The suppressing method of coking tower inner foam layer
Technical field
The present invention relates to petrochemical industry, in particular to a kind of suppressing method of coking tower inner foam layer.
Background technique
Delay coking process is referred to using the mink cell focus of poor hydrogen as raw material, and depth hot tearing is carried out under high temperature (about 500 DEG C)
Change and condensation reaction, to produce rich gas, raw gasoline, diesel oil, wax oil and the technique of coke.Wherein, refer to will be burnt for the delay
Change raw material (including feedstock oil and recycle oil) heated stove heating to be brought rapidly up to pyrogenetic reaction temperature, not given birth in reaction boiler tube
Coke, but it is transferred to coking tower progress pyrogenetic reaction rapidly, therefore referred to as Delayed Coking Technology.
In delayed coking production process, violent thermal response occurs in coking tower for coking oil, generates a large amount of oil gas
And coke.During the green coke, many intermediate products are all highly viscous colloidal bitumen shape substances, these colloidal bitumen shape objects
Matter will form stable froth bed under the agitating of oil gas in coking tower.As charging and reaction time increase, coking tower material
Face constantly increases, and froth bed also increases.Since gas velocity is higher in coking tower, so just will form when froth bed is higher
Entrainment.At this point, the coke powder in froth bed can be carried into Fat gas line and fractionating column, Fat gas line and fractionation are caused
Tower coking.So in order to reduce the adverse effect of entrainment, it is necessary to which, there are sufficient spatial altitude in coking tower, this is just
Reduce the utilization rate of coking tower.As it can be seen that providing a kind of coking tower inner foam layer during delay coking process can be effectively reduced
The method of thickness is very necessary.
The prior art provides a kind of coking delay process for reducing coking tower froth bed, comprising: when coking tower material
When face is more than the 15-20% of tower height at a distance from coking tower top, the coker gas oil of defoaming agent is free of from the injection of coking tower top;And
As coking tower charge level 15-20% of deficiency tower height at a distance from coking tower top, the coke containing defoaming agent is injected from coking tower top
Change diesel oil.This method can reduce the thickness of coking tower inner foam layer.
The inventor finds that the existing technology has at least the following problems:
The method that the prior art provides uses more coker gas oil, higher cost and the production for being unfavorable for raising coker gas oil
Rate.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that provide a kind of coking tower inner foam layer of low cost
Suppressing method.Specific technical solution is as follows:
A kind of suppressing method of coking tower inner foam layer is used for delay coking process, comprising: the heated furnace of coking raw material adds
After heat, it is transferred in coking tower and carries out pyrogenetic reaction, and form froth bed in the coking tower, when the froth bed rises for the first time
To in the coking tower when pre-position, the coking tower tower bottom injection without silicon defoaming agent, the froth bed quilt at this time
Inhibit and falls after rise to the predetermined position;If the API degree of the coking raw material is greater than 16, continue in the coking
The tower bottom of tower injects the no silicon defoaming agent, at the end of the green coke process carried out in the coking tower until;If institute
The API degree for stating coking raw material is less than or equal to 16, then when the froth bed rises to the predetermined position in the coking tower again
When place, contain silicon defoaming agent in the tower top injection of the coking tower, at the end of the green coke process carried out in the coking tower
Until;
The predetermined position is the position that the height apart from the coking tower tower bottom is the coking tower height degree 40%-80%
It sets.
Specifically, preferably, it is the coking tower height that the predetermined position, which is height apart from the coking tower tower bottom,
Spend the position of 60%-75%.
Specifically, preferably, the injection rate of the no silicon defoaming agent is 70-90 μ g without silicon defoaming agent/g coking raw material.
Specifically, preferably, the no silicon defoaming agent is selected from polyethers defoaming agent, polyisobutene compounds defoam
At least one of agent, organic sulfonic acid salt defoaming agent, plant oil defoaming agent, animal oils defoaming agent.
Specifically, preferably, the injection rate containing silicon defoaming agent is that 15-30 μ g contains silicon defoaming agent/g coking raw material.
