CN107418614A - Online decoking method for hydrocarbon fuel tubular cracking furnace - Google Patents
Online decoking method for hydrocarbon fuel tubular cracking furnace Download PDFInfo
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- CN107418614A CN107418614A CN201710605465.3A CN201710605465A CN107418614A CN 107418614 A CN107418614 A CN 107418614A CN 201710605465 A CN201710605465 A CN 201710605465A CN 107418614 A CN107418614 A CN 107418614A
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- coke cleaning
- cracking furnace
- coke
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- reaction tube
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The inventionRelates to an on-line decoking method for a hydrocarbon fuel tubular cracking furnace, which comprises the step of introducing H into the tubular cracking furnace in which coking is performed2O2The aqueous solution is decoked, and the temperature in the tubular cracking furnace is set to be 600-850 ℃. In the invention, the coke cleaning agent H is used after the fuel is cracked2O2The aqueous solution is directly introduced into the reaction tube for on-line coke cleaning, and other tube valves are not required to be arranged on the reaction tube. The invention adopts the hydrogen peroxide decoking technology, and the hydrogen peroxide is decomposed into steam and oxygen under the high-temperature condition to decoke the tube furnace on line, so that the use of the cracking furnace can be quickly recovered after decoking. The coke cleaning effect is evaluated through the pressure difference and the wall temperature of the reaction tube, the coke cleaning effect is obvious, and the reuse of the reaction tube can be ensured.
Description
Technical field
The invention belongs to the tubular heater attended operation field in petrochemical industry, and in particular to a kind of hydrocarbon fuel
The online coke cleaning method of tube cracking furnace.
Background technology
Hydrocarbon fuel, especially Endothermic Hydrocarbon Fuel are the preferred fuels for realizing hypersonic vehicle, are not only had
Excellent combustibility, and the cooling requirement of hypersonic vehicle is disclosure satisfy that, turn into each spacefaring nation fuel at present
The emphasis and focus of research.Endothermic Hydrocarbon Fuel is in Pintsch process by on-catalytic and catalysis two ways in reactor
Wall forms burnt body.On-catalytic coking refers to that the coking presoma in pyrolysis product is diffused into reactor surface, at high temperature through poly-
The reactions such as conjunction, cyclisation, annelation and deep dehydrogenation form coking.Catalytic coking refers to coking forerunner's physical culture active surface
Absorption is learned, dehydrogenation occurs under catalytic action, produces coking.This can not only influence the heat transfer efficiency of reactor, while can cause
Conversion zone pressure difference increases, and cracking is in a kind of extreme unstable state.
At present, it is the most ripe with pyrolysis in tubular furnace technology in the device of simulation hypersonic vehicle fuel-pyrolysis, tool
There is the features such as simple in construction, heat-transfer capability is big, operating is stable.But because tube furnace diameter is smaller, certain to coke cleaning band is tired
It is difficult.The coke cleaning of tube cracking furnace is divided into two kinds of offline coke cleaning and online coke cleaning, and the former needs will reaction after cracking reaction terminates
Pipe, which unloads to be put into wood charcoal burning furnace, carries out coke cleaning, and the method not only wastes time and energy, and also reaction pipe outer wall can be caused a certain degree of
Damage, advantage is that the coke cleaning time is abundant, and coke cleaning is thorough.Online coke cleaning by by vapor and air according to a certain percentage with fuel
It is passed through after mixing in conversion zone boiler tube and carries out coke cleaning, its principle is mixed with vapor and air under the high temperature conditions using coke
Compound carries out reaction generation COx(COxIncluding CO and CO2, CO can further be oxidized to CO2), reach the purpose except carbon.Advantage
It is that coke cleaning speed is fast, easy to operate, shortcoming is that oxygen therein can react life with fuel molecule after introducing air in fuel
Into alkyl peroxide.Alkyl peroxide is unstable, easily generates free radical, is reacted by taking hydrogen and collateralization by force, final to turn
Turn to ketone or aldehyde is deposited on reaction tube and forms colloid.
The B of patent CN 101852557 provide a kind of decoking method of tubular heater of urea dewaxing device, by repeatedly
The hot water and steam of certain temperature are passed through, biuret coking caused by flushing dissolved urea reaches the purpose of thorough coke cleaning.Patent
The B of CN 104353403 provide a kind of system realized energy recovery and coupled with continuous coke cleaning, the energy recovery of the system with
The technique of continuous coke cleaning coupling is to be used to producing steam by the heat of thermal plasma torch and the loss of reactor wall, and by steam
Continuous coke-removing procedure for reactor.The general character of both patents is to set hot-water line, steam pipe, cold water certainly on tube furnace
The coke cleaning pipeline such as pipe, gas-liquid separator, this body structure of system is set to become complicated and complex for operation step.
