CN101870633A - Method for producing low-carbon olefins by using petroleum hydrocarbon - Google Patents
Method for producing low-carbon olefins by using petroleum hydrocarbon Download PDFInfo
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Abstract
The invention discloses a method for producing low-carbon olefins by using petroleum hydrocarbon. The method comprises the following steps of: making a preheated petroleum hydrocarbon raw material contact a hydrogen combustion catalyst in a hydrogen combustion heating area to directly obtain heat, which is required by the dehydrogenization of the petroleum hydrocarbon, of a hydrogen combustion reaction; allowing the petroleum hydrocarbon to contact a dehydrogenization catalyst in a dehydrogenization area to obtain petroleum hydrocarbon material flow which contains unsaturated olefin compounds, wherein the conversion rate of a dehydrogenization reaction is at least 20 percent; and allowing the obtained petroleum hydrocarbon material flow which contains the unsaturated olefin compounds to contact an olefin cracking catalyst in an olefin cracking reaction area to obtain a petroleum hydrocarbon material flow which contains C2 to C9 olefins and separating the petroleum hydrocarbon material flow which contains C2 to C9 olefins to obtain low-carbon products. When the technical process of the invention is used for producing the low-carbon olefins, the heat transfer effect and the heat transfer efficiency are improved, the energy is saved, the environment is protected, the energy consumption in a separation process is reduced and the low-carbon olefin selectivity of the petroleum olefin raw materials is obviously improved.
Description
Technical field
The present invention relates to a kind of method of producing alkene, more specifically, the present invention relates to a kind of with C by the oil stable hydrocarbon
4-C
35Stable hydrocarbon is the method for raw material production low-carbon alkene, especially ethene, propylene and butylene.
Background technology
As everyone knows, be a strong endothermic process of high temperature by petroleum hydrocarbon through producing low-carbon olefins by cracking.The method that present modal oil stable hydrocarbon is produced low-carbon alkene such as ethene, propylene and divinyl etc. is a steam splitting process.About in the world 99% ethene and 50% above propylene are produced by this method.Because steam cracking method production is operated at present in very harsh conditions, for example the temperature in latter stage of crack furnance radiation section furnace tube reaches or surpasses 1125 ℃, and the residence time of material in radiant coil shortens to 0.2s even shorter.Under existing state of the art, the improved possibility that oil stable hydrocarbon steam cracking method is produced low-carbon alkenes such as ethene, propylene and divinyl is very little.In light of this situation, studying the fixed-bed catalytic cracking technique that is applicable to petroleum naphtha at present, as CN02129551, CN1380898A, CN200510028797, CN03141148.With respect to the steam heat cracking, because the existence of catalyzer not only can reduce cracking temperature, and can improve the selectivity of low-carbon alkene (propylene/ethylene), thereby be subjected to paying attention to widely.But solid catalyst adds the reduction of the external energy efficiency of supply that is caused behind the reaction tubes and the uneven shortcoming of bringing thus of reaction temperature profile, becomes a difficult problem in the evolution of fixed-bed catalytic cracking technique.
As seen, because the strong endothermic character of high temperature of petroleum hydrocarbon cracking process needs a large amount of heat supplies, to reach the severe condition that scission reaction needs.The steam heat cracking technology of existing industrial employing and petroleum naphtha fixed-bed catalytic cracking technology process just under study for action are faced with huge energy demand and the low problem of heat transfer efficiency that ultrahigh-temperature is provided by outside indirect heating mode respectively.Transform the development of producing the low-carbon alkene technology in order to continue to promote petroleum hydrocarbon, in today and the future that the energy is becoming tight day by day, need provide a kind of is the raw material production low-carbon alkene with the petroleum hydrocarbon, the method that the while energy consumption reduces significantly.
