CN103788989A - Steam cracking method - Google Patents
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- CN103788989A CN103788989A CN201210419845.5A CN201210419845A CN103788989A CN 103788989 A CN103788989 A CN 103788989A CN 201210419845 A CN201210419845 A CN 201210419845A CN 103788989 A CN103788989 A CN 103788989A
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Abstract
The invention discloses a steam cracking method implemented in a cracking furnace, the cracking furnace comprises a convection section and a radiation section, the method comprises the following steps: mixing an olefin, hydrogen and water vapor mixture with a liquid cracking feedstock, heating an obtained cracking feedstock mixture in the convection section for vaporization of the cracking feedstock mixture, heating up to the stretch-across temperature, adding the vaporized cracking feedstock mixture into the radiation section for cracking reaction. According to the steam cracking method, coking of the olefin as a cracking feedstock in the convection section of the cracking furnace can be reduced, and the cracking furnace operation can be long-term and stable.
Description
Technical field
The present invention relates to a kind of steam cracking method.
Background technology
The low-carbon alkenes such as ethene, propylene and divinyl are the important foundation raw materials of petrochemical industry.The method of at present, producing low-carbon alkene is take tube furnace cracking petroleum hydrocarbon vapor technique as main.According to statistics, in the world divinyl more than about 99% ethene, more than 50% propylene and 90% by this explained hereafter.
The production equipment of being set up for core technology with the deep cooling process for separating in steam cracking in pipe type cracking furnace technique and downstream thereof is called ethylene unit.The nucleus equipment of this device is tube cracking furnace, and it is made up of convection zone and radiation section.Cracking stock and dilution water steam heat first respectively in heating tube in section of convection chamber, and the two mixing the post-heating that gasifies, to initial cracking temperature (i.e. " cross-over temperature "), then enter radiant coil cracking.In industrial pyrolysis furnace radiation section, the some groups of boiler tubes that configuration is identical of conventionally having arranged.In boiler tube, pass into cracking stock, the outer employing of boiler tube heated tube wall by liquid fuel or gas fuel combustion institute liberated heat, and by the heat transfer of tube wall, transfers heat to the cracking stock in boiler tube.
As everyone knows, cracking refers to that bubble point oil hydrocarbon is under hot conditions, and the process of carbochain fracture or dehydrogenation reaction generation alkene and other products occurs.The object of cracking be produce ethene, propylene is main, the simultaneously alkene such as by-product butylene, divinyl and pyrolysis gasoline, diesel oil, fuel wet goods product.
In recent years, the synthetic rubber take divinyl as monomer and synthetic resins fast development, the price of product butadiene also climbs up and up, and product butadiene also becomes the important source of profit of ethylene unit.The corresponding divinyl yield of different cracking stocks is also not quite similar, and for gas cracking stock (low-carbon alkanes below C5), the yield of divinyl is lower, such as the yield of divinyl in the cracking product of normal butane is only in 4% left and right; For liquid cracking stock (as petroleum naphtha, hydrogenation tail oil etc.), divinyl yield is relatively high, such as the yield of divinyl in the cracking product of hydrogenation tail oil is up to 7%.It has been generally acknowledged that for those can not be as for the alkene of cracking stock, the divinyl yield of some alkene is quite high, such as, the divinyl yield of maleic can shockingly reach 18%, if therefore wishing increases divinyl output, alkene as being added to pyrolyzer, maleic can be carried out to scission reaction.
Typically, the cracking section of ethylene unit is made up of some liquid pyrolyzer and a gas pyrolyzer.The raw material of gas pyrolyzer is generally ethane, propane and C4 alkane etc., and the phase of these cracking stocks in the time of charging is gas phase, vaporizes without the convection zone at pyrolyzer, and the convection zone design of pyrolyzer is often relatively simple; The raw material of liquid pyrolyzer is generally petroleum naphtha, diesel oil and hydrogenation tail oil etc., and the phase during due to these cracking stock chargings is liquid phase, need to vaporize at the convection zone of pyrolyzer, and the design of the convection zone of this pyrolyzer is often relatively more complex.If wish to increase the yield of divinyl in normal situation, just must consider the cracking of unsaturated hydrocarbons in liquid starting material pyrolyzer, the quantity that reason is gas pyrolyzer is very little.