The B of patent CN 101872205 provide oneself of the online rapid decoking process of a kind of ethylene industry pyrolysis furnace radiant section
Flowing control method, by monitoring the carbon monoxide in coke cleaning tail gas, carbon dioxide and oxygen levels, adjust automatically water on-line
Steam, air mass flow and coil outlet temperature.This method can accurately control coke cleaning amount, but maximum to air and vapor
The limitation of mass velocity ratio is strict, and the coke cleaning time needs more than 6.5 hours.Coke cleaning overlong time, easily cause the waste of resource.
The content of the invention
Present invention aims to overcome that the deficiency in background technology, there is provided one kind saves raw material, saves the time, while does not change
Become the online coke cleaning method that tube cracking furnace constructs in itself.
The present invention solves the above problems by the following technical programs：
A kind of online coke cleaning method of hydrocarbon fuel tube cracking furnace, methods described include tubular type of coking into it and split
H is passed through in solution stove2O2The aqueous solution carries out coke cleaning, and the temperature in the tube cracking furnace is set as into 600~850 DEG C.
Wherein, the H2O2The mass percent concentration of the aqueous solution is 15~30%.
Preferably, the coke cleaning time is 10~60min.
Preferably, the H2O2The volume space velocity of the aqueous solution is 0.05 × 10-2s-1~1.06 × 10-2s-1, it is highly preferred that
Wherein described H2O2The volume space velocity of the aqueous solution is 0.80 × 10-2s-1。
Beneficial effects of the present invention：
1st, it is easy to operate.The present invention uses online coke cleaning mode, on the basis of original cracker structure is not changed, only
Need to be by H2O2Feed pump is directly connected to reaction tube porch, simplifies coke cleaning step.
2nd, the coke cleaning time is short.The coke cleaning agent that the present invention uses is H2O2, utilize H under hot conditions2O2Decompose and produce H2O and O2
Carry out coke cleaning.O2Can be by H with C reaction liberated heats2O and C reaction is utilized, and balances the heat of system.Meanwhile phase
For air, O2With C reaction rate faster, coke cleaning efficiency is improved.
3rd, coke cleaning efficiency is notable.The present invention is mainly decomposed into vapor and oxygen under the high temperature conditions using hydrogen peroxide,
And vapor and oxygen can react with coke, so as to play coke cleaning effect.As shown in present invention below embodiment, dioxygen
The volume space velocity of the aqueous solution is 0.80 × 10-2s-1, coke cleaning rate is 93.7%.
Brief description of the drawings
Fig. 1 is pyrolysis in tubular furnace schematic device of the present invention.
Fig. 2 is that reaction tube wall temperature tests distributed point.
Fig. 3 monitors that reaction tube pressure difference changes when being using online coke cleaning method.
Fig. 4 monitors that reaction tube wall temperature changes when being using online coke cleaning method.
Fig. 5 is reaction tube coke content comparison diagram before and after coke cleaning.
Reference implication in Fig. 1 is as follows：
1 is raw material storage tank, and 2 be pump, and 3 be valve, and 4 be pressure sensor, and 5 be temperature sensor, and 6 be electric heating tube, and 7 are
Condenser, 8 be filter, and 9 be counterbalance valve, and 10 be gas-liquid separator.
Embodiment
The present invention is expanded on further below by embodiment and accompanying drawing, purpose, which is only that, more fully understands present invention.
Embodiment 1
1) cracking experiment
(1) by the pipeline that has been linked in sequence in Fig. 1, and the air-tightness of whole system is checked；
(2) supply hydrocarbon fuel in starting from 1 to 6, flow velocity 1g/s, adjust the pressure of reaction tube to 4MPa, temperature from
Room temperature is gradually increased to 750 DEG C, and cracks 30min at this temperature；
(3) specified time is reached, stops heating, pressure release.
2) the pipe pressure difference and wall temperature measure after cracking experiment
(1) fuel, flow velocity 1g/s are entered again, 4MPa is arrived in pressure regulation；
(2) after being heated to 600 DEG C, stable 2min, pipe pressure difference P and wall temperature T now is write down；
(3) experiment, pressure release, cooling are stopped.Treat that temperature is down to after room temperature, dried up with ethanol detergent line, then with nitrogen.
