can be anti-by the coke by the coke coarse powder and/or coke fines
Answer device b solid to add mouth b29 to be introduced into the coke gasification reaction device b, the oxygen-containing high-temperature gas is acted on this part of coke powder
Deoxidation, while the fugitive constituent in coke blacking enters gas phase, it is reacted after the coke coarse powder and/or coke fines can pass through
The solid outlet b31 of the coke gasification reaction device b is drawn, and be can continue to stay in coke gasification reaction device b and is reacted.It is highly preferred that
The coke gasification reaction device b also include be arranged on it is below the coke gasification reaction device b and with the smoke inlet of the coke gasification reaction device b
The gas distributor b27 of connection, so can not only cause flue gas is realized more uniformly to be distributed, so that by oxygen content therein
Lower level is down to, but also can play the fluidisation state solid b28's supported in the coke gasification reaction device b at the initial stage of going into operation
Effect.The gas distributor b27 can for it is existing it is various can realize the equally distributed feed distributor of gas, specific knot
Structure is known to the skilled person, and therefore not to repeat here.
The interior bore of the atomizer c18 is preferably 0.5-50mm, so enables to coking heavy oil raw material through atomization
The droplet of size suitable (droplet size is about 20-500 μm) is obtained afterwards, so as to significantly improve the coking heavy oil of unit volume
Contact area between raw material and thermal medium deoxidation flue gas, increases heat and mass ability, and further improve liquid yield.It is described
It is reasonable that atomizer c18 quantity can be carried out according to the volume and the disposal ability of unit interval of the spraying coking tower c
Ground is selected, for example, when the volume of the spraying coking tower c is bigger, disposal ability of the unit interval is stronger, the atomizer
C18 quantity can accordingly increase；When the volume of the spraying coking tower c is smaller, disposal ability of the unit interval is weaker, institute
Stating atomizer c18 quantity can accordingly be reduced.As a rule, the quantity of the atomizer c18 can be 4-12.It is many
Individual atomizer c18 is preferably evenly distributed through the top of the top straight tube reaction zone c21.In addition, the atomizer c18 can
To set vertically downward, it can also set diagonally downward, and the acute angle between the axial line and horizontal plane of the atomizer c18
Angle can be 10-90 DEG C.The concrete structure of the atomizer c18 is known to the skilled person, and therefore not to repeat here.
In the coking heavy oil equipment, it is preferable that the spraying coking tower c also includes anti-positioned at the straight tube is arranged on
Gas distribution grid c30 that is at the top of area c21 and being connected with the hot-wind inlet c24, the gas distribution grid c30 is answered to be used for institute
State before deoxidation flue gas 4 introduces the spraying coking tower c and carry out gas distribution, so enable to the deoxidation flue gas 4 in institute
State and be uniformly distributed in spraying coking tower c, so that the contact area between the coking heavy oil raw material for further increasing and being atomized, and carry
High liquid yield.The concrete structure of the gas distribution grid c30 can be with the gas distributor b27 in the coking reactor b
It is identical, and can be the conventional selection of this area, therefore not to repeat here.
In the coking heavy oil equipment, it is preferable that the spraying coking tower c also includes being arranged on the side outlet
Chev(e)ron baffle c20 directly over c19, and the chev(e)ron baffle c20's is opening down, can so prevent the coke of generation
Particle packing is on side outlet c19 induced duct.The present invention is not special to the angle and length of the chev(e)ron baffle c20
Ground is limited, as long as the coke granule of generation can be prevented to be deposited on side outlet c19 induced duct.For example, the people
Font baffle plate c20 angle β can be 10-150 °, preferably 30-100 °.The angle of the chev(e)ron baffle c20, which is set, to be made
Obtain the angle of repose that the angle between baffle surface and horizontal plane is less than coke coarse powder.In addition, the side outlet c19 and herringbone
Baffle plate c20 can be arranged on the top straight tube reaction zone c21 and bottom cone collecting region c22 junction.
In addition, the negative-pressure operation of the spraying coking tower c is conducive to the raising of product liquid yield.Wherein, the spraying
Coking tower c internal pressure can turning by the air-introduced machine h being arranged on connection cyclone separator d and fractionating column e pipeline
Speed is adjusted, and is specifically known to the skilled person, and therefore not to repeat here.
