The suppressing method of coking tower inner foam layer
Technical field
The present invention relates to petrochemical industry, particularly to the suppressing method of a kind of coking tower inner foam layer.
Background technology
Delay coking process refers to the mink cell focus of lean hydrogen as raw material, carries out deep under high temperature (about 500 DEG C)
Degree thermal cracking and condensation reaction, with the technique producing rich gas, raw gasoline, diesel oil, wax oil and coke.Wherein,
Described delay refer to by coking raw material (including raw oil and recycle oil) heated stove heating be brought rapidly up to
Pyrogenetic reaction temperature, not green coke in reaction boiler tube, but proceed to rapidly coking tower and carry out pyrogenetic reaction, therefore
It is referred to as Delayed Coking Technology.
In delayed coking production process, there is violent thermal response in coking oil in coking tower, generates a large amount of
Oil gas and coke.During this green coke, many intermediate products are all full-bodied colloidal bitumen shape materials,
These colloidal bitumen shape materials, under the agitating of oil gas, will form stable froth bed in coking tower.Along with
Charging and response time increase, and coking tower charge level constantly raises, and froth bed also increases.Due to coking tower
Interior gas speed is higher, so when froth bed is higher, will form entrainment.Now, Jiao in froth bed
Powder can be carried in Fat gas line and fractionating column, causes Fat gas line and fractionating column coking.So, for
Reducing the adverse effect of entrainment, it is necessary to leave the spatial altitude of abundance in coking tower, this just reduces
The utilization rate of coking tower.Visible, it is provided that one can effectively reduce during delay coking process in coking tower
The method of froth bed thickness is the most necessary.
Prior art provides a kind of coking delay process reducing coking tower froth bed, including: work as Jiao
When the distance of change tower charge level and coking tower top exceedes the 15-20% of tower height, inject without froth breaking from coking tower top
The coker gas oil of agent;And as coking tower charge level and the 15-20% of the distance deficiency tower height of coking tower top, from Jiao
Change top of tower and inject the coker gas oil containing defoamer.The method can reduce the thickness of coking tower inner foam layer.
Inventor finds that prior art at least there is problems in that
The method that prior art provides uses more coker gas oil, relatively costly and be unfavorable for improving coking bavin
The productivity of oil.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, it is provided that bubble in the coking tower of a kind of low cost
The suppressing method of foam layer.Concrete technical scheme is as follows:
A kind of suppressing method of coking tower inner foam layer, for delay coking process, including: coking raw material warp
After heating furnace heating, carry out pyrogenetic reaction in proceeding to coking tower, and in described coking tower, form froth bed,
When pre-position in described froth bed rises to described coking tower first, in the tower rising pouring of described coking tower
Entering without silicon defoaming agent, the most described froth bed is suppressed and falls after rise to described precalculated position;If it is described
The API degree of coking raw material is more than 16, then continues the tower rising pouring at described coking tower and enters described without silicon defoaming agent,
Till at the end of the green coke process carried out in described coking tower;If the API degree of described coking raw material
Less than or equal to 16, then when described pre-position in described froth bed rises to described coking tower again,
The tower top of described coking tower injects containing silicon defoaming agent, until the green coke process carried out in described coking tower terminates
Time till;
Described precalculated position be apart from the height at the bottom of described coking tower tower be described coking tower height 40%-80%
Position.
Specifically, as preferably, described precalculated position be apart from the height at the bottom of described coking tower tower be described Jiao
Change the position of tower height degree 60%-75%.
Specifically, as preferably, the described injection rate without silicon defoaming agent is that 70-90 μ g is burnt without silicon defoaming agent/g
Change raw material.
Specifically, as preferably, described without silicon defoaming agent selected from polyethers defoamer, polyisobutylene compound
In class defoamer, organic sulfonic acid salt defoamer, plant oil defoamer, animal oils defoamer at least
A kind of.
Specifically, as preferably, the described injection rate containing silicon defoaming agent is that 15-30 μ g is burnt containing silicon defoaming agent/g
Change raw material.
Specifically, as preferably, described containing silicon defoaming agent selected from polysiloxane-based defoamer, polysilazane class
At least one in defoamer, silicone defoamer.
Specifically, as preferably, after the heated stove of described coking raw material is heated to 450-550 DEG C, coking is proceeded to
Pyrogenetic reaction is carried out in tower.