From the mode angle of energy supply, the SMART vinylbenzene technology that forms with patents such as US4812597 and US4914249 provides useful reference.This process using selective hydrogen burning catalyst makes the hydrogen selective combustion under the situation that hydrocarbon species such as ethyl benzene/styrene exist in the logistics of part dehydrogenation afterreaction, utilize energy that hydrogen burning produces with direct-fired mode the temperature of logistics bring up to dehydrogenation reaction can take place temperature (about 600 ℃) with dehydrogenation once more, thereby replaced traditional intersegmental indirect external heating mode.The key of SMART vinylbenzene technology successful implementation is to have developed high performance selective hydrogen burning catalyst, can be under the situation that hydrocarbon species exist burning hydrogen optionally, thereby provide energy to improve the heat-transfer effect of logistics high-temperature heat supply process in direct-fired mode, improve heat transfer efficiency, conserve energy.Owing to change into a certain amount of hydrogen of meeting generation in the low carbon olefin hydrocarbon at petroleum hydrocarbon, use for reference the SMART technological process, if can be this part hydrogen by mixing with petroleum hydrocarbon, under the selective hydrogen burning catalyst effect, discharge its chemical energy by selective combustion hydrogen mode, the temperature that improves petroleum hydrocarbon raw material in direct-fired mode reaches can carry out follow-up hydrocarbon conversion chemical reaction, to be to improve heat-transfer effect, improve heat transfer efficiency, conserve energy is improved petroleum hydrocarbon and is transformed one of effective way of preparation low-carbon alkene technology.
Transform preparation low-carbon alkene aspect from petroleum hydrocarbon, what cause concern is the carbon four and above olefins by catalytic cracking (abbreviation olefin cracking) the producing light olefins technology of fast development in recent years.Comprise with the LURGI being fixed-bed process (the Producing Propylene from Low Valued Olefins.Hydroca rbon Eng of representative, 1999,5 (4): 66～68 and Increase propylene yield cost-effectively, Hydrocarbon Processing, 2002,81 (12): 77～80) with KBR company is fluidized-bed process (the Producing propylene of representative, Hydrocarbon Engineering, 2004,9 (7): 69～72 and Consider Improving Refining and Petrochemical Integration as a Revenue-Generating Option.Hydrocarbon Process, 2001,80 (11): 47～53).The fact based on carbon four and the fast development of above olefins by catalytic cracking preparing ethylene and propylene technology, if can change into the petroleum hydrocarbon that mainly consists of saturated hydrocarbons with carbon number alkene, and then utilize carbon four and above olefins by catalytic cracking preparing ethylene and propylene technology to prepare low-carbon alkenes such as ethylene, propylene, will be the route by petroleum hydrocarbon production low-carbon alkene of a novelty undoubtedly.
There have been many companies that industrialized dehydrating alkanes technology can be provided at present in the world.For example relevant patents such as CN1037667C, CN1069226C, CN1013361B, CN1084224C are concentrated and to have been reported in low-carbon alkanes (carbon four and following) and long chain alkane (carbon 12 and more than) dehydrogenation and prepare the technological process of alkene and catalyzer accordingly.From these patents as seen, though use the carbon number difference of raw material hydro carbons, the catalyzer that uses belongs to carrier-precious metal type catalyzer substantially, thereby the proof petroleum hydrocarbon is feasible through the process that dehydrogenation reaction produces with carbon number alkene.Moreover, when the raw material of processing when identical since the bond energy of C-C, produce the energy requirement of the certain embodiments of same carbon number alkene much larger than the bond energy of C-H will be well below the energy requirement that produces low-carbon alkene cracking process such as ethene, propylene.
Advantage, the petroleum hydrocarbon multistep processes of this patent combined with hydrogen burning internal heating technology aspect transmission ofenergy transforms the low advantage of methane content in relative mitigation of each unit process energy requirement of producing light olefins technology and the product, proposed the technological process that a kind of new petroleum hydrocarbon transforms producing light olefins.
Summary of the invention
The purpose of this invention is to provide the advantage of a kind of combined with hydrogen burning internal heating technology aspect transmission ofenergy; Petroleum hydrocarbon transforms the producing light olefins technology in the advantage aspect the products distribution through dehydrogenation and this multistep processes of olefin cracking, has proposed the method that a kind of new petroleum hydrocarbon transforms producing light olefins:
According to method of producing low-carbon alkene of the present invention, may further comprise the steps by petroleum hydrocarbon:
1) preheating: petroleum hydrocarbon raw material is heated to 100～200 ℃;
2) hydrogen burning: the petroleum hydrocarbon material of preheating mixes with weight ratio 1: 0～5 with thinner, adds hydrogen and oxygen again, enters the hydrogen burning heating zone then so that logistics utilizes the hydrogen burning reaction to reach the temperature that dehydrogenation reaction needs;
3) dehydrogenation: will introduce dehydrogenation reactor from the logistics of hydrogen burning heating zone, and in the presence of dehydrogenation catalyst, carry out dehydrogenation reaction, and obtain containing the petroleum hydrocarbon mixture flow of hydrogen and unsaturated hydrocarbons compounds;
4) olefin cracking: the petroleum hydrocarbon mixture flow that contains hydrogen and unsaturated hydrocarbons compounds that certain embodiments produces is mixed introducing alkene cracking reactor in back with thinner with weight ratio 1: 0～2, in the presence of the olefin cracking catalyzer, carry out the olefin cracking reaction, obtain containing hydrogen and C
2～C
4The mixture flow of alkene;
5) separate: adopt conventional isolation technique to contain hydrogen and C what step 4) obtained
2～C
4The mixture flow of alkene is separated, and obtains hydrogen gas stream, C respectively
2Olefin stream, C
3Olefin stream and C
4Olefin stream.