Generally speaking, the effect of the convection zone of pyrolyzer mainly contains two, and the one, by cracking stock preheating, vaporize and be superheated to initial cracking temperature (cross-over temperature), the 2nd, the waste heat in recovered flue gas, to improve the thermo-efficiency of stove.Therefore, convection zone has different heat exchanging segment arrangement modes according to different processing requirements under normal circumstances, roughly comprises following heat exchanging segment: raw material preheating section, oiler feed preheating section, dilution steam generation superheat section, extra high pressure steam superheat section and Hybrid Heating section.Along with the development of technology, the also development of convection zone technology of pyrolyzer, the one, the hop count of convection section in cracking furnace is more and more, such as raw material preheating section can be divided into upper raw material preheating section, Raw preheating section and lower raw material preheating section according to the energy difference of fume afterheat; The 2nd, the injection mode variation of dilution steam generation, adopts different steam injection modes according to the difference of raw material, as steam injection and secondary steam injection.Adopting different steam injection modes is in order to prevent the coking of raw material at convection zone, for liquid starting materials such as petroleum naphtha, diesel oil and hydrogenation tail oils, in convection zone heat-processed, there is the process of vaporization in it, if there is alkene in raw material, at the vaporization initial stage, olefin(e) centent in gas phase is higher, easily causes coking; Vaporizing latter stage, the hydrocarbon component in liquid phase is heavier, equally easily causes coking.Once but serious coking appears in the convection zone of pyrolyzer, not only can have a strong impact on the heat transfer process of convection zone, and can cause that convection zone pressure drop increases suddenly, thereby the output of reduction pyrolyzer must be carried out mechanical decoking by pyrolyzer blowing out while reaching a certain limit.Therefore need to develop a kind of new steam cracking method, to adapt to the sneaking into operation under olefin component operating mode in raw material.
The convection zone that enters pyrolyzer for multiple different cracking stock, has proposed some embodiments in prior art.For example, CN1077978A has proposed a kind of convection zone and has adopted the method for the cracking petroleum hydrocarbon vapor ethene processed of twice steam injection, the method adopts 3 dispensing methods to inject the feeding manner of primary steam and some injection secondary steam, make pyrolyzer can adapt to lightweight material, also can adapt to heavy feed stock, and in the time that raw material switches, not need to change pipeline.The method of this patent application is only the change of steam injection mode, does not affect the final cracking yield of whole cracking technology and the quality of product.
CN1501898A has proposed the method for a kind of lightweight charging in the pyrolyzer cracking for the cracking of cracking heavy feedstocks, the method comprises to be sent into a part of lightweight charging in the feed entrance of convection section in cracking furnace, and other lightweight charging is sent into convection zone together with diluent gas.The method of this patent application has solved in the time that cracking stock is replaced by lightweight material by heavy feed stock, and how lightweight material enters the problem of pyrolyzer, and while making lightweight material by raw material preheating section, being unlikely to has excessive pressure drop.
US2009/0178956A1 has proposed a kind of for reducing the method for liquid cracking stock in convection zone coking, the method is that liquid starting material is equated to mode reduces its dividing potential drop by injected gas when the independent preheating, thereby improve liquid starting material with the mixed vaporization rate of dilution steam generation, thereby the formation of delays liquid raw material coking omen body, reduces and even eliminates the coking of liquid starting material at convection zone.
Current steam cracking method all concentrates on and how to make pyrolyzer adapt to more raw material of different nature, and as from lightweight material to heavy feed stock etc., or how pyrolyzer slows down or eliminate the generation of coking in the time using heavy feed stock.But, in prior art, do not relate to using alkene as part cracking stock the method for injecting pyrolyzer and carry out steam cracking, more do not relate to and how to solve alkene and inject pyrolyzer and can occur the problem of coking as part cracking stock.
Summary of the invention
To the object of the invention is the problem of injecting pyrolyzer meeting generation coking using alkene as part cracking stock in order overcoming, a kind of new steam cracking method to be provided.