The present invention is not particularly limited to the size of the coking heavy oil equipment.For example, the spraying coking tower c's is upper
Portion straight tube reaction zone c21 ratio of height to diameter can be 2-10:1, preferably 2-8:1.The cone angle of the bottom cone collecting region c22
It can be 10-150 °, preferably 70-120 °.In addition, the hot-wind inlet c24 and side outlet c19 diameters can be ability
The conventional selection in domain, therefore not to repeat here.In addition, the spraying coking tower c's and cyclone separator d has been respectively arranged below Jiao
Charcoal coarse powder collecting tank k and coke fines collecting tank m, falls from the spraying coking tower c coke coarse powder settled by self gravitation
Enter in coke coarse powder collecting tank k, and fallen into by the cyclone separator d coke fines isolated in coke fines collecting tank m.This
Outside, in order to improve liquid yield, it is preferable that can be each led into coke coarse powder collecting tank k and coke fines collecting tank m
One stripped vapor 7 and the second stripped vapor 9, can so be purged to the coke granule of generation, the oil gas vapour adsorbed
Put forward, the coke coarse powder and a coke fines part after stripping are transported in coke gasification reaction device b as fluidisation state solid
b28。
The present invention is not particularly limited to the species of the cyclone separator d, as long as can be by coke fines and oil gas
Separated, so as to obtain coke fines in the bottom of the cyclone separator d, top obtains oil gas, specially ability
Known in field technique personnel, therefore not to repeat here.
According to the present invention a kind of embodiment, as shown in figure 4, the coke gasification reaction device b, spraying coking tower c and
Cyclone separator d is of coupled connections, now, and the coke gasification reaction device b is gas-solid fluidized bed reactor.Come self-spray coking tower c and
Cyclone separator d bottoms respectively through the first stripped vapor 7 and the second stripped vapor 9 stripping after coke granule be introduced directly into
As fluidisation state solid b28 in the coke gasification reaction device b, flue gas 3 is introduced from coke gasification reaction device b bottoms and consolidated with the fluidisation state
Body b28 is contacted to carry out deoxidation, and deoxidation flue gas after deoxidation is from the Base top contact of the coke gasification reaction device b, and it is burnt to enter spraying
Change and exchanged heat in tower c with the coking heavy oil raw material.
The above-mentioned coking heavy oil equipment that the present invention is provided it is main the improvement is that increased newly the coke gasification reaction device b and
Cyclone separator d and internal structure to coking tower c is improved, and the fractionating column e structurally and operationally can with it is existing
There is technology identical.For example, as shown in figure 1, the oil gas 10 from the cyclone separator d be fractionated into fractionating column e coking do
Air-liquid gas, coker gasoline, coker gas oil and wax tailings, i.e. be correspondingly provided with coking dry gas respectively on the fractionating column e
Export e11, liquefied gas outlet e12, coker gasoline outlet e13, coker gas oil outlet e14 and wax tailings outlet e15.
In the coking heavy oil equipment, it is preferable that evaporating more than 460 DEG C of bottom of towe atmospheric boiling point in the fractionating column e
Oil is divided to be used as bottom of towe withdrawing oil, i.e. correspondingly, the fractionating column e also includes the outer circulating tube for being arranged on the fractionating column e bottoms
Line, for recycle column bottom withdrawing oil 16, can so play elution be introduced into carried secretly in fractionating column e oil gas not by cyclonic separation
The effect for the coke fines that device d is isolated.In addition, being further preferably provided with heat exchanger in the reactor outer circulation pipeline.
The present invention is not particularly limited to the source of the coking heavy oil raw material and incorporation way, for example, described heavy
Oily coking raw material can be the existing various heavy oil feedstocks that can be used in coking, and the coking heavy oil raw material can be by adding
Hot stove heat is to being introduced into after 50-400 DEG C in the spraying coking tower c.A preferred embodiment of the invention, it is described
Heavy oil coking method also includes feedstock oil introducing the fractionation from the raw material oil-in e1 for being arranged on the fractionating column e side-lowers
In tower e, the feedstock oil introduces described after the fractionating column e bottom of towe is mixed with the bottom of towe withdrawing oil as coking raw material 17
It is atomized, exchanged heat and pyrogenetic reaction in spraying coking tower c, now, coking heavy oil raw material can be obtained directly in fractionating column
To preheat, heating furnace is set to preheat it without extra, therefore, it is possible to avoid the coking in heating furnace tube completely
Problem, and because the temperature of preheating is relatively low, therefore the coking heavy oil raw material also unobvious coking in conveyance conduit, operation
Cycle can be obviously prolonged.Correspondingly, the side-lower of the fractionating column e is provided with raw material oil-in e1, and the fractionation
Tower e bottom is connected with the feed(raw material)inlet c25 for the coking tower c that sprays, and feedstock oil is from the raw material oil-in e1 is introduced into fractionating column e
And with bottom of towe withdrawing oil 16 and coke fines that the hydrocarbons contact from the cyclone separator d is remained with capturing in oil gas simultaneously
After preheating, drawn as coking raw material 17 from the bottom of the fractionating column e and be atomized in entering spraying coking tower c, exchanged heat
And coking, fractionating column can not only be so made full use of as thermal source, but also can prevent coke fines in fractionating column e
Accumulation, great prospects for commercial application.In the preferred embodiment, the relative amount of feedstock oil and bottom of towe withdrawing oil can basis
Actual conditions carry out Reasonable adjustment, as long as the temperature of the mixture obtained after being preheated in fractionating column e reaches 50-400 DEG C
, in this regard, those skilled in the art can know that therefore not to repeat here.In addition, the feedstock oil can be existing various
It can be used in the raw material of coking, for example, can be decompression residuum, reduced crude, heavy crude, de-oiled asphalt, residual hydrogenation weight
Oil, thermal cracking heavy oil, the tapped oil of lube oil finishing, the recycle oil of catalytic cracking and clarified oil, the tar of cracking of ethylene, coal tar
At least one of oil, shale oil, oil-sand heavy oil, bitumen etc..