Preferably, described thinner is a water vapour.
Preferably, described hydrogen burning heating zone is made up of successively low temperature hydrogen burning heater and high temperature hydrogen burning heater or is single hop hydrogen burning well heater.
In the situation that described hydrogen burning heating zone is made of successively low temperature hydrogen burning heater and high temperature hydrogen burning heater, the petroleum hydrocarbon temperature of charge of preferred described low temperature hydrogen burning heater outlet is 150～500 ℃.The petroleum hydrocarbon temperature of charge of preferred described high temperature hydrogen burning heater outlet is 400～1000 ℃, more preferably 500～700 ℃.
Preferably, in described step 4) olefin cracking process, the petroleum hydrocarbon mixture flow that will contain hydrogen and unsaturated hydrocarbons compounds is introduced described alkene cracking reactor with thinner, in described alkene cracking reactor, contact, the olefin cracking reaction that carbonatoms reduces takes place with the olefin cracking catalyzer.Described thinner is thinners commonly used such as water vapour.
Preferably, in described step 5) sepn process, described separation comprises compression, low temperature separation process, rectifying and extraction process.In sepn process of the present invention, those skilled in the art can form according to material, at random selects suitable sepn process, is not limited to listed sepn process.
Preferably, described dehydrogenation reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of dehydrogenation catalyst, described hydrogen burning reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of hydrogen burning catalyst, and described alkene cracking reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of conversion of olefines catalyzer.
Preferably, described dehydrogenation catalyst is dehydrogenation catalyst or nickel catalyst for carried noble metal Pt, described hydrogen burning catalyst is that carried noble metal Pt or Pd are hydrogen burning catalyst, and described olefin cracking catalyzer is one or more the mixture in modification or unmodified ZSM-5, ZSM-11, ZSM-23, MCM-22 and the SAPO molecular sieve catalysts.
Preferably, described petroleum hydrocarbon raw material is for being selected from C
4-C
35The mixture of one or more in stable hydrocarbon, petroleum naphtha, diesel oil, whiteruss, solid paraffin, normal paraffin mixture, hydrogenation tail oil, tops and the reformate.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, the raising of petroleum hydrocarbon raw material temperature is by realizing with exchange of this flow process reacting rear material waste heat and hydrogen burning direct heating process.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, petroleum hydrocarbon raw material is preheating to 100～200 ℃ after finishing the residual heat of reaction utilization, with mixing diluents, sneak into appropriate amount of hydrogen and oxygen again, enter the hydrogen burning heating zone and carry out the hydrogen burning reaction, the stream temperature scope that petroleum hydrocarbon raw material leaves hydrogen burning direct heating district is 400～1000 ℃.Hydrogen burning direct heating district can be made up of one or several hydrogen burning reactors.According to the difference of logistics temperature out, the hydrogen burning reactor can be divided into low temperature hydrogen combustion reactor and high temperature hydrogen combustion reactor.For the low temperature hydrogen combustion reactor, the temperature out scope of logistics is 150～500 ℃, and preferable range is 150～300 ℃, and for the high temperature hydrogen combustion reactor, the temperature out scope of logistics is 400～1000 ℃, and preferable range is 500～700 ℃.Usually, the petroleum hydrocarbon raw material after the heat exchange at first enters low temperature hydrogen burning direct heating section (being made up of or several low temperature hydrogen combustion reactors), carries out the low temperature hydrogen direct heating that burns under the effect of low temperature hydrogen combustioncatalysts.After material flows out low temperature hydrogen burning direct heating section, mend to enter behind an amount of oxygen or an amount of oxygen and the hydrogen high temperature hydrogen burning direct heating section (forming), under the effect of high temperature hydrogen combustioncatalysts, carry out the high temperature hydrogen direct heating that burns by one or several high temperature hydrogen combustion reactors.After hydrogen burning direct heating district is left in the petroleum