The invention provides a kind of steam cracking method, the method is implemented in pyrolyzer, described pyrolyzer comprises convection zone and radiation section, described method comprises: the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, and the cracking stock mixture obtaining is heated in described convection zone, make described cracking stock mixture vaporize and be heated to cross-over temperature, then the cracking stock mixture of vaporization is added to radiation section and carries out scission reaction.
The present invention also provides a kind of steam cracking method, the method is implemented in pyrolyzer, described pyrolyzer comprises convection zone and radiation section, in described convection zone, be provided with raw material preheating section, dilution steam generation superheat section and mix preheating section, said method comprising the steps of: (1) is by the preheating in described raw material preheating section of liquid cracking stock; (2) by the preheating in described dilution steam generation superheat section of the mixture of alkene, hydrogen and water vapour; (3) mixture of alkene, hydrogen and water vapour through preheating that the liquid cracking stock through preheating step (1) being obtained obtains with step (2) mixes, and the cracking stock mixture obtaining is heated in described mixing preheating section, make described cracking stock mixture vaporize and be heated to cross-over temperature; (4) the cracking stock mixture of vaporization step (3) being obtained is added to radiation section and carries out scission reaction.
In described steam cracking method provided by the invention, in the process that cracking stock mixture is heated, because the alkene in described cracking stock mixture adds together with water vapour with hydrogen, therefore, at the vaporization initial stage of described cracking stock mixture, hydrogen and water vapour can play diluting effect to gas phase, make the olefin(e) centent in gas phase relatively low, thereby can alleviate the coking of even avoiding the vaporization initial stage to occur; And, in the vaporization latter stage of described cracking stock mixture, water vapour exists with the form of superheated vapour, can impel liquid cracking stock generation fast vaporizing, heavy constituents relatively many in cracking stock can be vaporized, thereby reach, alleviating vaporizes there is the object of coking latter stage.Therefore, can alleviate alkene coking in convection section in cracking furnace as cracking stock according to described method provided by the invention, make pyrolyzer can be for a long time, stably move.
And, the present inventor found through experiments, in the time that alkene contains a certain amount of 1-butylene and/or 2-butylene, carry out in the process of scission reaction at liquid cracking stock and alkene, for ethylene product, the copyrolysis effect of liquid cracking stock and alkene is born, and the ethylene yield that the two mixed pyrolysis obtains is lower than the ultimate production of the two ethene that cracking obtains separately separately; And for product butadiene, the copyrolysis effect of liquid cracking stock and alkene is positive, the divinyl output that the two mixed pyrolysis obtains is higher than the ultimate production of the two divinyl that cracking obtains separately separately.Therefore,, according to described steam cracking method provided by the invention, in the time that described alkene contains a certain amount of 1-butylene and/or 2-butylene, can obtain the divinyl yield significantly improving.
In addition, in described method of the present invention, in convection section in cracking furnace, in order to obtain the equal effect that alleviates coking, by a small amount of hydrogen is added together with alkene, can significantly reduce the consumption of water vapour.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is schematic diagram and the flow direction of material schematic diagram of the prior art cracker that comprises pyrolyzer and quenching apparatus;
Fig. 2 is schematic diagram and the flow direction of material schematic diagram of the present invention's cracker of comprising pyrolyzer and quenching apparatus.
Description of reference numerals
1 liquid cracking stock 2 oiler feed 3 water vapour
4 high pressure steam 5 blower fan 6 drums
7 quenching apparatus 8 flue gases are across section 9 radiation sections
10 convection zone 11 raw material preheating sections
12 oiler feed preheating section 13 dilution steam generation superheat sections
14 extra high pressure steam superheat section 15 Hybrid Heating sections
16 alkene 17 splitting gas house stewards
18 hydrogen
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
In the present invention, in the situation that not doing contrary explanation, the noun of locality of use typically refers to reference to shown in the drawings upper and lower as " upper and lower "; " inside and outside " refers to inside and outside with respect to the profile of each parts itself.