Specifically, described coking raw material selected from the reduced crude of any crude oil, decompression residuum, visbreaking residue,
At least one in catalytic cracked oil pulp, hydrocracking tail oil, ethylene residue, extract oil of lubricating oil.
Specifically, described delay coking process includes delay coking process and the delay of various improvement of routine
Coking process.
The technical scheme that the embodiment of the present invention provides has the benefit that
The suppressing method of the coking tower inner foam layer for delay coking process that the embodiment of the present invention provides is logical
When crossing pre-position in froth bed rises to coking tower first, the tower rising pouring at coking tower enters without silicon froth breaking
Agent.Now, can mix homogeneously with reaction mass without silicon defoaming agent and arrive the upper of froth bed with reaction mass
Portion, thus effectively eliminate partial foam, make froth bed be suppressed and fall after rise.If the API of coking raw material
Degree more than 16, enters without silicon defoaming agent in the tower rising pouring of coking tower by continuing, until carry out in coking tower
Till at the end of green coke process;If the API degree of coking raw material is less than or equal to 16, then again go up when froth bed
When rising to coking tower this pre-position interior, the tower top at coking tower injects containing silicon defoaming agent, until in coking
Till at the end of the green coke process carried out in tower.Visible, the method that the embodiment of the present invention provides is at specified conditions
Under, enter without silicon defoaming agent in tower rising pouring when coking raw material API degree is more than 16, and at coking raw material API
When degree is less than or equal to 16, tower rising pouring being entered and combine containing silicon defoaming agent with tower top injection without silicon defoaming agent, this is just
Achieve targetedly, and fast and effeciently suppress the bubble that dissimilar coking raw material produces because of delayed coking
Foam layer also ensure that foam time is the most effective.And, reduce siliceous froth breaking by using without silicon defoaming agent
The usage amount of agent, can not only reduce cost and reduce the silicon carrying amount of coking distillate, and then significantly reducing
The probability of downstream hydrogenation catalyst poisoning.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, institute in embodiment being described below
The accompanying drawing used is needed to be briefly described, it should be apparent that, the accompanying drawing in describing below is only the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is in the delay coking process that the embodiment of the present invention provides, the suppression system of coking tower inner foam layer
Structural representation.
Reference represents respectively:
1 feed pump,
2 heating furnaces,
3 without silicon defoaming agent storage tank,
4 storage tanks Han silicon defoaming agent,
5 first coking towers,
6 second coking towers,
7 fractionating columns,
8 level-sensing devices.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to the present invention
Embodiment is described in further detail.
A kind of suppressing method of coking tower inner foam layer, for delay coking process, including: coking raw material warp
After heating furnace heating, carry out pyrogenetic reaction in proceeding to coking tower, and in this coking tower, form froth bed.When
When froth bed rises to pre-position in coking tower first, the tower rising pouring at coking tower enters without silicon defoaming agent,
Now froth bed is suppressed and falls after rise to precalculated position.If the API degree of coking raw material is more than 16, continue
Continue the tower rising pouring at coking tower to enter without silicon defoaming agent, until at the end of the green coke process carried out in coking tower being
Only.If the API degree of coking raw material is not more than 16, then in froth bed rises to coking tower again, this makes a reservation for
During position, the tower top at this coking tower injects containing silicon defoaming agent, until the green coke carried out in this coking tower
Till at the end of process.Wherein, described precalculated position refers to distance height at the bottom of coking tower tower is coking tower
The position of highly 40%-80%.
Wherein, " API degree " described in the embodiment of the present invention is also weight index number, and its computing formula is as described below:
API degree=141.5/d-131.5, wherein, d is the relative density (with water ratio) when 15.6 DEG C.