hydrocarbon logistics that has reached temperature requirement, enter the petroleum hydrocarbon dehydrogenation reaction zone.In the hydrogen burning heating zone, the low temperature hydrogen combustion reactor number in the low temperature hydrogen burning direct heating section is 0～8, is preferably 0～4; The number of high temperature hydrogen combustion reactor is 1～8 in the high temperature hydrogen burning direct heating section, is preferably 1～4.Promptly the number of the low temperature hydrogen combustion reactor that adopts of this method and high temperature hydrogen combustion reactor can be according to practical situations, regulates as parameters such as raw material inlet amount and feeding manner, hydrogen burning catalyst loadings, the required temperature of follow-up petroleum hydrocarbon dehydrogenation reaction.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, in low temperature hydrogen combustion reactor and high temperature hydrogen combustion reactor, two types hydrogen burning catalyst is housed respectively.For the catalyzer that is applicable to the low temperature hydrogen combustion reactor, active ingredient adopts platinum, palladium or the mixture of the two usually, carrier is generally organism class hydrophobic carrier, the advantage of this class catalyzer is can keep good activity in the environment that liquid water exists, for example the BHO-L catalyzer of Beijing Chemical Research Institute's development.For the catalyzer that is applicable to the high temperature hydrogen combustion reactor, active ingredient adopts platinum, palladium or the mixture of the two mostly, carrier selects for use the mineral-type hydrophilic carrier (as aluminum oxide usually, porous ceramics or the like), the advantage of this class catalyzer is to use temperature higher (reaching as high as 2000 ℃), for example the BHO-H catalyst series of Beijing Chemical Research Institute's development.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, an amount of oxygen of alleged introducing or an amount of oxygen and hydrogen, for hydrogen, the enough heated stream of the heat that combustion of hydrogen discharged that are interpreted as in right amount in the logistics arrive needed temperature; For oxygen, be interpreted as the reaction carried out according to stoichiometric equation according to hydrogen and oxygen in right amount, oxygen can satisfy the needs that the hydrogen burning reaction requires liberated heat, and is too much unsuitable.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, the reaction conditions of logistics in the hydrogen burning heating zone is: reaction pressure 0～0.5MPa, preferred 0.1～0.3MPa, weight hourly space velocity are 0.3～10h
-1, preferred 0.5～5h
-1, the hydrogen-oxygen mol ratio is 0.5～2, preferred 0.8～1.5.
It needs to be noted, low temperature hydrogen burning direct heating process and high temperature hydrogen burning direct heating process can be respectively in each independent reactor carries out, also the hydrogen burning catalyzing sequential of two types can be contained in the reactor, perhaps simultaneously petroleum hydrocarbon conversion reactor and hydrogen burning direct heating district be concentrated in the reactor.
In the method by petroleum hydrocarbon production low-carbon alkene of the present invention, described petroleum hydrocarbon raw material is introduced described dehydrogenation reaction zone with thinner, in described dehydrogenation reaction zone, contact, obtain the unsaturated hydrocarbons compounds with the dehydrogenation catalyst of forming by precious metals pt and alumina catalyst support or ZSM-5 molecular sieve (for example Beijing Chemical Research Institute produce BDH catalyzer); In described step (4), the described logistics that contains the petroleum hydrocarbon of unsaturated hydrocarbons compounds is introduced described olefin cracking reaction zone with thinner, the olefin cracking catalyzer of being made up of process P or alkali-earth metal modified ZSM-5 molecular sieve in described olefin cracking reaction zone (for example BOC catalyzer of Beijing Chemical Research Institute's production) contact obtains the mixed olefins that carbonatoms reduces.
The dehydrogenation reaction of described step (3) is usually at 300～700 ℃, preferred 400～600 ℃, and reaction pressure is to carry out under 0～1000kPa, the preferred 0～300kPa.The weight hourly space velocity of described petroleum hydrocarbon raw material can be 0.5～30h
-1, preferred 1～10h
-1
The per pass conversion of the dehydrogenation reaction of described step (3) is preferably at least 20%, more preferably at least 30%.