Fig. 2 is schematic diagram and the flow direction of material schematic diagram that comprises the cracker of pyrolyzer.Described cracker comprises pyrolyzer, rapid-cooling heat exchanger 7, drum 6, blower fan 5 and splitting gas house steward 17, and described pyrolyzer comprises convection zone 10 and radiation section 9.Cracking stock enters radiation section 9 through convection zone 10.In radiation section 9, by combustion of liquid fuel or geseous fuel institute liberated heat, the material being obtained by described cracking stock is further heated to scission reaction occurs after convection zone 10 preheatings.Split product injection rapid-cooling heat exchanger 7 carries out cooling, is separated into splitting gas and steam.Steam enters in drum 6 and carries out gas-liquid separation, and isolated high pressure steam can enter convection zone and heat, and to obtain extra high pressure steam, isolated water can be used as the water coolant of rapid-cooling heat exchanger 7; Splitting gas enters and in later separation device, isolates the target product of wanting through splitting gas house steward 17.The high-temperature flue gas that the interior burning of radiation section 9 produces enters convection zone 10 through flue gas across section 8.Described quenching apparatus 7 is preferably rapid-cooling heat exchanger, is also indirect quenching apparatus.
In order to make full use of the heat from the high-temperature flue gas of radiation section 9, the convection zone 10 of described pyrolyzer is provided with multiple sections for reclaiming heat conventionally.Conventionally, described convection zone 10 can be provided with one or more in raw material preheating section 11, oiler feed preheating section 12, dilution steam generation superheat section 13, extra high pressure steam superheat section 14 and Hybrid Heating section 15.Described raw material preheating section 11 is generally used for cracking stock to carry out preheating.Preheating is carried out in the oiler feed that described oiler feed preheating section 12 is generally used for being supplied in drum 6.Described dilution steam generation superheat section 13 is generally used for dilution steam generation (as water vapour) to carry out preheating.Described extra high pressure steam superheat section 14 is generally used for heating to obtain extra high pressure steam from the high pressure steam of drum 6.Described Hybrid Heating section 15 is generally used for cracking stock to be heated to cross-over temperature.For above mentioned these sections, can arrange according to actual needs, for example, in the time that described cracking stock need to first carry out preheating and mixes with other logistics (as dilution steam generation), need to arrange described raw material preheating section 11, on the contrary, do not need to arrange described raw material preheating section 11.
And according to needs of production, described convection zone 10 can be provided with one or more raw material preheating sections 11.In one embodiment, when described cracking stock injects by multiply logistics, and per share logistics is while all needing in advance mutually to mix through preheating again, multiple raw material preheating sections 11 are set described convection zone 10 is interior, each raw material preheating section 11 is carried out preheating to one logistics respectively.In another embodiment, when described cracking stock need to be preheated to higher temperature, and target temperature can not be preheated to through a raw material preheating section time, need to multiple raw material preheating sections 11 be set described convection zone 10 is interior, so that described cracking stock is carried out to repeatedly preheating.
According to needs of production, in order to obtain the extra high pressure steam of specified temp and pressure, can one or more extra high pressure steam superheat sections 14 be set described convection zone 10 is interior.
According to needs of production, in order cracking stock to be heated to cross-over temperature to alleviate the load of radiation section, can one or more Hybrid Heating sections be set described convection zone 10 is interior.
In described pyrolyzer, in the time being provided with the plural section being selected from raw material preheating section 11, oiler feed preheating section 12, dilution steam generation superheat section 13, extra high pressure steam superheat section 14 and Hybrid Heating section 15 in described convection zone 10, position between each section can be determined according to actual needs, when the medium to be heated in a certain section need to carry out the heating of higher-strength, also while being heated to higher temperature, this section can be arranged on to the position across section 8 near described flue gas, because relatively high across the temperature of the position flue gas of section 8 near described flue gas; When the medium to be heated in a certain section need to carry out more low intensive heating, while being also heated to lower temperature, this section can be arranged on to the position across section 8 away from described flue gas because from described flue gas across section 8 more away from the temperature of flue gas lower.For example, in one embodiment, as shown in Figure 2, in described convection zone 10, along the flow direction of high-temperature flue gas, be disposed with Hybrid Heating section 15, extra high pressure steam superheat section 14, dilution steam generation superheat section 13, oiler feed preheating section 12 and raw material preheating section 11.
Steam cracking method according to the present invention is implemented in cracker, described pyrolyzer comprises convection zone 10 and radiation section 9, described method comprises: the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, and by the cracking stock mixture obtaining in the interior heating of described convection zone 10, make described cracking stock mixture vaporize and be heated to cross-over temperature, then the cracking stock mixture of vaporization is added to radiation section 9 and carries out scission reaction.
