CN1173904C - Reverse jet flow mixing heating cracking equipment and method of producing ethylene - Google Patents
Reverse jet flow mixing heating cracking equipment and method of producing ethylene Download PDFInfo
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- CN1173904C CN1173904C CNB011451300A CN01145130A CN1173904C CN 1173904 C CN1173904 C CN 1173904C CN B011451300 A CNB011451300 A CN B011451300A CN 01145130 A CN01145130 A CN 01145130A CN 1173904 C CN1173904 C CN 1173904C
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Abstract
The present invention relates to a reverse jet mixing and heating cracking device and a method for producing ethylene. Hydrogen or methane is used as fuel, oxygen flows into a combustion chamber with the chemical equivalent ratio, carrier gas is formed by the complete combustion, carrier gas is regulated by steam and is lowered to required temperature, and carrier gas flows into a cracking section after being accelerated to a supersonic speed through a de Laval nozzle. After the temperature of raw gas is raised to be approached to temperature for starting cracking, raw gas flows in a raw material ejector and is ejected in a cracking section, raw gas is rapidly mixed with reverse supersonic carrier gas flows for raising temperature, and cracking is started. After cracking is carried out for required lime, mixed material flows are cooled by a water cooling heat exchanger, and products obtained by cracking are frozen. The present invention can be used for preparing ethylene and other products of chemical industry by cracking. The present invention has the advantages of rapid temperature rise, no limitation by the refractory property of wall materials, raised cracking temperature and greatly improved yield of ethylene than tube cracking furnaces.
Description
Technical field
The present invention relates to a kind of method of the equipment of ethene being made in the raw material cracking and being utilized this device fabrication ethene.
Background technology
Chemical kinetics and industrial practice all draw: when oil or natural gas pyrolysis, the condition that improves ethylene yield is for big calorimetric in (1) short period of time; (2) short residence time of high cracking temperature and (3).
At present, 99% in the whole world ethylene yield is by the tube cracking furnace output, and raw material heats up and cracking institute heat requirement is that combustion gas passes to mobile raw material in the pipe by tube wall outside managing.Be subjected to the qualification of pipe wall material resistance to elevated temperatures, the raw material cracking temperature is high not enough; Limit by the tube wall heat-transfer intensity, temperature-rise period is slow, and the residence time is oversize.The productive rate gap that can reach under the more satisfactory condition of actual product productive rate is also quite big.From the sixties, adopt to reduce the boiler tube diameter and shorten boiler tube length, the increase heat-transfer intensity also reduces the residence time, and ethylene yield is progressively improved." millisecond pyrolyzer " its boiler tube internal diameter 254mm from the outset of the eighties design is reduced to 25.4mm, and the residence time is reduced to tens of milliseconds from second-time.When adopting ethane to make raw material, the more conventional tube furnace of ethylene yield improves 5-10%; And when adopting heavier feedstocks, ethylene yield even can improve 20-30%.If can further shorten the residence time, improve cracking temperature, ethylene yield also can improve.Yet because sectional area is little in the boiler tube, single tube yields poorly, and in order to reach big output, boiler tube group number and radical are a lot, are difficult to make the raw material uniformly distributing.Also because the boiler tube diameter is little, resistance is big, and slightly coking is arranged, the cracking condition rapid deterioration.Therefore, this " millisecond pyrolyzer " is difficult to promote the use of.The cracking furnace tube internal diameter that industry is at present widely applied is greater than 50mm, and key cut has been totally to dwindle potentiality that the boiler tube internal diameter improves ethylene yield.
United States Patent (USP) NO 3,146,015 (on June 7th, 1977) has invented a kind of new method that raw material is heated to cracking temperature.Fuel (hydrogen or methane) mix with water vapor the back ignition, the high-temperature fuel gas of generation with subcritical flow to nozzle throat.Liquid starting material just sprays in the gas-flow with vaporific at throat's upstream end, with combustion gas mixing and evaporation, preliminary cracking takes place.Mixture accelerates to supersonic speed in throat's downstream convergent divergent channel, after this Supersonic stream passed shock wave, temperature sharply raise, and the further cracking of raw material is to quench area.Air communication over-heat-exchanger behind the quenching reclaims useful heat energy.The ethylene yield of this method can improve 7% by tube furnace more at that time.
Russian patent SU 392723 (July 15 nineteen eighty-three) has invented the method for oxicracking methane generation acetylene and ethene, methane is heated to 820 ℃ of oxygen with 200 ℃ mixes mutually, thinks that entering the cycle weak point can directly not light.The methane rich mixture accelerates to supersonic speed by De Laval noz(zle), and this supersonic airstream bumps against with target body outside nozzle exit, forms detached shock wave before target.Shock wave downstream airflow temperature sharply rises, and methane is by ignition, and temperature further raises significantly.Methane cracking more than needed generates acetylene and ethene.