Before the olefin cracking reaction zone was introduced in the logistics of the petroleum hydrocarbon that will contain the unsaturated hydrocarbons compounds, preferred advanced promoting the circulation of qi liquid separated, and the carbon four following components and the Hydrogen Separation that exist in the logistics after the dehydrogenation are come out.Simultaneously, the petroleum hydrocarbon logistics that contains the unsaturated hydrocarbons compounds of liquid state is introduced the olefin cracking reaction that described olefin cracking reaction zone carries out step 4).
Preferably, the temperature of reaction of the olefin cracking that carries out in the described step 4) is not less than 400 ℃, preferred 500 ℃～600 ℃, more preferably 500～550 ℃; Reaction pressure is 0.05～0.5MPa, preferred 0.05～0.2MPa; The weight hourly space velocity is 1.0～30h
-1, preferred 1.5～20h
-1, comprise the combination of above-mentioned scope.
In the step 5) of method of the present invention, comprise C with what step 4) obtained
2～C
9The logistics of alkene separates.As required, isolate and be rich in C
2Alkene, C
3Alkene and C
4The product of alkene perhaps is rich in C
5, C
6, C
7, C
8And/or C
9The product of alkene.
In described step 5), described separation circuit can comprise compression, rectifying, extraction.In non-limiting embodiments of the present invention, can be according to the composition and the ratio of olefin product, in separating device, extract respectively or rectifying etc. to obtain required target product.
Method of the present invention has the following advantages:
1, utilize the selective hydrogen burning technology adopt the direct heating mode heat petroleum hydrocarbon to proper temperature to carry out dehydrogenation reaction process.Compare with the indirect outer heat-processed of existing petroleum hydrocarbon, can improve heat-transfer effect, improve heat transfer efficiency, conserve energy is also protected environment.
2, the method according to this invention, the temperature of carrying out the reaction of petroleum hydrocarbon dehydrogenation and olefin cracking is significantly less than existing steam cracking.Therefore, can save big energy, reduce or avoid the use of high temperature resistant equipment, thereby reduce the cost of maintenance of the equipment and investment.
3, the method according to this invention behind dehydrogenation step, utilizes simple gas-liquid separation that hydrogen and methane and other logistics are separated.And, in follow-up olefin cracking step, seldom or not generate hydrogen and methane.Thereby in technological process, reduced separating of hydrogen and low carbon number materials such as methane and purpose product low-carbon alkene, and do not had simultaneously with the alkane of carbon atom and separating of alkene, greatly reduce isolating energy consumption.
Specific embodiments
Below, be described more specifically method of the present invention by embodiment.Be to be understood that scope of the present invention should not be limited to the scope of embodiment.Any variation or change that does not depart from purport of the present invention can be understood by those skilled in the art.Protection scope of the present invention is determined by the scope of appended claims.Except as otherwise noted, percentage ratio that is occurred among the embodiment and umber are all based on weight.
In following embodiment and Comparative Examples, use the light naphthar of following composition:
Table 1 light naphthar is formed
| Carbonatoms | Alkane | Alkene | Naphthenic hydrocarbon | Aromatic hydrocarbons | Amount to |
| ??4 | ??2 | ??0.02 | ??0 | ??0 | ??2.02 |
| ??5 | ??32.7 | ??0.3 | ??0.58 | ??0 | ??33.58 |
| ??6 | ??24.12 | ??0.28 | ??3.57 | ??2.29 | ??30.26 |
| ??7 | ??12.96 | ??0.12 | ??4.12 | ??2.37 | ??19.57 |
| ??8 | ??6.59 | ??0 | ??1.72 | ??2.09 | ??10.4 |
| ??9 | ??2.62 | ??0 | ??0.11 | ??0.72 | ??3.45 |
| ??10 | ??0.72 | ??0 | ??0 | ??0 | ??0.72 |
| ??11 | ??0 | ??0 | ??0 | ??0 | ??0 |
| ??12 | ??0 | ??0 | ??0 | ??0 | ??0 |
| Amount to | ??81.71 | ??0.73 | ??10.1 | ??7.47 | ??100.00 |
The exemplary distribution of the dehydrogenation reaction zone product of the inventive method is listed in the table 2:
The products distribution of table 2 dehydrogenation reaction zone
The exemplary distribution of the olefin cracking district product of the inventive method is listed in the table 3:
Table 3 olefin cracked product distributes
Embodiment 1
Above-mentioned light naphthar (C through the desulfurization dearsenification
5～C
10) be preheating to about 100 ℃ through interchanger, with enter hydrogen burning direct heating district after water, hydrogen and the oxygen mix, the hydrogen burning heating zone is made up of a low temperature hydrogen combustion reactor and two high temperature hydrogen combustion reactors, and reaction conditions is in the hydrogen burning heating zone: weight hourly space velocity 4h
-1, reaction pressure 0.15MPa, water vapour and oil weight ratio 0.5.The low temperature hydrogen combustion reactor is equipped with hydrogen burning Pt/Al
2O
3Catalyzer (Beijing Chemical Research Institute produces, trade mark BHO-L), the stream temperature of leaving the low temperature hydrogen combustion reactor is 150 ℃, enters then hydrogen burning catalyst Pt/Al is housed
2O
3The high temperature hydrogen combustion reactor generation hydrogen burning reaction of (Beijing Chemical Research Institute produces, trade mark BHO-H1), the stream temperature of leaving the hydrogen burning reactor is 550 ℃, enters then hydrogen burning catalyst Pt/Al is housed
2O
3The high temperature hydrogen combustion reactor generation hydrogen burning reaction of (Beijing Chemical Research Institute produces, trade mark BHO-H2), the stream temperature of leaving the hydrogen burning reactor is 700 ℃; Enter dehydrogenation reactor subsequently, under 0.15MPa pressure with Pt/Al
2O
3Dehydrogenation catalyst (Beijing Chemical Research Institute produces, trade mark BDH) contact is at weight hourly space velocity 4h
-1, carry out catalytic dehydrogenating reaction under the condition of reaction pressure 0.15MPa, obtain containing hydrogen, unreacted alkane and with the mixture flow of reaction raw materials with the alkene of carbon number; Is 0.5 to mix this logistics and dilution water steam with weight ratio, is 550 ℃ through heat exchange control stream temperature; Mix the logistics that obtains and enter alkene cracking reactor, under the condition of the weight ratio 0.5 of pressure 0.15MPa and water vapour and oil, be carrier and be that (Beijing Chemical Research Institute produces for the catalyzer of active ingredient with alkaline-earth metal and nonmetal phosphorus by being equipped with ZSM-5, trade mark BOC) fixed bed, the product that obtains is formed as shown in table 4.
Embodiment 2
Except that the stream temperature of leaving the hydrogen burning reactor changes into 650 ℃, produce low-carbon alkene with method identical and condition with embodiment 1.
Embodiment 3
Except that the stream temperature of leaving the hydrogen burning reactor changes into 600 ℃, produce low-carbon alkene with method identical and condition with embodiment 1.
Comparative example 1
This comparative example is a Deep Catalytic Cracking process.
With identical feed naphtha (C
5～C
10) be preheated to 600 ℃ through convection zone, enter the catalytic cracking reaction device, weight ratio 0.5 at reaction pressure 0.1MPa, water and oil, temperature of reaction is respectively under 700,750 and 800 ℃ of temperature, carry out catalyzed reaction with the ZSM-5 molecular sieve fixed bed catalyst that supports rare earth metal (Beijing Chemical Research Institute produces, trade mark BAC) contact.The product that obtains is formed as shown in table 4.
Comparative example 2
This comparative example is a steam cracking process.
With identical feed naphtha (C
5～C
10) through 630 ℃ of convection zone preheatings, enter radiation section and carry out heat scission reaction, the residence time is 0.22 second, water and oily weight ratio 0.5, and wherein the radiation section temperature out is respectively 830 ℃ and 850 ℃.
The product that obtains is formed as shown in table 4.
Table 4 different process flow process lower carbon number hydrocarbons distributes
Remarks: in table 4, as shown in table 3 except that low-carbon alkene, surplus is mainly C
5～9Alkane and alkene.
From the data of table 4 as can be seen, reaction process temperature of reaction at different levels of the present invention are low than the temperature of reaction of other two kinds of technologies, and this causes energy saving, owing to adopt the mode of internal heating, compare with outside heat supply simultaneously, and capacity usage ratio improves.