The suppressing method of the coking tower inner foam layer for delay coking process that the embodiment of the present invention provides, bag
Include: after the heating of coking raw material heated stove, in proceeding to coking tower, carry out pyrogenetic reaction, and in this coking tower
Form froth bed.Wherein, froth bed be formed at reaction mass top and with coking raw material lasting injection and
Constantly raise.When froth bed rises to be positioned at the height of coking tower height 40-80% the most from bottom to up,
Without silicon defoaming agent, froth bed is carried out foam inhibition treatment first by entering in the tower rising pouring of coking tower.Owing to disappearing without silicon
Infusion enters from tower rising pouring, and it can be mixed homogeneously with reaction mass, and with reaction mass through whole froth bed
Arrive the top of froth bed, so since can not only effectively eliminate partial foam, make froth bed be subject to this
Suppress and fall after rise, but also can guarantee that the longer suds time.Then, along with the lasting injection of coking raw material,
This froth bed rises again, is positioned at coking tower height 40%-80% in this froth bed rises to coking tower again
Height at time, if the API degree of coking raw material is more than 16, then continue the tower rising pouring at coking tower and enter nothing
Silicon defoaming agent, at the end of the green coke process carried out in coking tower till.Visible, big for API degree
In the coking raw material of 16, simply using the suppression that can complete froth bed without silicon defoaming agent, froth breaking is with low cost,
And do not result in downstream hydrogenation catalyst poisoning.If the API degree of coking raw material is less than or equal to 16, then Jiao
The tower top changing tower injects containing silicon defoaming agent, at the end of the green coke process carried out in coking tower till, from
And froth bed is carried out lasting foam inhibition treatment.API degree is not more than to the later stage froth bed of the coking raw material of 16
Control particularly significant, owing to there is stronger defoaming capacity containing silicon defoaming agent, by it is injected energy at tower top
Its Rapid contact froth bed is enough made to carry out fast and effeciently froth breaking.From the foregoing, the embodiment of the present invention provides
Method, for different types of coking raw material, it is achieved that fast and effeciently suppression froth bed ensure that disappears
The bubble time is the most effective.And, by use cost cheap can effectively reduce relatively costly without silicon defoaming agent
The consumption containing silicon defoaming agent, can not only reduce froth bed suppression cost and also coking distillate can be significantly reduced
Silicon carrying amount, and then reduce downstream hydrogenation catalyst poisoning probability.
As preferably, it is coking tower height that above-mentioned precalculated position is preferably distance height at the bottom of coking tower tower
Position at 60%-75%.By this precalculated position is carried out above-mentioned restriction, it provides the benefit that at this predetermined
Position, coking froth bed is in a higher level of security, injects defoamer in this position and can reach preferable
Economic effect, and coking froth bed will not overflow coking tower and affect the safe and stable operation of device.
Specifically, as preferably, this is that 70-90 μ g is without silicon defoaming agent/g coking without the injection rate of silicon defoaming agent
Raw material, preferably 80 μ g are without silicon defoaming agent/g coking raw material.The nothing of the amount of being preferably injected is added bottom coking tower
After silicon defoaming agent, the froth bed thickness in coking tower can maintain a relatively low steady water within a certain period of time
Flat, and when the injection rate without silicon defoaming agent exceedes the amount of being preferably injected, the reduction of coking tower inner foam layer thickness
Degree is the most inconspicuous.
It will be appreciated by persons skilled in the art that described in the embodiment of the present invention be existing skill without silicon defoaming agent
Art, it can be the compounds without silicon with broken bubble function that delay coking process field is conventional, it is possible to
Obtained by commercial.For example, it is selected from polyethers froth breaking without silicon defoaming agent used by the embodiment of the present invention
Agent, polyisobutylene compounds defoamer, organic sulfonic acid salt defoamer, plant oil defoamer, animal
At least one in oils defoamer, preferred, polyethers class defoamer.
Specifically, as preferably, this injection rate containing silicon defoaming agent is that 15-30 μ g is containing silicon defoaming agent/g coking
Raw material, preferably 20 μ g contain silicon defoaming agent/g coking raw material.The nothing of the amount of being preferably injected is added bottom coking tower
After silicon defoaming agent, the froth bed thickness in coking tower can maintain a relatively low steady water within a certain period of time
Flat, but carrying out over time, the froth bed in coking tower gradually rises, until again reaching precalculated position.
Now, if the API degree of coking raw material is more than 16, then continue the tower rising pouring at coking tower and enter to be preferably injected
Amount without silicon defoaming agent, at the end of the green coke process carried out in coking tower till.If coking raw material
API degree less than or equal to 16, then inject from coking tower top the amount of being preferably injected containing silicon defoaming agent, can be fast
The thickness of coking froth bed in the low coking tower of prompt drop, and the froth breaking persistent period is longer, until reaction terminates, bubble
Foam layer thickness can maintain a relatively low plateau.
It will be appreciated by persons skilled in the art that described in the embodiment of the present invention be existing skill containing silicon defoaming agent
Art, it can be the siliceous compounds with broken bubble function that delay coking process field is conventional, it is possible to
Obtained by commercial.For example, disappearing selected from polysiloxane-based containing silicon defoaming agent used by the embodiment of the present invention
At least one in infusion, polysilazane class defoamer, silicone defoamer, the most polysiloxane-based disappears
Infusion.