All adopted shock wave to add the thermal control residence time in above-mentioned two patents.When unstripped gas is crossed shock wave with supersonic flow, air-flow slows down and is subsonic speed, and temperature raise in the extremely short time, has created prerequisite for shortening the residence time.Yet in aforesaid United States Patent (USP), when liquid fuel sprays in the high-temperature fuel gas, be heated cracking, shock wave subsequently adds the thermal control cracking can be played much effects actually and be difficult to determine.In aforesaid russian patent, when 820 ℃ methane when 200 ℃ oxygen mixes, be difficult to prevent ignition.Shock wave mixed downstream thing temperature is lower than the initial mixing temperature.If the shock wave heat temperature raising can be lighted a fire and be ignited, then initial mixing also can be lighted a fire.It is also difficult definite that shock wave adds the effect of the thermal control residence time.
In order to overcome the deficiency of above-mentioned two patents, United States Patent (USP) NO 5,219,530 (on June 15th, 1993) proposes new shock wave heating means, adopts superheated vapour to make carrier gas, and carrier gas is accelerated into the multiply supersonic flow by the array jet pipe.After the unstripped gas preheating by array jet pipe interior passageway with in the middle of the supersonic speed carrier gas stream is injected each strand air-flow with paralleling.Both turbulent flows in mixing section are mixed formation supersonic speed mixed flow.In mixing process, unstripped gas will remain its temperature and be positioned at inferior crack temperature range, and cracking does not take place.After the supersonic speed mixed flow was crossed shock wave, temperature raise rapidly and begins cracking generation desired product.This heating means can strictly be controlled the residence time, thereby can obviously improve product yield.Yet because carrier gas when mixing with fuel gas, should avoid in the mixing process raw material temperature degree above inferior cracking temperature, again with the carrier gas transmission ofenergy to unstripped gas, difficulty is very big.Adopted excessive carrier gas (water vapor surpasses 96%) for this reason.When making raw material with ethane, when cracking generated ethene, ethylene yield exceeded about 20% than tube furnace.Yet, consume excessive water steam, cause the running cost costliness, hold it back in industrial practicality.
Summary of the invention
The object of the present invention is to provide a kind of reverse jet flow mixing heating cracking equipment, it is cheap, and anti-coking performance is strong, the product yield height.
Another purpose of the present invention is to provide a kind of method of utilizing said apparatus to produce ethene.
For achieving the above object, reverse jet flow mixing heating cracking equipment provided by the invention, its integral body is a wind-tunnel tubulose, includes:
A combustion chamber is used to produce higher temperature carrier gas;
An atomizing nozzle is used for injection water steam, carrier gas is adjusted to temperature required;
A De Laval noz(zle) accelerates to supersonic speed and enters the cracking section when making carrier gas by this jet pipe;
A preheating heat exchanger is used for unstripped gas is warmed up near beginning cracked temperature;
A former material ejector is provided with jet hole, is used for the unstripped gas near the beginning cracking temperature is injected into the cracking section;
An oil-to-water heat exchanger is used for freezing and accepts the cracking product;
A fuel gas potentiostat and an oxygen stabilizer place the body of heater outside, are used for the pressure of steady fuel gas and oxygen respectively, and enter the combustion chamber by critical jet pipe separately.
Described former material ejector is provided with row's jet hole, places on the axis of supersonic speed carrier gas stream, and the unstripped gas jet of formation and carrier gas stream direction are mutually 180 °.
Described former material ejector is provided with two row's jet holes, and its angle beta is 10-90 °, and the unstripped gas jet and the carrier gas stream of formation is mutually (180-β) °.
Distance between described former material ejector and the preheating heat exchanger can be regulated.
A kind of method of utilizing said apparatus to produce ethene provided by the invention is a carrier gas with high-temperature water vapor or water vapor and carbon dioxide mix gas, and the pressure in the combustion chamber is 0.5-2.0Mpa; Regulate reduction carrier gas temperature with the water vapor of atomizing nozzle ejection, its carrier gas flows through De Laval noz(zle) and forms supersonic speed carrier gas stream, its Mach number Ma=1.5-4; Be preheating to and in the cracking section, oppositely inject in the supersonic speed carrier gas stream near the unstripped gas of beginning cracking temperature; By quenching, desired product is freezed behind the stop required time.
Described high-temperature water vapor is to adopt hydrogen and oxygen mixed firing to generate.
Described water vapor and carbon dioxide mix gas are to adopt methane and oxygen mixed firing to generate.
It is to use atomized water that described adjusting reduces the carrier gas temperature.