As can be seen, two kinds of technologies of method of the present invention and other are compared, and significantly reduce the productive rate of by-product methane, have saved raw material effectively from reaction result, and the higher low-carbon alkene production method of ratio of a kind of propylene and ethene is provided simultaneously.
Claims (10)
1. a method of producing low-carbon alkene by petroleum hydrocarbon is characterized in that, said method comprising the steps of:
1) preheating: petroleum hydrocarbon raw material is heated to 100～200 ℃;
2) hydrogen burning: the petroleum hydrocarbon material of preheating is mixed with weight ratio 1: 0～5 with thinner,, enter the hydrogen burning heating zone then so that logistics utilizes the hydrogen burning reaction to reach the temperature that dehydrogenation reaction needs again with hydrogen and oxygen mix;
3) dehydrogenation: will introduce dehydrogenation reactor from the logistics of hydrogen burning heating zone, and in the presence of dehydrogenation catalyst, carry out dehydrogenation reaction, and obtain containing the petroleum hydrocarbon mixture flow of hydrogen and unsaturated hydrocarbons compounds;
4) olefin cracking: the petroleum hydrocarbon mixture flow that contains hydrogen and unsaturated hydrocarbons compounds that certain embodiments produces is mixed introducing alkene cracking reactor in back with thinner with weight ratio 1: 0～2, in the presence of the olefin cracking catalyzer, carry out the olefin cracking reaction, obtain containing hydrogen and C
2～C
4The mixture flow of alkene;
5) separate: adopt conventional isolation technique to contain hydrogen and C what step 4) obtained
2～C
4The mixture flow of alkene is separated, and obtains hydrogen gas stream, C respectively
2Olefin stream, C
3Olefin stream and C
4Olefin stream.
2. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1 is characterized in that described thinner is a water vapour.
3. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1 is characterized in that, described hydrogen burning heating zone is made up of successively low temperature hydrogen burning heater and high temperature hydrogen burning heater or is single hop hydrogen burning well heater.
4. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 3 is characterized in that, the petroleum hydrocarbon temperature of charge of described low temperature hydrogen burning heater outlet is 150～500 ℃.
5. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 3 is characterized in that, the petroleum hydrocarbon temperature of charge of described high temperature hydrogen burning heater outlet is 400～1000 ℃, is preferably 500～700 ℃.
6. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1, it is characterized in that, in described step 4) olefin cracking process, the petroleum hydrocarbon mixture flow that will contain hydrogen and unsaturated hydrocarbons compounds is introduced described alkene cracking reactor with thinner, in described alkene cracking reactor, contact, the olefin cracking reaction that carbonatoms reduces takes place with the olefin cracking catalyzer.
7. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1 is characterized in that in described step 5) sepn process, described separation comprises compression, low temperature separation process, rectifying and extraction process.
8. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1, it is characterized in that, described dehydrogenation reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of dehydrogenation catalyst, described hydrogen burning reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of hydrogen burning catalyst, and described alkene cracking reactor is for adding the fixed-bed reactor or the fluidized-bed reactor of conversion of olefines catalyzer.
9. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 8, it is characterized in that, described dehydrogenation catalyst is dehydrogenation catalyst or nickel catalyst for carried noble metal Pt, described hydrogen burning catalyst is that carried noble metal Pt or Pd are hydrogen burning catalyst, and described olefin cracking catalyzer is one or more the mixture in modification or unmodified ZSM-5, ZSM-11, ZSM-23, MCM-22 and the SAPO molecular sieve catalysts.
10. method of producing low-carbon alkene by petroleum hydrocarbon as claimed in claim 1 is characterized in that described petroleum hydrocarbon raw material is for being selected from C
4-C
35The mixture of one or more in stable hydrocarbon, petroleum naphtha, diesel oil, whiteruss, solid paraffin, normal paraffin mixture, hydrogenation tail oil, tops and the reformate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554811A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | The Application way of benzene-enriched cut in de-pentane oil |
| CN114426856A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for changing composition of catalytic cracking product |
-
2009
- 2009-04-27 CN CN200910082942A patent/CN101870633A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554811A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | The Application way of benzene-enriched cut in de-pentane oil |
| CN114426856A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for changing composition of catalytic cracking product |
| CN114426856B (en) * | 2020-10-29 | 2023-06-09 | 中国石油化工股份有限公司 | Method for changing composition of catalytic cracking product |
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Application publication date: 20101027 |