The fine particle coke of the spraying coking tower c outputs is mainly the coke of spheroidal, the diameter one of coke granule
As be 0.001-1mm.The mobility of these spheroidal coke preferably, can be easier and rapidly from spraying coking tower c rows
Go out.Wherein, the particle diameter that the coke coarse powder of the spraying coking tower c bottoms can be deposited on by self gravitation can be 0.01-
1mm, preferably 0.02-1mm；And need the particle diameters of the coke fines by cyclone separator d and Oil-gas Separation can be
0.001-0.1mm, preferably 0.001-0.05mm.It is possible to be stained with a small amount of coke on the inwall of the spraying coking tower c
Particle adhesion thing, can be in shut-down (breakdown) mainteance using conventional hydraulic decoking method removing.
In the coking heavy oil equipment, in order to which preheated coking raw material smooth delivery of power is extremely located at into the spraying coking
Feed(raw material)inlet c25 at the top of tower c, can set pump g on the pipeline connected between the fractionating column e and spraying coking tower c.
The present invention will be described in detail by way of examples below.
In following examples coking heavy oil equipment used as Figure 1-3, including：(volume is coke gasification reaction device b
0.8m3), spraying coking tower c, cyclone separator d and fractionating column e；The coke gasification reaction device b is gas-solid fluidized bed reactor, its
The fluidisation state solid b28 of middle filling is the mixture of coke coarse powder and coke fines；The spraying coking tower c includes being interconnected
Top straight tube reaction zone c21 and bottom cone collecting region c22, be arranged at the top of the top straight tube reaction zone c21 and with
(quantity is 6 to the atomizer c18 symmetrically arranged vertically downward of spraying coking tower c feed(raw material)inlet c25 connections, described
Be uniformly arranged at the top of the straight tube reaction zone c21 of top, interior bore be 0.5mm), be arranged at the top of the straight tube reaction zone c21
And with spray coking tower c hot-wind inlet c24 connect gas distribution grid c30, be arranged on top straight tube reaction zone c21 and bottom
The side outlet c19 of cone collecting region c22 junctions and it is arranged on directly over side outlet c19 and downward opening herringbone
Shape baffle plate c20 (angle β is 90 °), the top straight tube reaction zone c21 of spraying coking tower c ratio of height to diameter is 5:1 (is highly
10m, internal diameter is 2m), bottom cone collecting region c22 cone angle is 60 °, hot-wind inlet c24 a diameter of 400mm, side outlet
C19 a diameter of 300mm, spraying coking tower c each part use thickness to be manufactured for 5mm stainless steel pipe；The fractionating column e
The ring-like dumped packings of θ are inside filled with, filling batch is highly 5m, and fractionating column e internal diameter is 0.5m, and fractionating column e top is set
There is coking dry gas to export e11, bottom is provided with reactor outer circulation pipeline, and side-lower is provided with raw material oil-in e1, and the fractionating column e
Bottom connected with the feed(raw material)inlet c25 of the spraying coking tower c.
In following examples and comparative example：
Feedstock oil is same residual oil (its property is shown in Table 1), and inlet amount is 25kg/h；It is in fractionating column e that bottom of towe is normal
The cut that more than 460 DEG C of pressure boiling point, which is extracted out, is used as bottom of towe withdrawing oil；Recycle ratio refers to the non-fresh feedstock oil portion in fractionating column base oil
Divide the weight ratio with the oily part of fresh feed；Spraying coking tower c and cyclone separator d lower section collecting tank is passed through stripped vapor
Discharging again after STRENGTH ON COKE particle is purged.Flue gas is that same catalytic cracking catalyst carries out the regeneration cigarette that generation is burnt in regeneration
Tail gas property after gas, regenerated flue gas and coking is shown in Table 2.