3)H2O2Coke cleaning
(1) pipeline is reequiped, changes the fuel in Fig. 11 into H2O2；
(2) after system average rate being heated into 750 DEG C, logical H is started2O2Solution carries out coke cleaning, H2O2Concentration is 30wt%, H2O2
The volume space velocity of solution is 0.80 × 10-2s-1；
(3) after coke cleaning reaction carries out 30min, logical H is stopped2O2, cooling.After temperature is down to room temperature, lead to ethanol detergent line
In water.
4) the reacted pipe pressure difference of coke cleaning and wall temperature measure
(1) pipeline is reequiped, by the H in Fig. 112O2Change fuel into；
(2) after reaction tube is heated to 600 DEG C, stable 2min, pipe pressure difference P ' and wall temperature T ' now is write down；
(3) experiment, pressure release, cooling are stopped.Treat that temperature is down to after room temperature, dried up with ethanol detergent line, then with nitrogen.
5) coke cleaning effect assessment
H is evaluated by pipe pressure difference and wall temperature2O2Coke cleaning effect.
(1) pipe pressure difference
Pressure differential deltap P=P-P ' between being imported and exported using reaction tube is evaluated coke cleaning effect, as a result such as Fig. 3 institutes
Show.It can be seen that between reaction tube pressure difference maintains 45~70KPa before coke cleaning, and pressure difference is near 30KPa after coke cleaning
Fluctuation, pressure difference substantially reduce, and represent coke cleaning significant effect.
(2) wall temperature
Thermocouple is welded in the reaction pipe outer wall at 6 in Fig. 1, reacts pipe outer wall for testing in cracking, coke-removing procedure
Temperature change, the welding position of thermocouple is as shown in Fig. 2 totally 12 points.Before and after coke cleaning, by the wall temperature T and T ' at this 12 points
Contrasted, coke cleaning effect is evaluated, as a result as shown in Figure 4.It can be seen that after coke cleaning, from reaction tube inlet
Wall temperature to pipe range 80cm sections is decreased obviously, and the coke content that wall temperature declines on explanation tube wall declines.But 80~95cm section wall temperature differences
Away from little.
(3) coke content
(hydrocarbon fuel flow velocity is 1g/s, the pressure of reaction tube to 4MPa, highest cracking temperature under identical cracking condition
750 DEG C, and cracking 30min is kept at this temperature), carry out the sign of control group and experimental group coke content.Control group only enters
Row cracking, but and unused H2O2Coke cleaning, experimental group utilize H after once cracking terminates2O2Coke cleaning is carried out by above-mentioned steps.Most
Afterwards, carry out reaction tube coke content using method of making charcoal and characterize to find, the total coke content of experimental group is 2.0mg, the coke content of control group
For 31.6mg, coke cleaning rate reaches 93.7%.
Embodiment 2
It is only 30wt%H concentration therein substantially with embodiment 12O2The aqueous solution replaces with mol ratio
10.8:1 water and the mixture of oxygen, the ratio exactly 30wt%H2O2The aqueous solution water and oxygen resulting after decomposing completely
The mol ratio of gas.Control the mixture is passed through speed so that it is with being passed through 30wt%H2O2Water and oxygen caused by aqueous solution decomposition
The mole of gas is identical.And calculate coke cleaning rate with same method, it is found that coke cleaning rate only has 73.
It can be seen that use H2O2The aqueous solution can not only coke cleaning, and than and H in catabolite2O：O2Mol ratio same ratio
Water and oxygen mixture coke cleaning efficiency it is taller go out about 29% or so.This explanation H2O2Aqueous solution coke cleaning is not to be only
The simple superposition of the coke cleaning effect of the water of same ratio and the mixture of oxygen, but effect is better than above-mentioned simple superposition.
Embodiment 3
Cracking process coke cleaning reagent selection deionized water, water is gasificated into using hot conditions deionised water with embodiment 1
Steam carries out coke cleaning with coke reaction.After system average rate is heated into 750 DEG C, start logical deionized water, volume space velocity 0.80
×10-2s-1.After coke cleaning reaction carries out 30min, stop logical deionized water, cooling.After temperature is down to room temperature, lead to ethanol cleaning
Water in pipeline.Equally, reaction tube coke content is characterized using the method for making charcoal.As a result show that last coke content is
13.8mg, compared with the control group in embodiment 1, coke cleaning rate is 56.3%.
Thus prove, under the conditions of identical cracking, coke cleaning, H2O2The coke cleaning efficiency of solution is higher than the coke cleaning efficiency of vapor, and
Significant effect.
Claims (4)
1. a kind of online coke cleaning method of hydrocarbon fuel tube cracking furnace, it is characterised in that methods described includes having tied into it
H is passed through in burnt tube cracking furnace2O2The aqueous solution carries out coke cleaning, and the temperature in the tube cracking furnace is set as into 600~850
℃。
2. according to the method for claim 1, it is characterised in that the H2O2The mass percent concentration of the aqueous solution be 15~
30%.