Said apparatus provided by the invention is oppositely injected in the high enthalpy supersonic speed carrier gas stream unstripped gas, and unstripped gas is risen rapidly.Carrier gas adopts hydrogen and oxygen or methane and oxygen mixed firing generation high-temperature water vapor or water vapor and carbon dioxide mix gas.Reduce the carrier gas temperature by the spray water xi that sprays in the combustion chamber, be adjusted to temperature required carrier gas and flow through De Laval noz(zle) formation supersonic speed carrier gas stream.Be preheating near the unstripped gas of beginning cracking temperature and in the cracking section, oppositely inject in the supersonic speed carrier gas stream.Unstripped gas jet and fast velocity of sound carrier gas stream interfere with each other strongly, and mixed gas mixture is reduced to subsonic speed, the temperature beginning cracking that raises rapidly.By quenching, desired product is freezed behind the stop required time.
Description of drawings
Below in conjunction with accompanying drawing structure of the present invention and principle are described in detail, wherein:
Fig. 1 is a structural representation of the present invention;
Fig. 2 is a raw material emitter construction synoptic diagram of the present invention.
Embodiment
As shown in Figure 1, fuel (hydrogen or methane) and oxygen make pressure keep constant respectively by potentiostat 1 and 2, enter combustion chamber 5 by critical jet pipe 3 and 4 respectively then.As long as critical nozzle throat is sonic flow, then the flow rate of fuel and oxygen will not be subjected to the combustion chamber magnitude of back pressure and influences and keep constant.Fuel metering and oxygen pressurizer pressure and nozzle throat sectional area size can make the flow rate of fuel and oxygen reach into stoichiometric ratio inflow combustion chamber respectively, make its perfect combustion, form carrier gas.5 downstreams in the combustion chamber spray into water vapor by atomizing nozzle 6 and incite somebody to action or atomized water, carrier gas are regulated being reduced to required temperature.Carrier gas stream flows into cracking section 8 after accelerating to supersonic speed by De Laval noz(zle) 7.
Unstripped gas is warmed up in preheating heat exchanger 9 near flowing into former material ejector 10 behind the beginning cracking temperature, and by the 11 reverse or oblique cracking sections 8 of injecting of the jet hole on this injector 10, the unstripped gas jet disturbs strongly with reverse supersonic speed carrier gas stream, and short mix heats up, the beginning cracking.After stopping required time, mixture flow is preheated heat exchanger 9 earlier, is cooled off by oil-to-water heat exchanger 12 then, and the product that cracking is obtained freezes.Mixture flow can be regulated by the distance that changes between former material ejector 10 and the preheating heat exchanger 9 in 8 residence time of cracking section.
See also Fig. 2, this figure is the sectional view of former material ejector 10.Mention jet hole 11 reverse or oblique the inject cracking sections 8 of unstripped gas from the former material ejector 10 in the narration of front, this depends on the setting of the jet hole 11 on the former material ejector 10.Fig. 2 a and Fig. 2 b have shown two kinds of settings of jet hole 11.What Fig. 2 a showed is single jet hole 11, be positioned on the axis of supersonic speed carrier gas stream, the material jet of formation and carrier gas stream direction antithesis, 180 ° each other.What Fig. 2 b showed is two row's jet holes 11, and angle beta of this two rows jet hole 11 is 10-90 °, and the unstripped gas jet and the carrier gas stream of formation is mutually (180-β) °.
Embodiment: after room temperature hydrogen and oxygen passed through potentiostat 1 and 2 respectively from separately gas-holder, control pressure stabilized to 1Mpa.Hydrogen is the critical jet pipe 3 of 3.8cm by throat diameter, and oxygen is the critical jet pipe 4 of 5.5cm by throat diameter, injects combustion chamber 5 simultaneously and mixes the back ignition.The mass flow rate of the water vapor that burning produces is 6.5Kg/sec.The rear portion of combustion chamber sprays into the water vapor through preheating, its mass flow rate 5.5Kg/sec, and temperature range is 500-600K (temperature of the water vapor that this temperature produces after far below fuel combustion for ease of narration, is called high-temperature water vapor and water at low temperature steam).The mixed temperature of high and low temperature water vapor is 1800K, and total flow rate is 12Kg/sec; De Laval noz(zle) 7 throat diameters are 18.5cm, and the water vapor stagnation pressure is 0.6Mpa.Water vapor accelerates to Ma=3 in De Laval noz(zle) 7 exits.With ethane is raw material, sprays into the cracking section 8 that diameter is 50cm from the jet hole 11 of former material ejector 10 is oblique.The long 3cm of former material ejector 10 oval cross-section transverse axis, the long 5cm of major axis, wall thickness 0.5cm; Jet hole 11 is two rows, every row 5 holes, totally 10 holes, bore dia 2cm.Ethane is heated to inferior cracking temperature (this temperature is controlled at less than 700K) through preheat exchanger 9, is heated to 600K, and pressure is 0.5Mpa, and per second can spray into 3Kg ethane.Straying quatity rises with pressure, and rising with temperature descends.