Embodiment 1-3
Embodiment 1-3 is used for the heavy oil coking method for illustrating that the present invention is provided.
By feedstock oil from fractionating column e raw material oil-in e1 be introduced into fractionating column e in preheated, it is preheated after obtained original
Material oil is introduced into spraying coking tower c via feed(raw material)inlet c25 and is atomized by atomizer c18, and obtaining liquid size is
20-500 μm of atomization droplet, regenerated flue gas 3 carries out deoxidation, (its of deoxidation flue gas 4 after deoxidation by coke gasification reaction device b
Middle oxygen content is 0.1 volume %) it is introduced into by the hot-wind inlet c24 at the top of spraying coking tower c in spraying coking tower c simultaneously
Contacted with above-mentioned atomization state droplet to reach coking temperature and carry out pyrogenetic reaction, the coke in pyrogenetic reaction product is thick
Powder (particle diameter is 0.02-1mm) is by settlement from the oil in bottom cone collecting region c22 bottom collections, coke gasification reaction product
The mixture 6 of gas and coke fines (particle diameter is 0.001-0.05mm) from side outlet c19 be introduced into cyclone separator d in carry out oil
The separation of gas and coke fines, the oil gas 10 from cyclone separator d, which is introduced into fractionating column e, carries out fraction seperation, in fractionating column e
Bottom, carrys out self-spray coking tower c oil gas 10 shape with bottom of towe withdrawing oil 16 and after the heat exchange of the feedstock oil from raw material oil-in e1
Into coking raw material, coking raw material circulation is introduced into as coking heavy oil raw material via feed(raw material)inlet c25 in the coking tower c of spraying and according to
It is secondary to be atomized, exchanged heat and pyrogenetic reaction.Wherein, after regenerated flue gas and coking the property of tail gas as shown in table 2, reaction condition
As shown in table 3, as a result as shown in table 4.
Comparative example 1
Comparative example 1 is used for the delayed coking method for illustrating to contrast with embodiment 1-3.
Delayed coking equipment used in comparative example includes：Heating furnace, coking tower and fractionating column；The inside of the coking tower is
Hollow structure；The bottom of fractionating column is provided with reactor outer circulation pipeline, and side-lower is provided with raw material oil-in, and the bottom of the fractionating column
Portion is connected with the heating furnace.During feedstock oil is introduced into fractionating column from the raw material oil-in of fractionating column, and and then from the fractionation
The bottom of towe of tower is introduced into the radiant heating area of heating furnace and is heated to coking temperature, is introduced into afterwards in coking tower and carries out pyrogenetic reaction,
Then pyrogenetic reaction product is subjected to fraction seperation in fractionating column.In fractionation column base, oil gas and bottom of towe from coking tower
Coking raw material is formed after withdrawing oil and feedstock oil heat exchange from raw material oil-in, coking raw material circulation is used as coking heavy oil former
Expect to be used for pyrogenetic reaction.Wherein, reaction condition is as shown in table 3, as a result as shown in table 4.
Table 1
| Project name | Index |
| 20 DEG C of density, kg/m3 | 1009 |
| Sulfur content, weight % | 3 |
| Carbon residue content, weight % | 20.0 |
| Pour point, DEG C | >50℃ |
| Composition, w% | |
| Saturated hydrocarbon content, weight % | 17.0 |
| Arene content, weight % | 55.1 |
| Resin and asphalt total content, weight % | 27.6 |
| Content of beary metal, μ g/g | |
| Ni | 57.1 |
| V | 60.1 |
Table 2
Table 3
| Project name | Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 |
| Coking reactor porch flue-gas temperature, DEG C | 650 | - | 620 | 720 |
| Raw material oil temperature at spraying coking tower feed(raw material)inlet, DEG C | 350 | 491 | 400 | 300 |
| Deoxidation flue-gas temperature at spraying coking tower hot-wind inlet, DEG C | 600 | - | 590 | 650 |
| Fractionation column bottoming cycle ratio | 0.13 | 0.19 | 0.13 | 0.13 |
| Spraying coking tower enters gas flow, m3/min | 25 | - | 20 | 30 |
| Spraying coking tower oil inlet quantity, kg/min | 0.41 | - | 0.41 | 0.41 |
| Coking temperature, DEG C | 491 | 491 | 490 | 501 |
| Spraying coking tower tower top pressure, MPa | -0.005 | - | 0.02 | -0.01 |
| Coke drum tower top pressure in comparative example, MPa | - | 0.13 | - | - |
| Residence time of the coking raw material in coking tower | 120s | 15.9h | 120s | 120s |
Table 4
Note：In table 4, liquid yield is the total recovery of coker gasoline, coker gas oil and wax tailings.