Specifically, preferably, it is described containing silicon defoaming agent be selected from polysiloxane defoamer, polysilazane class defoaming agent,
At least one of organic silicon defoaming agent.
Specifically, preferably, the heated stove heating of the coking raw material to after 450-550 DEG C, be transferred in coking tower into
Row pyrogenetic reaction.
Specifically, the coking raw material is selected from reduced crude, decompression residuum, the visbreaking residue, catalytic cracking of any crude oil
At least one of slurry oil, hydrocracking tail oil, ethylene residue, extract oil of lubricating oil.
Specifically, the delay coking process includes conventional delay coking process and various improved delay coke chemical industry
Skill.
Technical solution provided in an embodiment of the present invention has the benefit that
The suppressing method of coking tower inner foam layer provided in an embodiment of the present invention for delay coking process, by steeping
When foam layer rises to pre-position in coking tower for the first time, inject in the tower bottom of coking tower without silicon defoaming agent.At this point, being defoamed without silicon
Agent can be uniformly mixed with reaction mass and reach the top of froth bed with reaction mass, so that partial foam is effectively eliminated,
It is suppressed froth bed and falls after rise.If the API degree of coking raw material is greater than 16, by continuing the tower bottom injection nothing in coking tower
Silicon defoaming agent, at the end of the green coke process carried out in coking tower until;If the API degree of coking raw material is less than or equal to
16, then when froth bed rises to the pre-position in coking tower again, contain silicon defoaming agent in the tower top injection of coking tower, directly
Until at the end of the green coke process carried out in coking tower.As it can be seen that method provided in an embodiment of the present invention is under given conditions,
It is injected in tower bottom without silicon defoaming agent when coking raw material API degree is greater than 16, and when coking raw material API degree is less than or equal to 16, it will
Tower bottom injection, which is injected without silicon defoaming agent with tower top, to be combined containing silicon defoaming agent, which achieves targetedly, and it is fast and effective
Froth bed that ground inhibits different type coking raw material to generate by delayed coking simultaneously ensure that foam time is persistently effective.Moreover, logical
Crossing reduces the usage amount containing silicon defoaming agent using no silicon defoaming agent, can not only reduce cost and reduce the silicon of coking distillate
Carrying amount, and then a possibility that significantly reduce downstream hydrogenation catalyst poisoning.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the structure of the inhibition system of coking tower inner foam layer in delay coking process provided in an embodiment of the present invention
Schematic diagram.
Appended drawing reference respectively indicates:
1 feed pump,
2 heating furnaces,
3 without silicon defoaming agent storage tank,
4 storage tanks containing silicon defoaming agent,
5 first coking towers,
6 second coking towers,
7 fractionating columns,
8 level-sensing devices.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
A kind of suppressing method of coking tower inner foam layer is used for delay coking process, comprising: the heated furnace of coking raw material adds
After heat, it is transferred in coking tower and carries out pyrogenetic reaction, and form froth bed in the coking tower.When froth bed rises to coking for the first time
In tower when pre-position, inject in the tower bottom of coking tower without silicon defoaming agent, froth bed is suppressed and falls after rise to pre-determined bit at this time
Set lower section.If the API degree of coking raw material is greater than 16, continue the tower bottom injection in coking tower without silicon defoaming agent, until in coking
Until at the end of the green coke process carried out in tower.If the API degree of coking raw material is not more than 16, when froth bed rises to again
In coking tower when the pre-position, contain silicon defoaming agent in the tower top injection of the coking tower, until carried out in the coking tower
Until at the end of green coke process.Wherein, the predetermined position refers to that the height apart from coking tower tower bottom is coking tower height degree
The position of 40%-80%.
Wherein, " API degree " described in the embodiment of the present invention is also weight index number, and calculation formula is as described below: API degree=
141.5/d-131.5, wherein relative density when d is 15.6 DEG C (with water ratio).