In the present invention, liquid cracking stock enters separately the process that described convection zone 10 carries out heat exchange, and at least one in alkene, hydrogen and water vapour enter the process that described convection zone 10 carries out heat exchange and be called warm, the mixture of alkene, hydrogen and water vapour and liquid cracking stock mix (being also cracking stock mixture) and enter the process that described convection zone 10 carries out heat exchange and be called heat-processed.
In a kind of preferred implementation, described method also comprises: before the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, described liquid cracking stock is carried out to preheating in described convection zone 10.According to this implementation method, by making liquid cracking stock carry out in advance preheating before mixing with the mixture of alkene, hydrogen and water vapour, can reach the object that further alleviates coking.Preferably, the temperature of described liquid cracking stock after described convection zone 10 preheatings is 120-300 ℃, more preferably 150-250 ℃.
In another embodiment, described method also comprises: before the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, the mixture of alkene, hydrogen and water vapour is carried out to preheating in described convection zone 10.The temperature of the mixture of described alkene, hydrogen and water vapour after described convection zone preheating is preferably 480-560 ℃, more preferably 500-540 ℃.
In above-mentioned various embodiments, each warm carrying out in described convection zone 10 carries out respectively in the different sections of described convection zone 10.Particularly, the warm of described liquid cracking stock carries out in the raw material preheating section 11 of described convection zone 10.The warm of the mixture of described alkene, hydrogen and water vapour carries out in the dilution steam generation superheat section 13 of described convection zone 10.
In the preferred embodiment of one, described pyrolyzer comprises convection zone 10 and radiation section 9, is provided with raw material preheating section 11, dilution steam generation superheat section 13 and mixes preheating section 15 in described convection zone 10, and described steam cracking method comprises the following steps:
(1) by liquid cracking stock in the interior preheating of described raw material preheating section 11;
(2) by the mixture of alkene, hydrogen and water vapour in the interior preheating of described dilution steam generation superheat section 13;
(3) mixture of alkene, hydrogen and water vapour through preheating that the liquid cracking stock through preheating step (1) being obtained obtains with step (2) mixes, and by the cracking stock mixture obtaining in the interior heating of described mixing preheating section 15, make described cracking stock mixture vaporize and be heated to cross-over temperature;
(4) the cracking stock mixture of vaporization step (3) being obtained is added to radiation section 9 and carries out scission reaction.
In the above-described embodiment, step (1) and step (2) do not have the strict priority working order limiting, and preferably, step (1) and step (2) are synchronously carried out.
For above-mentioned embodiment, particularly, as shown in Figure 2, in described convection zone 10, liquid cracking stock 1 is carried out to preheating through raw material preheating section 11, the mixture of alkene 16, hydrogen 18 and water vapour 3 is carried out to preheating through dilution steam generation superheat section 13 simultaneously, afterwards the liquid cracking stock through described raw material preheating section 11 preheatings is mixed with the mixture of alkene 16, hydrogen 18 and water vapour 3 through described dilution steam generation superheat section 13 preheatings, obtain cracking stock mixture; Then described cracking stock mixture is heated through Hybrid Heating section 15, so that cracking stock mixture is heated to cross-over temperature, then inject radiation section 9 and carry out scission reaction; And then the split product obtaining is injected to described quenching apparatus 7 and carry out refrigerated separation.
In addition, above-mentioned preferred embodiment in, in order to make full use of the heat of the high-temperature flue gas in described convection zone 10, can optionally oiler feed 2 be heated by oiler feed preheating section 12, and the high pressure steam from drum 64 is heated by extra high pressure steam superheat section 14, obtain ultra-high voltage superheated vapour.In this preferred implementation, in described convection zone 10, along the flow direction of high-temperature flue gas, be preferably disposed with Hybrid Heating section 15, extra high pressure steam superheat section 14, dilution steam generation superheat section 13, oiler feed preheating section 12 and raw material preheating section 11.