Further, in the suppressing method described in the embodiment of the present invention, coking raw material is carried out pyrogenetic reaction
Operation and operating condition are prior art to those skilled in the art.As preferably, coking raw material warp
After heating furnace is heated to 450 DEG C-550 DEG C, in proceeding to coking tower, carry out pyrogenetic reaction.Wherein, coking raw material choosing
From the reduced crude of any crude oil, decompression residuum, visbreaking residue, catalytic cracked oil pulp, hydrocracking tail oil,
At least one in ethylene residue, extract oil of lubricating oil.Wherein, described delay coking process includes routine
Delay coking process and the delay coking process of various improvement.And the delay coking process of this improvement can
Including one-way delay coking process, partial circulating than delay coking process, systemic circulation than delay coking process, many
Intermediate oil delay coking process and production needle coke delay coking process.
In order to be more fully described the method described in the embodiment of the present invention, below with reference to accompanying drawing 1 to the method
It is illustrated:
As shown in Figure 1, coking raw material enters bottom fractionating column 7 through pipeline, mixes with recycle oil and carries out
After heat exchange, then inputted the radiation chamber of heating furnace 2 by feed pump 1, after heat temperature raising, enter the first coking tower 5
Or second coking tower 6 carry out pyrogenetic reaction.Wherein, in order to monitor the material position of reaction mass in coking tower,
Level-sensing device 8 it is mounted on one coking tower 5 and the second coking tower 6, and the peace of the level-sensing device 8 of middle position
The 65-75% that height at the bottom of tower is coking tower height of holding position distance coking tower.Material position when middle position
When counting 8 primary detection to froth bed, open the valve without silicon defoaming agent storage tank 3, by pump from coking tower
Tower rising pouring enters without silicon defoaming agent, to reduce froth bed thickness.Hereafter, when middle position level-sensing device 8 again
Secondary when this froth bed being detected, close the valve without silicon defoaming agent storage tank 3, open containing silicon defoaming agent storage simultaneously
The valve of tank 4, disappears being injected in coking tower from the tower top of coking tower through pump and pipeline containing silicon defoaming agent
Bubble, and last till that green coke terminates.The oil gas generated enters fractionating column 7 through overhead line, is fractionated into obtaining Jiao
Activating QI body, coker gasoline, coker gas oil and wax tailings.
Hereinafter will be further described through the present invention by specific embodiment.In specific examples below, involved
And the unreceipted condition person of operation, the condition all advised according to normal condition or manufacturer is carried out.Used former
Expect unreceipted production firm and specification person be can by city available from conventional products.
Wherein, following example and comparative example are all carried out on certain delayed coking medium-sized tester, this device
Treating capacity 15 kgs/hr, the height of coking tower is 1.8 meters.Following example and comparative example are used
Coking raw material is decompression residuum, and its character is as shown in table 1;Being polyether antifoam agent without silicon defoaming agent, it is purchased
From Jiangsu Sixin Surfactant Technology Co., Ltd., model is NPE-108;It is that polysiloxanes disappears containing silicon defoaming agent
Infusion, it is purchased from Dongguan City De Feng Chemical Co., Ltd. De Feng defoamer factory, and model is DF-805;Taked
Coking period be 20 hours.
Table 1
Embodiment 1
The heated stove of decompression residuum is brought rapidly up 500 DEG C, and input coking tower carries out pyrogenetic reaction, in coking tower
Reaction mass reaction generate oil gas agitating under, can reaction mass top formed froth bed, froth bed
Gradually rise with the lasting input of reaction mass.(should when froth bed arrives the pre-position of coking tower
Precalculated position is the distance position that height is coking tower tower height 70% at the bottom of coking tower tower), from the bottom of the tower of coking tower
Injecting without silicon defoaming agent, in the process, froth bed is suppressed, and its thickness reduces.Hereafter, coking tower is worked as
When inner foam layer reaches this precalculated position again, owing to the API degree of coking raw material is less than 16, therefore select from
The tower top of coking tower injects containing silicon defoaming agent, until the green coke process in this coking tower terminates and is switched to another
Till when individual coking tower produces.
Comparative example 1
Compared with Example 1, difference is: be not injected into any without silicon or siliceous during coking tower green coke
Defoamer.