As can be seen from the above results, the heavy oil coking method that the present invention is provided can not only improve liquid yield, and
Green coke amount is relatively low and feedstock oil can be heated without using heating furnace tube, adds therefore, it is possible to reduce to even completely avoid
Coking in hot stove boiler tube, and reduce the coking in conveyance conduit.In addition, the heavy oil coking method that the present invention is provided can also be saved
Go flue gas carrying out the step of desulfurization, denitrogenation and dedusting, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (6)
1. a kind of heavy oil coking method, this method includes temperature being atomized for 50-400 DEG C of coking heavy oil raw material, then
The deoxidation smoke contacts that the coking heavy oil raw material of state will be atomized with temperature is 490-750 DEG C, make the coking heavy oil of the atomization state
Raw material reaches coking temperature and carries out pyrogenetic reaction, then isolated from pyrogenetic reaction product coke coarse powder, coke fines and
Oil gas, then the oil gas is subjected to fraction seperation；It is 490-515 DEG C, coking that the condition of the pyrogenetic reaction, which includes coking temperature,
Pressure is -0.01MPa to 0.1MPa, and scorch time is 0.01-20min；
Being atomized of the coking heavy oil raw material, coking heavy oil raw material contact with deoxidation flue gas of the atomization state and Jiao
The separation of charcoal coarse powder and coke fines and oil gas is carried out in spraying coking tower (c), and the separation of the coke fines and oil gas exists
Carried out in cyclone separator (d), the fraction seperation of the oil gas is carried out in fractionating column (e)；
The distillate of more than 460 DEG C of bottom of towe atmospheric boiling point is regard as bottom of towe withdrawing oil in the fractionating column (e)；
Feedstock oil is introduced into the fractionating column (e) from the raw material oil-in (e1) for being arranged on fractionating column (e) side-lower, institute
State feedstock oil and introduce the spraying as coking heavy oil raw material after fractionating column (e) bottom of towe is mixed with the bottom of towe withdrawing oil
It is atomized in coking tower (c).
2. according to the method described in claim 1, wherein, the condition of the atomization makes the coking heavy oil raw material of obtained atomization state
Droplet size be 20-500 μm.
3. according to the method described in claim 1, wherein, the deoxidation flue gas be by catalytic cracking catalyst progress regeneration burn
Gas after the regenerated flue gas deoxidation of generation.
4. method according to claim 3, wherein, the mode of the deoxidation is that the regenerated flue gas and the coke is thick
Powder and/or coke fines carry out redox reaction.
5. the method according to any one in claim 1-4, wherein, the oxygen content in the deoxidation flue gas is 2 bodies
Product below %.
6. the method according to any one in claim 1-4, wherein, the feedstock oil be decompression residuum, reduced crude,
Heavy crude, de-oiled asphalt, residual hydrogenation heavy oil, thermal cracking heavy oil, the tapped oil of lube oil finishing, the recycle oil of catalytic cracking
With the one or more in clarified oil, the tar of cracking of ethylene, coal tar, shale oil, oil-sand heavy oil and bitumen.
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| EP0520977A2 (en) * | 1991-06-25 | 1992-12-30 | Oberösterreichische Ferngas Aktiengesellschaft | Process and apparatus for the low temperature carbonization of at least partially organic waste |
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| CN102220165A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Process for delaying coking |
| CN102220166A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Delayed coking method |
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| CN101451073B (en) * | 2007-12-06 | 2012-07-18 | 中国石油化工股份有限公司 | Method for combination processing heavy oil by pyrolysis and gasification |
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| EP0520977A2 (en) * | 1991-06-25 | 1992-12-30 | Oberösterreichische Ferngas Aktiengesellschaft | Process and apparatus for the low temperature carbonization of at least partially organic waste |
| CN101481626A (en) * | 2008-01-11 | 2009-07-15 | 山东科技大学 | Process for producing spherical coke by cracking heavy oil |
| CN102010745A (en) * | 2009-07-08 | 2011-04-13 | 琳德股份公司 | Heavy oil cracking method |
| CN102220165A (en) * | 2010-04-13 | 2011-10-19 | 中国石油化工集团公司 | Process for delaying coking |
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