In addition, the heat of high temperature of the cleavage reaction product being produced by radiation section for effective recycling, the exit that described steam cracking method of the present invention is preferably also included in described radiation section 9 adds the mixture of alkene or alkene and hydrogen and/or water vapour, utilizes the heat of high temperature of cleavage reaction product further to carry out scission reaction.
In described method provided by the invention, the weight ratio of the consumption of described liquid cracking stock and water vapour can be 1-4:1, is preferably 1.5-2.5:1.
In described method provided by the invention, the weight ratio of the consumption of described alkene and water vapour can be 1:1-30, is preferably 1:5-20.
In described method provided by the invention, the weight ratio of the consumption of described liquid cracking stock and hydrogen can be 500-10000:1, is preferably 800-4000:1.
In described method provided by the invention, the scission reaction occurring in the radiation section 9 of pyrolyzer in described scission reaction and conventional steam cracking method is basic identical, and therefore, described scission reaction can be implemented according to conventional crack reacting condition.In the preferred case, the condition of described scission reaction comprises: described is 560-660 ℃ cross-over temperature, is preferably 580-640 ℃; The temperature out of described radiation section is 780-850 ℃, is preferably 790-840 ℃; Reaction times (being also the cracking stock mixture of the described vaporization residence time in described radiation section 9) is 0.1-0.5 second, is preferably 0.2-0.3 second.
In described method provided by the invention, described alkene can be the alkene of various routines, for example, can be the alkene of C4-C6.In the preferred case, described alkene contains 1-butylene and/or 2-butylene more than 10 % by weight, more preferably contains more than 50 % by weight 1-butylene and/or 2-butylene.Such alkene can be for example conventional hybrid C 4 alkene.When the 1-butylene that comprises above-mentioned content when described alkene and/or 2-butylene, method according to the present invention can significantly improve the yield of divinyl.
In described method provided by the invention, described liquid cracking stock can be the conventional various liquid cracking stocks that use in this area, for example, can be petroleum naphtha and/or hydrogenation tail oil.
The invention will be further described by the following examples.
Embodiment 1
The present embodiment is used for illustrating described steam cracking method provided by the invention.
Adopt the cracker shown in Fig. 2 to carry out scission reaction.Detailed process comprises:
By as shown in table 2 the petroleum naphtha 1(correlation parameter of 60 ℃) carry out preheating through raw material preheating section 11; To form as shown in table 1 by hybrid C 4 alkene 16(simultaneously), the gas phase mixture stream that mixes of hydrogen 18 and water vapour 3 carries out preheating through dilution steam generation superheat section 13; Then the petroleum naphtha through preheating is mixed with the gas phase mixture stream through preheating, and the cracking stock mixture obtaining is heated through Hybrid Heating section 15, then enter radiation section 9 and carry out scission reaction; Then, the cleavage reaction product obtaining is injected to rapid-cooling heat exchanger 7 and carry out refrigerated separation, be separated into high pressure steam and splitting gas, splitting gas is entered to later separation device through splitting gas house steward 17.Wherein, the charging capacity of petroleum naphtha 1 is 43130kg/h, in described gas phase mixture stream, the injection rate of water vapour is 22700kg/h, and the charging capacity of hybrid C 4 alkene is 2270kg/h, and the injection rate of hydrogen is 25kg/h, the temperature flowing through the gas phase mixture of preheating is 500 ℃, (XOT) is 590 ℃ cross-over temperature, and the temperature out (COT) of the radiation section of pyrolyzer is 830 ℃, and the scission reaction time in radiation section 9 is 0.24 second.Other processing parameters of pyrolyzer are as shown in table 3, and by dividing the analysis of variance to learn to splitting gas, the composition of splitting gas is as shown in table 4.
Table 1
Table 2
Table 3
Table 4
| Component | % by weight |
| Hydrogen | 0.87 |
| Methane | 11.68 |
| Ethane | 3.23 |
| Ethene | 28.27 |
| Acetylene | 0.32 |
| Propane | 0.48 |
| Propylene | 16.9 |
| Propine | 0.31 |
| Propadiene | 0.23 |
| Trimethylmethane | 0.03 |
| Normal butane | 0.35 |
| Butene-1 | 2.11 |
| Iso-butylene | 2.79 |
| Anti-butylene | 1.04 |
| Maleic | 1.41 |
| Divinyl | 5.53 |
| Other | 24.45 |
| Add up to | 100.00 |
Comparative example 1
Carry out steam cracking according to the method for embodiment 1, difference is as shown in Figure 1, do not inject described hybrid C 4 alkene 16 and hydrogen 18, and the charging capacity of petroleum naphtha to be 45400kg/h in described gas phase mixture stream.Wherein, other processing parameters of pyrolyzer are as shown in table 5, and by dividing the analysis of variance to learn to splitting gas, the composition of splitting gas is as shown in table 6.