The suppressing method of coking tower inner foam layer provided in an embodiment of the present invention for delay coking process, comprising: burnt
After changing the heated stove heating of raw material, it is transferred in coking tower and carries out pyrogenetic reaction, and form froth bed in the coking tower.Wherein,
Froth bed is formed in the top of reaction mass and constantly increases with the lasting injection of coking raw material.When froth bed for the first time from lower and
When Shangdi is risen at the height of coking tower height degree 40-80%, injected by the tower bottom in coking tower without silicon defoaming agent pair
Froth bed carries out foam inhibition treatment for the first time.Since no silicon defoaming agent is injected from tower bottom, can be uniformly mixed with reaction mass, and with
Reaction mass passes through the top that entire froth bed reaches froth bed, can not only effectively eliminate partial foam since then, make
Froth bed is fallen after rise by the inhibition, and also ensures the longer foam inhibition time.Then, with the lasting note of coking raw material
Enter, which rises again, when the froth bed rises to the height in coking tower positioned at coking tower height degree 40%-80% again
When place, if the API degree of coking raw material is greater than 16, continue the tower bottom injection in coking tower without silicon defoaming agent, until in coke
Until changing at the end of the green coke process carried out in tower.As it can be seen that being greater than 16 coking raw material for API degree, only Jin Shiyong disappears without silicon
The inhibition of froth bed can be completed in infusion, and defoaming is low in cost, and not will cause downstream hydrogenation catalyst poisoning.If coking is former
The API degree of material is less than or equal to 16, then contains silicon defoaming agent in the tower top injection of coking tower, until the green coke mistake carried out in coking tower
Until at the end of journey, to carry out continuing foam inhibition treatment to froth bed.The later period bubble of coking raw material for API degree no more than 16
Foam layer control is particularly significant, due to having stronger defoaming capacity containing silicon defoaming agent, by the way that it can be made it in tower top injection
Rapid contact froth bed is fast and effeciently defoamed.It can be seen from the above, method provided in an embodiment of the present invention, for inhomogeneity
The coking raw material of type realizes and fast and effeciently inhibits froth bed and ensure that foam time is persistently effective.Moreover, by using
Low-cost no silicon defoaming agent can effectively reduce cost the higher dosage containing silicon defoaming agent, can not only reduce froth bed inhibition
Cost and the silicon carrying amount that can significantly reduce coking distillate, and then a possibility that reduction downstream hydrogenation catalyst poisoning.
Preferably, height of the above-mentioned predetermined position preferably apart from coking tower tower bottom is coking tower height degree 60%-
Position at 75%.By carrying out above-mentioned restriction to the predetermined position, the beneficial effect is that in the predetermined position, coking froth bed
In a higher level of security, in this position, injection defoaming agent can reach preferable economic effect, and coking froth bed
It does not overflow coking tower and influences the safe and stable operation of device.
Specifically, excellent preferably, the injection rate without silicon defoaming agent is 70-90 μ g without silicon defoaming agent/g coking raw material
Select 80 μ g without silicon defoaming agent/g coking raw material.From coking tower bottom be added the amount of being preferably injected without silicon defoaming agent after, in coking tower
Froth bed thickness can maintain a lower plateau within a certain period of time, and when the injection rate without silicon defoaming agent is more than
When the amount of being preferably injected, the reduction degree of coking tower inner foam layer thickness is not obvious.
It will be appreciated by persons skilled in the art that described in the embodiment of the present invention without silicon defoaming agent be the prior art,
Can commonly have for delay coking process field brokenly bubble function without silicon class compound, and can be obtained by commercially available.It lifts
Example for, used in the embodiment of the present invention without silicon defoaming agent can be selected from polyethers defoaming agent, polyisobutene compounds defoaming agent,
At least one of organic sulfonic acid salt defoaming agent, plant oil defoaming agent, animal oils defoaming agent, the defoaming of preferred, polyethers class
Agent.