Comparative example 2
Compared with Example 1, difference is: when froth bed reaches described in embodiment 1 in coking tower for the first time
Precalculated position time, enter without silicon defoaming agent from the tower rising pouring of coking tower, and be continued until that green coke process terminates.
Comparative example 3
Compared with Example 1, difference is: when froth bed reaches described in embodiment 1 in coking tower for the first time
Precalculated position time, inject containing silicon defoaming agent from the tower top of coking tower, and be continued until that green coke process terminates.
Comparative example 4
Compared with Example 1, difference is: when froth bed reaches described in embodiment 1 in coking tower for the first time
Precalculated position time, enter coker gas oil from coking tower rising pouring, until froth bed reaches real in coking tower again
Execute the precalculated position described in example 1, now switch to and inject containing silicon defoaming agent from the tower top of coking tower, and always
Last till that green coke process terminates.
Wherein, the such as table 2 of the operating condition employed in the delayed coking of embodiment 1 and comparative example 1-4
Shown in:
Table 2
Operating condition |
Embodiment 1 |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Comparative example 4 |
Furnace outlet temperature (DEG C) |
500 |
500 |
500 |
500 |
500 |
Top of coke tower pressure (MPa) |
0.15 |
0.15 |
0.15 |
0.15 |
0.15 |
Recycle ratio |
0.10 |
0.10 |
0.10 |
0.10 |
0.10 |
Injection rate (μ g/g) |
Embodiment 1 |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Comparative example 4 |
Without silicon defoaming agent |
65 |
0 |
65 |
0 |
0 |
Containing silicon defoaming agent |
50 |
0 |
0 |
50 |
50 |
Coker gas oil |
0 |
0 |
0 |
0 |
12000 |
Wherein, the delayed coking result of the test of embodiment 1 and comparative example 1-4 is as shown in table 3:
Table 3
Result of the test |
Embodiment 1 |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Comparative example 4 |
Froth bed thickness (%) |
5-15 |
100 |
30-40 |
5-10 |
5-15 |
Silicone content (μ g/g) |
Embodiment 1 |
Comparative example 1 |
Comparative example 2 |
Comparative example 3 |
Comparative example 4 |
Coker gasoline |
6.2 |
<0.5 |
<0.5 |
35.8 |
6.2 |
Coker gas oil |
1.3 |
<0.5 |
<0.5 |
8.4 |
1.3 |
Wax tailings |
<1.0 |
<0.5 |
<0.5 |
5.4 |
<1.0 |
The productivity (%) of coker gas oil |
32.5 |
32.5 |
32.5 |
32.5 |
31.6 |
The yield (%) of gaseous product |
9.2 |
9.2 |
9.2 |
9.2 |
9.7 |
Wherein, the thickness of froth bed when being not injected into defoamer in comparative example 1 is calculated as 100%, and injects froth breaking
During agent, the thickness of froth bed is using the former as calculating benchmark.
As shown in Table 3, in embodiment 1, froth bed thickness is only 5-15%, in coker gasoline, coker gas oil
Silicone content is respectively 6.2 μ g/g, 1.3 μ g/g, and silicone content < 1.0 μ g/g, the simultaneously coking in wax tailings
The productivity of diesel oil reaches 32.1%.This explanation uses the suppressing method described in the embodiment of the present invention can effectively suppress bubble
Foam layer also reduces its thickness, and can effectively reduce the silicone content in distillate, and can improve the product of coker gas oil
Rate.
And froth bed thickness is still 30-40% in comparative example 2, this explanation individually enters nothing in the tower rising pouring of coking tower
Silicon defoaming agent, the inhibition of coking tower inner foam layer is relatively limited.And foam in coking tower in comparative example 3
Although layer thickness is 5-10%, but in coker gasoline, coker gas oil, wax tailings, silicone content is respectively 35.8
μg/g、8.4μg/g、5.4μg/g.It is visible, although individually the tower top injection at coking tower presses down containing silicon defoaming agent
The effect of froth bed processed is preferable, but cannot effectively reduce the silicone content in distillate, easily causes follow-up hydrogenation and urges
The intoxicating phenomenon of agent.Although coking tower inner foam layer thickness also can reach 5-15% in comparative example 4, but its
The productivity ratio embodiment 1 of coker gas oil reduces 0.9%, and the productivity of the cooking gas of low value adds 0.5%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the scope of the invention, all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, all should comprise
Within protection scope of the present invention.