Table 5
Table 6
| Component | % by weight |
| Hydrogen | 0.81 |
| Methane | 11.79 |
| Ethane | 3.38 |
| Ethene | 29.50 |
| Acetylene | 0.33 |
| Propane | 0.50 |
| Propylene | 16.94 |
| Propine | 0.32 |
| Propadiene | 0.24 |
| Trimethylmethane | 0.04 |
| Normal butane | 0.37 |
| Butene-1 | 2.11 |
| Iso-butylene | 2.93 |
| Anti-butylene | 0.00 |
| Maleic | 0.51 |
| Divinyl | 4.84 |
| Other | 25.39 |
| Add up to | 100.00 |
By embodiment 1 is compared and can be found out with comparative example 1, the divinyl yield of embodiment 1 is 5.53 % by weight, and the divinyl yield of comparative example 1 is 4.84 % by weight, in embodiment 1 by adding alkene to make divinyl yield improve 14.26% as cracking stock.And in comparative example 1, Hybrid Heating section is 122.7kPa in the pressure drop of end-of-run; And in embodiment 1, Hybrid Heating section is 123.9kPa in the pressure drop of end-of-run, and in embodiment 1, adding Hybrid Heating section after alkene is 122.7kPa with respect to comparative example 1(Hybrid Heating section in the pressure drop of end-of-run in the pressure drop of end-of-run) only increase by 0.98%.
As can be seen here, according to described method provided by the invention, by introducing alkene as part cracking stock in convection zone 10, can significantly improve divinyl yield, and the coking amount of the warm of convection zone does not significantly increase because having injected alkene.
The present embodiment is used for illustrating described steam cracking method provided by the invention.
Carry out steam cracking according to the method for embodiment 1, difference is, the charging capacity of petroleum naphtha is 40860kg/h, and in described gas phase mixture stream, the injection rate of water vapour is 22700kg/h, the charging capacity of hybrid C 4 alkene is 4540kg/h, the injection rate of hydrogen is 50kg/h, and the temperature of second burst of logistics of process preheating is 540 ℃, is 590 ℃ cross-over temperature, the temperature out (COT) of radiation section 9 is 830 ℃, and the scission reaction time in radiation section 9 is 0.3 second.Other processing parameters of pyrolyzer are as shown in table 7, and by dividing the analysis of variance to learn to splitting gas, the composition of splitting gas is as shown in table 8.
Table 7
Table 8
| Component | % by weight |
| Hydrogen | 0.93 |
| Methane | 11.57 |
| Ethane | 3.08 |
| Ethene | 27.04 |
| Acetylene | 0.31 |
| Propane | 0.46 |
| Propylene | 16.86 |
| Propine | 0.3 |
| Propadiene | 0.22 |
| Trimethylmethane | 0.04 |
| Normal butane | 0.34 |
| Butene-1 | 2.11 |
| Iso-butylene | 2.65 |
| Anti-butylene | 2.08 |
| Maleic | 2.31 |
| Divinyl | 6.22 |
| Other | 23.48 |
| Add up to | 100.00 |
The present embodiment is used for illustrating described steam cracking method provided by the invention.
Carry out steam cracking according to the method for embodiment 1, difference is, the charging capacity of petroleum naphtha is 43130kg/h, and in described gas phase mixture stream, the injection rate of water vapour is 22700kg/h, the charging capacity of hybrid C 4 alkene is 2270kg/h, the injection rate of hydrogen is 25kg/h, and the temperature of second burst of logistics of process preheating is 520 ℃, is 590 ℃ cross-over temperature, the temperature out (COT) of radiation section 9 is 830 ℃, and the scission reaction time in radiation section 9 is 0.25 second.Other processing parameters of pyrolyzer are as shown in table 9, and by dividing the analysis of variance to learn to splitting gas, the composition of splitting gas is as shown in table 10.