Specifically, excellent preferably, the injection rate for containing silicon defoaming agent is 15-30 μ g containing silicon defoaming agent/g coking raw material
Select 20 μ g containing silicon defoaming agent/g coking raw material.From coking tower bottom be added the amount of being preferably injected without silicon defoaming agent after, in coking tower
Froth bed thickness can maintain a lower plateau within a certain period of time, but with the progress of time, in coking tower
Froth bed gradually rise, until reach predetermined position again.At this point, continuing if the API degree of coking raw material is greater than 16
Coking tower the tower bottom injection amount of being preferably injected without silicon defoaming agent, until carried out in coking tower green coke process at the end of be
Only.If the API degree of coking raw material is less than or equal to 16, contain silicon defoaming agent from the coking tower top injection amount of being preferably injected,
The thickness of coking froth bed in coking tower can be reduced rapidly, and it is longer to defoam the duration, until reaction terminates, froth bed thickness
A lower plateau can be maintained.
It will be appreciated by persons skilled in the art that containing silicon defoaming agent described in the embodiment of the present invention is the prior art,
Can commonly have the siliceous class compound of brokenly bubble function for delay coking process field, and can be obtained by commercially available.It lifts
For example, polysiloxane defoamer, polysilazane class defoaming agent, organic is selected from containing silicon defoaming agent used in the embodiment of the present invention
At least one of silicon class defoaming agent, preferably polysiloxane defoamer.
Further, in suppressing method described in the embodiment of the present invention, to coking raw material carry out pyrogenetic reaction operation and
Operating condition is the prior art to those skilled in the art.Preferably, the heated stove heating of coking raw material is to 450
After DEG C -550 DEG C, it is transferred in coking tower and carries out pyrogenetic reaction.Wherein, coking raw material is selected from the reduced crude of any crude oil, decompression
At least one of residual oil, visbreaking residue, catalytic cracked oil pulp, hydrocracking tail oil, ethylene residue, extract oil of lubricating oil.Its
In, the delay coking process includes conventional delay coking process and various improved delay coking process.And this changes
Into delay coking process again may include that one-way delay coking process, partial circulating than delay coking process, systemic circulation compare delay coke
Chemical industry skill, more intermediate oil delay coking process and production needle coke delay coking process.
For method described in the present invention will be described in more detail embodiment, this method is explained below with reference to attached drawing 1
It states:
As shown in Fig. 1, coking raw material enters 7 bottom of fractionating column through pipeline, after mixing and exchanged heat with recycle oil, then
The radiation chamber of heating furnace 2 is inputted by feed pump 1, and the first coking tower 5 is entered after heat temperature raising or the progress coking of the second coking tower 6 is anti-
It answers.Wherein, in order to monitor the material position of reaction mass in coking tower, material position is mounted on the first coking tower 5 and the second coking tower 6
Meter 8, and the height of tower bottom of the installation site of the level-sensing device 8 of middle position apart from coking tower is the 65- of coking tower height degree
75%.When 8 primary detection of level-sensing device of middle position is to froth bed, the valve without silicon defoaming agent storage tank 3 is opened, pump is passed through
It injects from the tower bottom of coking tower without silicon defoaming agent, to reduce froth bed thickness.Hereafter, when the level-sensing device of middle position 8 again
When detecting the froth bed, the valve without silicon defoaming agent storage tank 3 is closed, while opening the valve of storage tank containing silicon defoaming agent 4, will contained
Silicon defoaming agent is injected into coking tower from the tower top of coking tower through pump and pipeline and is defoamed, and continues to that green coke terminates.It gives birth to
At oil gas enter fractionating column 7 through overhead line, be fractionated obtain cooking gas, coker gasoline, coker gas oil and wax tailings.
Hereinafter the present invention will be further described through by specific embodiment.In following specific embodiments, related behaviour
It is not specified condition person, according to normal conditions or the condition suggested of manufacturer carries out.It is raw materials used that production firm is not specified
And specification person be can be with conventional products that are commercially available.
Wherein, following embodiment and comparative example carry out on certain delayed coking medium-sized tester, the processing of the device
15 kgs/hr of amount, the height of coking tower are 1.8 meters.Coking raw material used in following embodiment and comparative example is decompression
Residual oil, property are as shown in table 1;No silicon defoaming agent is polyether antifoam agent, is purchased from Jiangsu Sixin Surfactant Technology Co., Ltd.,
Model NPE-108;It is polysiloxane defoaming agent containing silicon defoaming agent, is purchased from the rich defoaming of Dongguan City De Feng Chemical Co., Ltd. moral
Agent factory, model DF-805;The coking period taken is 20 hours.