3. according to the method for claim 1, it is characterised in that the coke cleaning time is 10~60min.
4. according to the method for claim 2, it is characterised in that the H2O2The volume space velocity of the aqueous solution is 0.05 × 10-2s-1~1.06 × 10-2s-1。
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| CN201710605465.3A CN107418614B (en) | 2017-07-24 | 2017-07-24 | Online decoking method for hydrocarbon fuel tubular cracking furnace |
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| CN201710605465.3A CN107418614B (en) | 2017-07-24 | 2017-07-24 | Online decoking method for hydrocarbon fuel tubular cracking furnace |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452732A (en) * | 2019-09-10 | 2019-11-15 | 天津大学 | Low-temperature coke cleaning method |
| CN113701172A (en) * | 2020-05-20 | 2021-11-26 | 中国石化工程建设有限公司 | Method for treating coke-burning gas of ethylene cracking furnace |
| CN113831930A (en) * | 2020-06-08 | 2021-12-24 | 中国石化工程建设有限公司 | Decoking device and decoking method for ethylene cracking furnace |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU266736A1 (en) * | В. С. Комаров , Н. И. Плющевский Институт общей , неорганической химии Белорусской ССР | METHOD FOR REGULATING ZEOLITHNB1X CATALYSTS | ||
| US2882237A (en) * | 1956-05-29 | 1959-04-14 | Shell Dev | Method for oxidizing carbonaceous deposits |
| US4849025A (en) * | 1987-06-05 | 1989-07-18 | Resource Technology Associates | Decoking hydrocarbon reactors by wet oxidation |
| JPH06248310A (en) * | 1993-02-26 | 1994-09-06 | Sumitomo Metal Ind Ltd | Operation of blast furnace |
| CN101372630A (en) * | 2007-08-23 | 2009-02-25 | 中国石油化工股份有限公司 | On-line coke cleaning method for tube cracking furnace |
| CN101423453A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Control method for accelerating on-line coke burning for industrial pyrolysis furnace |
| CN101872205B (en) * | 2009-04-27 | 2011-11-02 | 中国石油化工股份有限公司 | Automatic control method of online rapid decoking of cracking furnace |
| CN103254962A (en) * | 2013-04-27 | 2013-08-21 | 晟通科技集团有限公司 | Boiler coke restraining and removing agent |
-
2017
- 2017-07-24 CN CN201710605465.3A patent/CN107418614B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU266736A1 (en) * | В. С. Комаров , Н. И. Плющевский Институт общей , неорганической химии Белорусской ССР | METHOD FOR REGULATING ZEOLITHNB1X CATALYSTS | ||
| US2882237A (en) * | 1956-05-29 | 1959-04-14 | Shell Dev | Method for oxidizing carbonaceous deposits |
| US4849025A (en) * | 1987-06-05 | 1989-07-18 | Resource Technology Associates | Decoking hydrocarbon reactors by wet oxidation |
| JPH06248310A (en) * | 1993-02-26 | 1994-09-06 | Sumitomo Metal Ind Ltd | Operation of blast furnace |
| CN101372630A (en) * | 2007-08-23 | 2009-02-25 | 中国石油化工股份有限公司 | On-line coke cleaning method for tube cracking furnace |
| CN101423453A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Control method for accelerating on-line coke burning for industrial pyrolysis furnace |
| CN101872205B (en) * | 2009-04-27 | 2011-11-02 | 中国石油化工股份有限公司 | Automatic control method of online rapid decoking of cracking furnace |
| CN103254962A (en) * | 2013-04-27 | 2013-08-21 | 晟通科技集团有限公司 | Boiler coke restraining and removing agent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452732A (en) * | 2019-09-10 | 2019-11-15 | 天津大学 | Low-temperature coke cleaning method |
| CN113701172A (en) * | 2020-05-20 | 2021-11-26 | 中国石化工程建设有限公司 | Method for treating coke-burning gas of ethylene cracking furnace |
| CN113701172B (en) * | 2020-05-20 | 2024-03-12 | 中国石化工程建设有限公司 | Method for treating burnt gas of ethylene cracking furnace |
| CN113831930A (en) * | 2020-06-08 | 2021-12-24 | 中国石化工程建设有限公司 | Decoking device and decoking method for ethylene cracking furnace |
| CN113831930B (en) * | 2020-06-08 | 2023-04-07 | 中国石化工程建设有限公司 | Decoking device and decoking method for ethylene cracking furnace |
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