Table 9
Table 10
| Component | % by weight |
| Hydrogen | 0.86 |
| Methane | 11.69 |
| Ethane | 3.22 |
| Ethene | 28.28 |
| Acetylene | 0.31 |
| Propane | 0.49 |
| Propylene | 16.95 |
| Propine | 0.31 |
| Propadiene | 0.23 |
| Trimethylmethane | 0.03 |
| Normal butane | 0.34 |
| Butene-1 | 2.10 |
| Iso-butylene | 2.78 |
| Anti-butylene | 1.02 |
| Maleic | 1.43 |
| Divinyl | 5.52 |
| Other | 24.44 |
| Add up to | 100.00 |
Data by table 3-4, table 7-8 and table 9-10 can be found out, steam cracking method according to the present invention, by introducing alkene as part cracking stock in the convection zone of pyrolyzer, can obtain higher divinyl yield, and can not cause the warm of convection zone to produce serious coking.
Claims (12)
1. a steam cracking method, the method is implemented in pyrolyzer, described pyrolyzer comprises convection zone and radiation section, described method comprises: the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, and the cracking stock mixture obtaining is heated in described convection zone, make described cracking stock mixture vaporize and be heated to cross-over temperature, then the cracking stock mixture of vaporization is added to radiation section and carries out scission reaction.
2. method according to claim 1, wherein, described method also comprises: before the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, described liquid cracking stock is carried out to preheating in described convection zone.
3. method according to claim 2, wherein, the temperature of described liquid cracking stock after described convection zone preheating is 120-300 ℃, is preferably 150-250 ℃.
4. according to the method described in any one in claim 1-3, wherein, described method also comprises: before the mixture of alkene, hydrogen and water vapour is mixed with liquid cracking stock, the mixture of alkene, hydrogen and water vapour is carried out in described convection zone to preheating.
5. method according to claim 4, wherein, the temperature of the mixture of described alkene, hydrogen and water vapour after described convection zone preheating is 480-560 ℃, is preferably 500-540 ℃.
6. according to the method described in any one in claim 1-5, wherein, the weight ratio of the consumption of described alkene and water vapour is 1:1-30, is preferably 1:5-20.
7. according to the method described in any one in claim 1-5, wherein, the weight ratio of the consumption of described liquid cracking stock and water vapour is 1-4:1, is preferably 1.5-2.5:1.
8. according to the method described in any one in claim 1-5, wherein, the weight ratio of the consumption of described liquid cracking stock and hydrogen is 500-10000:1, is preferably 800-4000:1.
9. according to the method described in any one in claim 1-8, wherein, described alkene contains 1-butylene and/or 2-butylene more than 10 % by weight, preferably contains more than 50 % by weight 1-butylene and/or 2-butylene.
10. according to the method described in any one in claim 1-8, wherein, described liquid cracking stock is petroleum naphtha and/or hydrogenation tail oil.
11. according to the method described in any one in claim 1-10, and wherein, the condition of described scission reaction comprises: described is 560-660 ℃ cross-over temperature, is preferably 580-640 ℃; The temperature out of described radiation section is 780-850 ℃, is preferably 790-840 ℃; Reaction times is 0.1-0.5 second, is preferably 0.2-0.3 second.
12. 1 kinds of steam cracking methods, the method is implemented in pyrolyzer, and described pyrolyzer comprises convection zone and radiation section, is provided with raw material preheating section, dilution steam generation superheat section and mixes preheating section in described convection zone, said method comprising the steps of:
(1) by the preheating in described raw material preheating section of liquid cracking stock;
(2) by the preheating in described dilution steam generation superheat section of the mixture of alkene, hydrogen and water vapour;
(3) mixture of alkene, hydrogen and water vapour through preheating that the liquid cracking stock through preheating step (1) being obtained obtains with step (2) mixes, and the cracking stock mixture obtaining is heated in described mixing preheating section, make described cracking stock mixture vaporize and be heated to cross-over temperature;
(4) the cracking stock mixture of vaporization step (3) being obtained is added to radiation section and carries out scission reaction.
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