Table 1
Embodiment 1
The heated furnace of decompression residuum is brought rapidly up to 500 DEG C, and input coking tower carries out pyrogenetic reaction, the reaction in coking tower
Material can form froth bed, froth bed continues with reaction mass under the agitating that reaction generates oil gas at the top of reaction mass
It inputs and gradually rises.When froth bed reaches the pre-position of coking tower, (predetermined position is apart from coking tower tower bottom
Height is the position of coking tower tower height 70%), it injects from the tower bottom of coking tower without silicon defoaming agent, in the process, froth bed quilt
Inhibit, thickness reduces.Hereafter, when coking tower inner foam layer reaches the predetermined position again, due to the API degree of coking raw material
It less than 16, therefore selects to contain silicon defoaming agent from the injection of the tower top of coking tower, until the green coke process in the coking tower terminates and cuts
Until changing to when another coking tower is produced.
Comparative example 1
Compared with Example 1, difference is: any no silicon or siliceous defoaming are not injected into during coking tower green coke
Agent.
Comparative example 2
Compared with Example 1, difference is: when froth bed reaches pre-determined bit described in embodiment 1 for the first time in coking tower
When setting, inject from the tower bottom of coking tower without silicon defoaming agent, and be continued until that green coke process terminates.
Comparative example 3
Compared with Example 1, difference is: when froth bed reaches pre-determined bit described in embodiment 1 for the first time in coking tower
When setting, contain silicon defoaming agent from the injection of 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 pre-determined bit described in embodiment 1 for the first time in coking tower
When setting, enter coker gas oil from coking tower rising pouring, until froth bed reaches pre-determined bit described in embodiment 1 again in coking tower
It sets, is switched at this time from the injection of the tower top of coking tower containing silicon defoaming agent, and be continued until that green coke process terminates.
Wherein, operating condition employed in embodiment 1 and the delayed coking of comparative example 1-4 is as shown in table 2:
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, embodiment 1 and the delayed coking test result of comparative example 1-4 are as shown in table 3:
Table 3
Test result |
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 yield (%) 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, when the thickness of froth bed when being not injected into defoaming agent in comparative example 1 being calculated as 100%, and injecting defoaming agent, bubble
The thickness of foam layer is using the former as calculating benchmark.
As shown in Table 3, froth bed thickness is only 5-15% in embodiment 1, the silicone content in coker gasoline, coker gas oil point
Not Wei 6.2 μ g/g, 1.3 μ g/g, and the silicone content in wax tailings < 1.0 μ g/g, while the yield of coker gas oil reaches
32.1%.This explanation can effectively be inhibited froth bed and be reduced its thickness using suppressing method described in the embodiment of the present invention, and energy
The silicone content in distillate is effectively reduced, and the yield of coker gas oil can be improved.
And froth bed thickness is still 30-40% in comparative example 2, this explanation is individually defoamed in the tower bottom injection of coking tower without silicon
The inhibitory effect of agent, coking tower inner foam layer is relatively limited.Although and coking tower inner foam layer thickness is 5- in comparative example 3
10%, but silicone content is respectively 35.8 μ g/g, 8.4 μ g/g, 5.4 μ g/g in coker gasoline, coker gas oil, wax tailings.It can
See, although individually inhibiting the effect of froth bed preferable containing silicon defoaming agent in the tower top injection of coking tower, can not be effectively reduced and evaporate
Divide the silicone content in oil, easily causes the intoxicating phenomenon of follow-up hydrogenation catalyst.Although coking tower inner foam layer thickness in comparative example 4
Also it can reach 5-15%, but the productivity ratio embodiment 1 of its coker gas oil reduces 0.9%, and the production of the cooking gas of low value
Rate increases 0.5%.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.