The present invention is converted into ethene by 68% ethane, is that 80% (year work 7000 hours) is calculated with the work period, utilizes the present invention can produce 50,000 tons of ethene per year.
Claims (10)
1, a kind of reverse jet flow mixing heating cracking equipment, its integral body are a wind-tunnel tubulose, include:
A combustion chamber is used to produce higher temperature carrier gas;
An atomizing nozzle is used for injection water steam, carrier gas is adjusted to temperature required;
A De Laval noz(zle) accelerates to supersonic speed and enters the cracking section when making carrier gas by this jet pipe;
A preheating heat exchanger is used for unstripped gas is warmed up near beginning cracked temperature;
A former material ejector is provided with jet hole, is used for the unstripped gas near the beginning cracking temperature is injected into the cracking section;
An oil-to-water heat exchanger is used for freezing and accepts the cracking product;
A fuel gas stabilizer and an oxygen stabilizer place the body of heater outside, are used for the pressure of steady fuel gas and oxygen respectively, and enter the combustion chamber by critical jet pipe separately.
2, reverse jet flow mixing heating cracking equipment as claimed in claim 1 is characterized in that, described former material ejector is provided with row's jet hole, places on the axis of supersonic speed carrier gas stream, and the unstripped gas jet of formation and carrier gas stream direction are mutually 180 °.
3, reverse jet flow mixing heating cracking equipment as claimed in claim 1 or 2 is characterized in that, described former material ejector is provided with two row's jet holes, and its angle beta is 10-90 °, and the unstripped gas jet and the carrier gas stream of formation is mutually (180-β) °.
4, reverse jet flow mixing heating cracking equipment as claimed in claim 1 or 2 is characterized in that, the distance between described former material ejector and the preheating heat exchanger can change.
5, reverse jet flow mixing heating cracking equipment as claimed in claim 3 is characterized in that, the distance between described former material ejector and the preheating heat exchanger can change.
6, a kind of method of utilizing said apparatus to produce ethene is a carrier gas with high-temperature water vapor or water vapor and carbon dioxide mix gas, and the pressure in the combustion chamber is 0.5-2.0Mpa; Regulate reduction carrier gas temperature with the water vapor of atomizing nozzle ejection, its carrier gas flows through De Laval noz(zle) and forms supersonic speed carrier gas stream, its Mach number Ma=1.5-4; Be preheating to and in the cracking section, oppositely inject in the supersonic speed carrier gas stream near the unstripped gas of beginning cracking temperature; By quenching, desired product is freezed behind the stop required time.
7, method as claimed in claim 6 is characterized in that, described high-temperature water vapor is to adopt hydrogen and oxygen mixed firing to generate.
8, method as claimed in claim 6 is characterized in that, described water vapor and carbon dioxide mix gas are to adopt methane and oxygen mixed firing to generate.
9, method as claimed in claim 6 is characterized in that, the steam temperature of described atomizing nozzle ejection is 400-700K.
10, method as claimed in claim 6 is characterized in that, it is to use atomized water that described adjusting reduces the carrier gas temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011451300A CN1173904C (en) | 2001-12-30 | 2001-12-30 | Reverse jet flow mixing heating cracking equipment and method of producing ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011451300A CN1173904C (en) | 2001-12-30 | 2001-12-30 | Reverse jet flow mixing heating cracking equipment and method of producing ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1429798A CN1429798A (en) | 2003-07-16 |
| CN1173904C true CN1173904C (en) | 2004-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB011451300A Expired - Fee Related CN1173904C (en) | 2001-12-30 | 2001-12-30 | Reverse jet flow mixing heating cracking equipment and method of producing ethylene |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102518534B (en) * | 2011-12-30 | 2014-01-29 | 中国人民解放军国防科学技术大学 | Heating device of hydrocarbon fuel |
| US20140058149A1 (en) * | 2012-08-21 | 2014-02-27 | Uop Llc | High efficiency processes for olefins, alkynes, and hydrogen co-production from light hydrocarbons such as methane |
| CN103087760A (en) * | 2012-12-28 | 2013-05-08 | 深圳市力科气动科技有限公司 | Pneumatic heating and quick warming process and equipment for same |
| CN108915909B (en) * | 2018-06-04 | 2020-01-31 | 湖南吉利汽车部件有限公司 | methanol cracking device |
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| CN1429798A (en) | 2003-07-16 |
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Granted publication date: 20041103 Termination date: 20131230 |